CN106830670B - Lanthanum crown LaK3 series space radiation-resistant optical glass and preparation method thereof - Google Patents
Lanthanum crown LaK3 series space radiation-resistant optical glass and preparation method thereof Download PDFInfo
- Publication number
- CN106830670B CN106830670B CN201611260938.2A CN201611260938A CN106830670B CN 106830670 B CN106830670 B CN 106830670B CN 201611260938 A CN201611260938 A CN 201611260938A CN 106830670 B CN106830670 B CN 106830670B
- Authority
- CN
- China
- Prior art keywords
- glass
- lak3
- temperature
- optical glass
- radiation resistance
- 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.)
- Active
Links
- 239000005304 optical glass Substances 0.000 title claims abstract description 82
- 230000005855 radiation Effects 0.000 title claims abstract description 68
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 26
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 146
- 239000000463 material Substances 0.000 claims description 65
- 238000000137 annealing Methods 0.000 claims description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 56
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 238000012360 testing method Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 12
- 238000005352 clarification Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 51
- 230000001186 cumulative effect Effects 0.000 abstract description 2
- 238000010998 test method Methods 0.000 description 24
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 15
- 238000013461 design Methods 0.000 description 12
- 230000005251 gamma ray Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000010309 melting process Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000008030 elimination Effects 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 238000010583 slow cooling Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000005308 flint glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 2
- 230000003471 anti-radiation Effects 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005305 interferometry Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to lanthanum crown LaK3 series space radiation-resistant optical glass mainly used for an optical system of a spacespace satellite-borne star sensor and a preparation method thereof. The series of space radiation-resistant optical glass comprises the following raw materials in percentage by mass: 10-13% SiO213-17% of B2O311-14% of Al2O30.5-4% of ZnO and 0.5-3% of ZrO251-55% of La2O31.5-6% of Y2O30.3-1.5% of CeO2. The lanthanum crown LaK3 series space radiation-resistant optical glass provided by the invention has high radiation resistance, can meet the requirement that a space optical star sensor optical system can endure high-dose cumulative radiation in a space environment for a long time, and can meet the requirements of high orbit and 10-25 years of service life in space.
Description
Technical field
The present invention relates to a kind of lanthanum crown LaK3 series spaces for being mainly used for the spaceborne optical system of star sensor of aerospace
Radiation resistance optical glass and preparation method thereof.
Background technique
Exact posture acquisition of information and gesture stability of the spaceborne optics star sensor of aerospace in space aircraft
Aspect plays key effect.Optics star sensor is stared starry sky imaging on the detector by optical system, institute Cheng Xingxiang
Quality needs to meet long-term in-orbit, the attitude measurement requirements for high precision of space aircraft.
For middle high orbit satellite, needing one kind can be suitble to middle high orbit 10 years or more even meet 25 year service life need
The optical system of star sensor asked.Since in space space environment, the long-term accumulated space of high-energy rays and particle radiates effect
The optical system of star sensor transmitance that common designations optical glass structure should be will lead to rapidly decays to opaque, system
Image quality, which reduces, not to be available even.The domestic anti-radiation performance because lacking space optics optical system of star sensor, which is reformed, to be set
Meter with reinforce needed for high-quality radiation resistance optical glass material, there is no such long-life (high orbit, 15 to 25 in space before
Year service life) optical system.
Domestic radiation resistance optical glass material single variety, so that middle high orbit, long-life aerospace load optical system
The Radiation hardness design of system is limited by the available optical glass material of optical system with the promotion of spaceborne star sensor key performance
Material, thus the design difficulty of the spaceborne optical system of star sensor of aerospace greatly increases, and constrains China in middle high orbit, length
The development of service life Space Optical System and space optics load technical aspect.
Space optics star sensor mostly uses transmission-type or Zigzag type optical system, and optical system is by one group of refractive index, color
The positive and negative lens combination that different optical glass materials is process is dissipated to constitute.Wherein, the lanthanum crown of high-refractivity and low-dispersion is utilized
It is (LaK) stabilized glass material, in conjunction with the positive negative lens of dense flint system (ZF) stabilized glass material composition, is used for space star
The aberration balancing and optimization design of sensor optical system in correction disc of confusion energy mass center colo(u)r bias, improve space optics star
While sensor imaging performance, the space radiation resistance of space optics star sensor is effectively improved.
Traditional LaK3 optical glass contains the toxic heavy metals oxides such as cadmium oxide (CdO).Environment-protecting and non-poisonous LaK3 light
It learns glass and largely uses titanium oxide (TiO2), niobium pentaoxide (Nb2O5) etc. non-posinous heavy metals oxide replace toxic oxidation
Cadmium.Traditional LaK3 optical glass and environmental protection LaK3 optical glass its transmitance under space radiation cumulative function can all decline,
Therefore it cannot be used under the use environment of the high total dose effect of space radiation environment.
Summary of the invention
In order to solve at present, domestic radiation resistance optical glass material single variety is spaceborne to aerospace, long-life star is sensitive
Radiation hardness lens material type selecting bring problem in device Optical System Design, the present invention provide a kind of high refractive index, low dispersion
Lanthanum crown LaK3 series space radiation resistance optical glass and preparation method thereof.
The technical solution of the invention is as follows: a kind of lanthanum crown LaK3 series space radiation resistance optical glass, special character
Be: material composition is environment-protecting and non-poisonous, quality proportioning are as follows: the SiO of 10-13%2, 13-17% B2O3, 11-14% Al2O3、
The ZrO of ZnO, 0.5-3% of 0.5-4%2, 51-55% La2O3, 1.5-6% Y2O3, 0.3-1.5% CeO2。
Preferably, SiO2Mass fraction be 10.5-11.8%；B2O3Mass fraction be 14.7-15.7%；Al2O3's
Mass fraction is 11-12.5%；La2O3Mass fraction be 52.6-54%；ZrO2, ZnO and Y2O3The sum of mass fraction be 5-
10.5%；CeO2Mass fraction be 0.4-1%.
The present invention also provides a kind of preparation method of lanthanum crown LaK3 series space radiation resistance optical glass, special character exists
In: the following steps are included:
1] it according to above-mentioned raw materials ingredient and quality proportioning precise raw material and is uniformly mixed；
2] height of bubble-free and striped is obtained after raw material after mixing being carried out high-temperature fusion, stirring clarification and homogenizing
Warm glass metal；
3] large-size glass blank is formed using leakage note method；
4] lanthanum crown LaK3 series radiation resistance optical glass is obtained after annealing to chunk glass.
Above-mentioned steps 2] the following steps are included:
2.1] raw material after mixing is added portionwise in the platinum crucible for be heated to 1230 DEG C and is melted in advance；
2.2] after keeping the temperature 2h, 1400 DEG C is to slowly warm up to and carries out constant speed promotion and high-speed stirred with blender；
2.3] glass metal of bubble-free and striped is obtained after 5~7h of clarifying and homogenizing.
Above-mentioned steps 2] in further include the steps that refractive index adjust:
2.4] post-processing refraction index test sample is sampled；
2.5] refractive index n of the measurement sample at 587.6nm wavelengthd；
2.6] judge ndWhether in 1.7397 ± 0.0003 ranges；If so, executing step after continuing stirring promotion 4h
3]；If it is not, thening follow the steps 2.7]；
2.7] if ndLower than 1.7394, then lanthana is added into glass metal in the ratio of 0.35g/kg glass metal；If ndIt is high
In 1.7400, then boric acid is added into glass metal in the ratio of 0.42g/kg glass metal and carries out refractive index adjustment；
2.8] after stirring evenly and clarify, return step 2.4].
Above-mentioned steps 3] the following steps are included:
3.1] high-temperature glass liquid is cooled to 1220 DEG C under the rate of temperature fall of 1 DEG C/min；
3.2] high-temperature glass liquid after cooling is slowly injected into the mold for being preheating to 420 DEG C, carries out large-size glass
Blank molding.
Above-mentioned steps 4] the following steps are included:
4.1] it will be transferred to have warmed up into 710 DEG C of Muffle furnace after the demoulding of molding chunk glass and carry out black annealing, keep the temperature
12~for 24 hours after cooled down 100 DEG C with the rate of temperature fall of 2 DEG C/h, then be cooled to 100 DEG C with the rate of temperature fall of 5 DEG C/h, close Muffle furnace
Black annealing chunk glass is obtained after so that glass sample is naturally cooling to room temperature with furnace；
4.2] black annealing chunk glass is embedded in the Muffle cabinet of stainless steel material with fine granularity glass sand, so
Muffle cabinet is placed in annealing furnace afterwards and is warming up to 710 DEG C；After keeping the temperature 48h, with the rate of temperature fall cooling 100 of 0.2~1.0 DEG C/h
DEG C, then 300 DEG C are cooled to the rate of temperature fall of 2 DEG C/h, then 100 DEG C are cooled to the rate of temperature fall of 4 DEG C/h；Close annealing furnace
Glass sample is set to be naturally cooling to obtain lanthanum crown LaK3 series radiation resistance optical glass after room temperature with furnace.
Above-mentioned steps 1] used in raw material be partial size in the specific pure dry powder of 100-120 purpose.
Above-mentioned steps 3.2] in mold above be provided with cover board.
The beneficial effects of the present invention are:
1, the high radiation-resistant property of material.In series radiation resistance optical glass material proposed by the present invention, as LaK503 is passed through
It is 1 × 10 by accumulated dose5Optical density increment Delta D≤0.015, Neng Gouman after rad (Si) gamma-ray irradiation on thickness per cm
The tolerance high dose accumulation irradiation for a long time in the space environment of sufficient space optics optical system of star sensor, can meet it in space
The requirement of high orbit, 10~25 years service life.
2, prepared device for Optical Properties of Materials is excellent.Mixed powder in the present invention melts, in advance again through platinum crucible high temperature
The method of melting preparation series LaK3 radiation resistance optical glass is easier to obtain the resistance to spoke of no platinum granule foreign, excellent in optical properties
According to optical glass material, bubble degree can reach A0 grades, striped degree up to A grades, optical homogeneity up to 1 class, stress birfringence
Up to 1 class, the refractive index of same batch material and the consistency of abbe number are A grades, and acid resistance, moisture resistivity are respectively 2 grades, 1
Grade.
3, through the invention in special fine annealing heat treatment process, can be realized the folding of radiation resistance optical glass material
Penetrate rate ndAccurate increment is to 1.7469 ± 0.0002, Abbe number (υd) accurately increment is to 50.95 ± 0.15, and sufficiently eliminates glass
Stress in material, radiation resistance optical glass and LaK3 common designations optical glass, which can be effectively controlled, has comparable optical constant,
The refringence (± 2 × 10 of the two-4) and abbe number difference (± 0.3%) can control simultaneously in 0 class, stress birfringence is low can
Up to 1 class (< 2nm/cm).
4, the multi items seriation of material.By optimizing and revising radiation resistance optical glass composition and radiation stabilized agent content,
The balance for realizing visible light shortwave transmitance and resistance to high-energy ray irradiation ability, takes into account different spaces optical system of star sensor pair
The material tolerance performance designs such as space radiation accumulated dose and shortwave transmitance require to stress difference, can prepare with phase advancing coloud nearside
The serial radiation resistance optical glass material such as LaK303, LaK403, LaK503, LaK603, LaK703 of property is dissipated, to meet
The different anti-radiation resistance abilities such as high and low track, the design of the space optical system of star sensor in different designs service life and strong nuclear radiation
The requirement of protection observation optical window under environment.
5, space radiation resistance optical glass material stable chemical performance of the invention, be suitable for mass production.
Detailed description of the invention
Fig. 1 is the interior of the non-irradiated sample (LaK303, LaK403, LaK503, LaK603, LaK703,10mm) of the present invention
Cross rate curve.
Fig. 2 is different accumulated doses (1 × 103rad(Si)、1×104rad(Si)、1×105rad(Si)、1×106rad
(Si)) LaK503 does not plate the optical transmission spectra of membrane sample (Ф 20mm × 2mm) after gamma-rays irradiates respectively.
Specific embodiment
High orbit, the serial radiation resistance optical glass material of long-life space optics load, enrich China in development and production
The trade mark of space radiation resistance optical glass material can fundamentally solve the material of Space Optical System radiation resistance Design of Reinforcement
Expect support problem.In addition, the radiation resistance optical glass material for being resistant to high irradiation dose also can be used as the observation under nuclear radiation environment
Optical window protective materials constitutes imaging optical system as optical system important Parts, is applied to atomic energy industry, high energy object
The key areas such as reason and nuclear activity.
In order to meet the space optical system of star sensor of the different radiation-resistant properties such as high and low track, different service lifes
Radiation resistance reinforces protection under design and strong nuclear radiation environment and observes optical system to serial radiation resistance optical glass material
Requirement, the invention discloses a kind of lanthanum crown LaK3 series radiation resistance optical glass material and its crucial preparation process sides
Method, by combining the critical control point such as glass ingredient adjustment, stokehold refractive index modulation and fine annealing technique, it can be achieved that accurate control
587.6nm refractive index (n after LaK3 series radiation resistance optical glass material essence annealing processedd) in 1.7469 ± 0.0002 ranges,
Abbe number (υd) in 50.95 ± 0.15 ranges.
Lanthanum crown LaK3 series radiation resistance optical glass material it is specific the preparation method is as follows:
(1) according in table 1 ingredient and proportion weigh raw material and be uniformly mixed.
1 material composition of table and proportion (mass percent):
The sum of each oxide composition proportion is 100%, weighs corresponding raw material according to the weight percent of each oxide component
It is uniformly mixed.
SiO2、B2O3Body is generated mainly as glass network.Wherein, SiO2Total content is 10~13%, it is optimal be 10.5~
11.8% (wt), it can reduce the thermal expansion coefficient of glass, improve the thermal stability of glass, chemical stability, softening temperature, resistance to
Hot, hardness and mechanical strength etc..B2O3Total content is 13~17%, and optimal is 14.7~15.7% (wt), and it is molten can to reduce glass
Temperature processed, while improving the above-mentioned performance of glass, but when its content is more than 17%, will increase the tendency towards devitrification of this kind of glass, it drops
The chemical stability of low glass.
ZrO is added2, ZnO and Al2O3For adjusting the refractive index and thermal expansion coefficient of glass, the chemical stabilization of glass is improved
Property and machining property.Meanwhile ZrO2、Al2O3、Y2O3Addition can improve the crystallization property of glass, improve glass, steady at glass
Qualitative, thermal stability and chemical stability, can effectively extend the material of glass, and the large-size glass blank of anti-leak-stopping injection forming exists
It is burst in cooling procedure in mold；Again can the refractive index to glass effectively adjusted.But ZrO2, ZnO and Y2O3Total content is unsuitable
More than 10%, otherwise this kind of glass can be made to be easy to devitrification, reduce the formation range of glass, while will increase the viscosity of glass, made
Glass smelting and forming temperature increase, and prepare more difficult；ZrO2, ZnO and Y2O3Summation it is optimal be 5~10.5% (wt).Net
Network intermediate oxide Al2O3Optimal is 11~12.5% (wt).
Different accumulated doses are subjected to through rate score and glass by interior at 470nm wavelength of radiation resistance optical glass sample
The optimum experimental of transmitance reduction amount between the two balances at the wavelength after gamma-ray irradiation, prepared different radiation resistance abilities
Serial LaK3 optical glass in CeO2Weight percent content control it is proper 0.3~1.5%.
(2) uniformly mixed powder is added in platinum crucible by several times, 1230 DEG C melt mixed powder in advance, keep the temperature 2h
Afterwards, slowly heating control platinum crucible in glass smelting temperature at 1400 DEG C or so, and with platinum leaf starch blender carry out constant speed
Promotion and high-speed stirred, keep glass liquid stirring uniform；After clarification starts 2h, stokehold sampling, cooling post-processing are carried out with sample spoon
The right angle refractive index test sample that angle is 90 ° ± 1 ' measures refractive index n of the sample at 587.6nm wavelengthd；Stokehold sampling
Refractive index ndControl is in 1.7397 ± 0.0003 ranges, if ndIt is relatively low, lanthana (0.35g/kg glass is added into glass metal
Liquid) refractive index can be turned up 0.0001；If ndIt is higher, boric acid (0.42g/kg glass metal) is added into glass metal by refractive index tune
Low 0.0001；ndAfter the value that makes it, continues clarification and eliminate bubble, futher stir homogenizing after sampling bubble-free, eliminate
Glass is because of the striped that unevenly generates.
(3) clarified after glass metal and eliminate bubble and after stirring, by high-temperature glass liquid slow cooling (- 1 DEG C/
Min it) to 1220 DEG C, is slowly injected into the copper mould for having been preheated with 420 DEG C via the elongated material leakage mouth in platinum crucible bottom, into
The molding of row large-size glass blank.
(4) it will quickly be transferred in the Muffle furnace for have warmed up 710 DEG C of annealing temperature after the demoulding of molding glass and slightly moved back
Fire: 710 DEG C of heat preservations 12~for 24 hours, first cooled down 100 DEG C with the rate of temperature fall of -2 DEG C/h, then be cooled to the rate of temperature fall of -5 DEG C/h
Near 100 DEG C, Muffle furnace power supply is closed, glass sample is made to be naturally cooling to room temperature with furnace, takes out chunk glass.
(5) black annealing chunk glass is embedded in the middle part of stainless steel material Muffle cabinet with high-purity fine granularity quartz sand, four
The filling of Zhou Junyong quartz sand is full, and the Muffle cabinet for placing chunk glass covers, and smart annealing is placed in after being separated with fire resisting tripod
It in furnace, carries out the increment of fine annealing refractive index and eliminates stress processing: 710 DEG C of heat preservation 48h, elder generation is with-(0.2~1.0) DEG C/h's
Rate of temperature fall cools down 100 DEG C, then is cooled to 300 DEG C, 100 DEG C respectively with the rate of temperature fall of -2 DEG C/h, -4 DEG C/h, closes essence annealing
Furnace power supply, makes glass sample be naturally cooling to room temperature with furnace.
Wherein (2), (3), the practical operation of (5) step are more crucial, and 1230 DEG C of mixed powders are pre- in platinum crucible
Be molten into after glassy state increase again temperature carry out clarifying and homogenizing, can relative reduction glass clarifying and homogenizing temperature, effectively reduce height
The La of content2O3、Y2O3Erosion under equal rare earth components high temperature to platinum crucible, avoids bringing platinum particle into and enters in glass；Silicon
During carbon-point electric smelting stove heating high temperature molten glass, promotion stirring is carried out using platinum leaf slurry blender, in a crucible
Successively realize clarification to high-temperature glass liquid, homogenization process, high-temperature glass liquid pass through after mixing evenly stokehold refractive index sample and
The refractive index of glass, accurately controls n in additional high/low refractive index component adjustment crucibledThe value that makes it 1.7397 ±
0.0003, it is that subsequent handle by fine annealing makes glass ndNumerical value is modulated to 1.7469 ± 0.0002 premise guarantee.Glass
High-temperature glass liquid is slowly injected into the copper mould having had been warmed up via the elongated material leakage mouth of crucible bottom when molding；Casting is opened
Beginning rear mold bottom ventilation is cooling, sticks together during preventing glass to be poured with copper mould and causes demoulding difficult；Above mold
Stainless steel cover board is covered, prevents the cooling too fast periphery in formed glass surface from bursting.
According to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: transmission in spectrum
Than ", it is measured, is obtained using transmitance of the ultraviolet-visible light-near infrared spectrometer to radiation resistance optical glass sample
The interior transmittance curve of 1cm thickness sample.According to national standard " 7962.1-2010 colouless optical glass test method of GB/T the 1st
Point: refractive index and abbe number " refractive index n of the test acquisition sample at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、
nC, by υd=(nd-1)/(nF-nC) Abbe number υ is calculatedd.According to GB/T 7962 respectively to radiation resistance optical glass sample
Optical homogeneity, stress birfringence, striped degree, bubble degree, acid resistance, moisture resistivity are tested, according to " GB 903-87 is colourless
Optical glass " determine correlated performance grade.
GB/T7962.2-2010 colouless optical glass test method part 2: the striking cable plane interferometry of optical homogeneity
The 5th part of GB/T7962.5-2010 colouless optical glass test method: stress birfringence
GB/T 7962.7-1987 colouless optical glass test method striped degree test method
The 8th part of GB/T7962.8-2010 colouless optical glass test method: bubble degree
The 14th part of GB/T7962.8-2010 colouless optical glass test method: acid-resistant stability
The 15th part of GB/T7962.8-2010 colouless optical glass test method: moisture resistance stability
60Co gamma-rays ionizing radiation total dose response test process is summarized as follows:
1) dosage is carried out to the Co-60 gamma ray projector that irradiation uses according to " ferrous sulfate dosimeter standard " (GB139-89)
The calibration of field；
2) sample is marked and predose inspection, the transmittance curve of test sample predose；
3) given dosage rate line is found according to calibration, the axis of sample is placed on the dosage rate line, sample is pressed
Irradiation test is carried out according to given dosage rate.
4) according to irradiation dose=radiation dose rate × irradiation time, when determining the corresponding irradiation of test plan accumulated dose
Between；
5) irradiation dose (or time) is added up, and reaches the accumulated dose or dose point of test plan in sample irradiation dosage
When, sample is taken out, immediately with the transmittance curve after spectrophotometer test irradiation.
6) irradiation test dosage rate: 5 × 103Rad (Si)/h, accumulated dose respectively reach: 1 × 103rad(Si)、1×
104rad(Si)、1×105rad(Si)、1×106rad(Si)、1×107rad(Si)。
Technical solution of the present invention and test result are described in detail combined with specific embodiments below:
The composition of each ingredient and the optical property of respective sample in 1 specific embodiment of table
Embodiment one:
By the formula of table 21#In glass form weight percent, weigh raw material in plastics mixer be uniformly mixed.By institute
The powder matched sequentially adds in platinum crucible to be melted for 1230 DEG C in advance, and platinum crucible heats up after keeping the temperature 2h, passes through silicon carbide electricity
Furnace heats melting, for the control of glass smelting temperature at 1400 DEG C or so, melting time is 5~7h, and platinum is used in melting process
Gold leaf slurry blender is stirred homogenizing to glass metal.High-temperature glass liquid after mixing evenly, by stokehold refractive index modulation, accurately
Control ndThe value that makes it 1.7397.It is after continuing clarification elimination bubble and stirring, high-temperature glass liquid is slow
1220 DEG C or so are cooled to, is injected into the copper mould for have been preheated with 420 DEG C by crucible bottom material leakage mouth and carries out glass fiber
Base molding, and quickly will be put into have warmed up into the Muffle furnace of 710 DEG C of annealing temperatures after the demoulding of formed glass sample and slightly be moved back
Fire: after heat preservation 12~for 24 hours, first cooled down 100 DEG C with the rate of temperature fall of -2 DEG C/h, then room is cooled to the rate of temperature fall of -5 DEG C/h
Temperature.Black annealing chunk glass is subjected to fine annealing processing: being embedded in stainless steel material Muffle cabinet with glass sand,
In smart annealing furnace, 48h is kept the temperature, is first cooled down 100 DEG C with the rate of temperature fall of -0.2 DEG C/h, then respectively with the drop of -2 DEG C/h, -4 DEG C/h
Warm rate is cooled near 300 DEG C, 100 DEG C, and closing power supply makes glass sample be naturally cooling to room temperature with furnace.
Sample after taking fine annealing processes a refraction index test right angle sample, according to national standard " GB/T 7962.1-
2010 colouless optical glass test method part 1s: refractive index and abbe number test method " test obtain LaK303 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7469, refractive index after fine annealing
Increment 0.0072；Its Abbe number υ is calculateddIt is 50.91.
Sample after annealing is processed into the two light pass surfaces polishing that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: spectrum internal transmittance ",
It is measured, is obtained with a thickness of 10mm sample using transmitance of the ultraviolet visible light-near infrared spectrometer to sample
Interior transmittance curve, interior transmitance τ of the LaK303 material in 470nm wavelength470It is 95.9%；According to GB/T 7962 respectively to resistance to
The optical homogeneity of illuminated optical glass sample, stress birfringence, striped degree, bubble degree are tested, grade is respectively 1,
1、A、A0Grade, acid resistance, moisture resistivity are respectively 2 grades, 1 grade；Through 1 × 103It is right on thickness per cm after rad (Si) gamma-ray irradiation
Answering the optical density increment Delta D of 470nm is 0.001.
Embodiment two:
By the formula of table 22#In glass form weight percent, weigh raw material in plastics mixer be uniformly mixed.By institute
The powder matched sequentially adds in platinum crucible to be melted for 1230 DEG C in advance, and platinum crucible heats up after keeping the temperature 2h, passes through silicon carbide electricity
Furnace heats melting, at 1400 DEG C or so, melting time is 5~7h for glass melting temperature control, and platinum leaf is used in melting process
Slurry blender is stirred glass metal.High-temperature glass liquid after mixing evenly, is sampled and is added high/low folding by stokehold refractive index
Rate component is penetrated, n is accurately controlleddThe value that makes it 1.7397.It, will be high after continuing clarification elimination bubble and stirring
Warm glass metal slow cooling is injected by crucible bottom material leakage mouth to 1220 DEG C or so and has been preheated with 420 DEG C of copper mould
Middle progress chunk glass molding, and quickly the Muffle having warmed up to 710 DEG C of annealing temperatures will be put into after the demoulding of formed glass sample
It carries out black annealing in furnace: after heat preservation 12~for 24 hours, first being cooled down 100 DEG C with the rate of temperature fall of -2 DEG C/h, then with the cooling speed of -5 DEG C/h
Rate is cooled to room temperature.Black annealing chunk glass is subjected to fine annealing processing: being embedded in stainless steel material horse with glass sand
Not in cabinet, in smart annealing furnace, keep the temperature 48h, first cooled down 100 DEG C with the rate of temperature fall of -0.5 DEG C/h, then respectively with -2 DEG C/
H, the rate of temperature fall of -4 DEG C/h is cooled near 300 DEG C, 100 DEG C, and closing power supply makes glass sample be naturally cooling to room temperature with furnace.
Sample after taking fine annealing processes a refraction index test right angle sample, according to national standard " GB/T 7962.1-
2010 colouless optical glass test method part 1s: refractive index and abbe number test method " test obtain LaK403 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7468, refractive index after fine annealing
Increment 0.0071；Its Abbe number υ is calculateddIt is 50.96.
Sample after annealing is processed into the two light pass surfaces polishing that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: spectrum internal transmittance ",
It is measured, is obtained with a thickness of 10mm sample using transmitance of the ultraviolet visible light-near infrared spectrometer to sample
Interior transmittance curve, interior transmitance τ of the LaK403 material in 470nm wavelength470It is 94.0%；According to GB/T 7962 respectively to resistance to
The optical homogeneity of illuminated optical glass sample, stress birfringence, striped degree, bubble degree are tested, grade is respectively 1,
1、A、A0Grade, acid resistance, moisture resistivity are respectively 2 grades, 1 grade；Through 1 × 104It is right on thickness per cm after rad (Si) gamma-ray irradiation
Answering the optical density increment Delta D of 470nm is 0.005.
Embodiment three:
By the formula of table 23#In glass form weight percent, weigh raw material in plastics mixer be uniformly mixed.By institute
The powder matched sequentially adds in platinum crucible to be melted for 1230 DEG C in advance, and platinum crucible heats up after keeping the temperature 2h, passes through silicon carbide electricity
Furnace heats melting, at 1400 DEG C or so, melting time is 5~7h for glass melting temperature control, and platinum leaf is used in melting process
Slurry blender is stirred glass metal.High-temperature glass liquid after mixing evenly, by stokehold refractive index modulation, accurately controls ndIt reaches
To predetermined target value 1.7400.After continuing clarification elimination bubble and stirring, extremely by high-temperature glass liquid slow cooling
1220 DEG C or so, progress chunk glass molding in the copper mould for have been preheated with 420 DEG C is injected by crucible bottom material leakage mouth,
And it quickly will be put into have warmed up into the Muffle furnace of 710 DEG C of annealing temperatures after the demoulding of formed glass sample and carry out black annealing: heat preservation
12~for 24 hours after, first cooled down 100 DEG C with the rate of temperature fall of -2 DEG C/h, then be cooled to room temperature with the rate of temperature fall of -5 DEG C/h.It will slightly move back
Flint glass blank carries out fine annealing processing: being embedded in stainless steel material Muffle cabinet with glass sand, in smart annealing furnace
In, 48h is kept the temperature, is first cooled down 100 DEG C with the rate of temperature fall of -1.0 DEG C/h, then cold with the rate of temperature fall of -2 DEG C/h, -4 DEG C/h respectively
But glass sample is made to be naturally cooling to room temperature with furnace near 300 DEG C, 100 DEG C, closing power supply.
Sample after taking fine annealing processes a refraction index test right angle sample, according to national standard " GB/T 7962.1-
2010 colouless optical glass test method part 1s: refractive index and abbe number test method " test obtain LaK503 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7470, refractive index after fine annealing
Increment 0.0070；Its Abbe number υ is calculateddIt is 50.87.
Sample after annealing is processed into the two light pass surfaces polishing that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: spectrum internal transmittance ",
It is measured, is obtained with a thickness of 10mm sample using transmitance of the ultraviolet visible light-near infrared spectrometer to sample
Interior transmittance curve, interior transmitance τ of the LaK503 material in 470nm wavelength470It is 92.1%；According to GB/T 7962 respectively to resistance to
The optical homogeneity of illuminated optical glass sample, stress birfringence, striped degree, bubble degree are tested, grade is respectively 1,
1、A、A0Grade, acid resistance, moisture resistivity are respectively 2 grades, 1 grade；Through 1 × 105It is right on thickness per cm after rad (Si) gamma-ray irradiation
Answering the optical density increment Delta D of 470nm is 0.011.
Example IV:
By the formula of table 24#In glass form weight percent, weigh raw material in plastics mixer be uniformly mixed.By institute
The powder matched sequentially adds in platinum crucible to be melted for 1230 DEG C in advance, and platinum crucible heats up after keeping the temperature 2h, passes through silicon carbide electricity
Furnace heats melting, at 1400 DEG C or so, melting time is 5~7h for glass melting temperature control, and platinum leaf is used in melting process
Slurry blender is stirred glass metal.High-temperature glass liquid after mixing evenly, by stokehold refractive index modulation, accurately controls ndIt reaches
To predetermined target value 1.7396.After continuing clarification elimination bubble and stirring, extremely by high-temperature glass liquid slow cooling
1220 DEG C or so, progress chunk glass molding in the copper mould for have been preheated with 420 DEG C is injected by crucible bottom material leakage mouth,
And it quickly will be put into have warmed up into the Muffle furnace of 710 DEG C of annealing temperatures after the demoulding of formed glass sample and carry out black annealing: heat preservation
12~for 24 hours after, first cooled down 100 DEG C with the rate of temperature fall of -2 DEG C/h, then be cooled to room temperature with the rate of temperature fall of -5 DEG C/h.It will slightly move back
Flint glass blank carries out fine annealing processing: being embedded in stainless steel material Muffle cabinet with glass sand, in smart annealing furnace
In, 48h is kept the temperature, is first cooled down 100 DEG C with the rate of temperature fall of -0.2 DEG C/h, then cold with the rate of temperature fall of -2 DEG C/h, -4 DEG C/h respectively
But glass sample is made to be naturally cooling to room temperature with furnace near 300 DEG C, 100 DEG C, closing power supply.
Sample after taking fine annealing processes a refraction index test right angle sample, according to national standard " GB/T 7962.1-
2010 colouless optical glass test method part 1s: refractive index and abbe number test method " test obtain LaK603 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7468, refractive index after fine annealing
Increment 0.0072；Its Abbe number υ is calculateddIt is 50.93.
Sample after annealing is processed into the two light pass surfaces polishing that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: spectrum internal transmittance ",
It is measured, is obtained with a thickness of 10mm sample using transmitance of the ultraviolet visible light-near infrared spectrometer to sample
Interior transmittance curve, interior transmitance τ of the LaK603 material in 470nm wavelength470It is 84.4%；According to GB/T 7962 respectively to resistance to
The optical homogeneity of illuminated optical glass sample, stress birfringence, striped degree, bubble degree are tested, grade is respectively 1,
1、A、A0Grade, acid resistance, moisture resistivity are respectively 2 grades, 1 grade；Through 1 × 106It is right on thickness per cm after rad (Si) gamma-ray irradiation
Answering the optical density increment Delta D of 470nm is 0.024.
Embodiment five:
By the formula of table 25#In glass form weight percent, weigh raw material in plastics mixer be uniformly mixed.By institute
The powder matched sequentially adds in platinum crucible to be melted for 1230 DEG C in advance, and platinum crucible heats up after keeping the temperature 2h, passes through silicon carbide electricity
Furnace heats melting, at 1400 DEG C or so, melting time is 5~7h for glass melting temperature control, and platinum leaf is used in melting process
Slurry blender is stirred glass metal.High-temperature glass liquid after mixing evenly, by stokehold refractive index modulation, accurately controls ndIt reaches
To predetermined target value 1.7400.After continuing clarification elimination bubble and stirring, extremely by high-temperature glass liquid slow cooling
1220 DEG C or so, progress chunk glass molding in the copper mould for have been preheated with 420 DEG C is injected by crucible bottom material leakage mouth,
And it quickly will be put into have warmed up into the Muffle furnace of 710 DEG C of annealing temperatures after the demoulding of formed glass sample and carry out black annealing: heat preservation
12~for 24 hours after, first cooled down 100 DEG C with the rate of temperature fall of -2 DEG C/h, then be cooled to room temperature with the rate of temperature fall of -5 DEG C/h.It will slightly move back
Flint glass blank carries out fine annealing processing: being embedded in stainless steel material Muffle cabinet with glass sand, in smart annealing furnace
In, 48h is kept the temperature, is first cooled down 100 DEG C with the rate of temperature fall of -0.5 DEG C/h, then cold with the rate of temperature fall of -2 DEG C/h, -4 DEG C/h respectively
But glass sample is made to be naturally cooling to room temperature with furnace near 300 DEG C, 100 DEG C, closing power supply.
Sample after taking fine annealing processes a refraction index test right angle sample, according to national standard " GB/T 7962.1-
2010 colouless optical glass test method part 1s: refractive index and abbe number test method " test obtain LaK703 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7471, refractive index after fine annealing
Increment 0.0071；Its Abbe number υ is calculateddIt is 50.86.
Sample after annealing is processed into the two light pass surfaces polishing that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: spectrum internal transmittance ",
It is measured, is obtained with a thickness of 10mm sample using transmitance of the ultraviolet visible light-near infrared spectrometer to sample
Interior transmittance curve, interior transmitance τ of the LaK703 material in 470nm wavelength470It is 76.7%；According to GB/T 7962 respectively to resistance to
The optical homogeneity of illuminated optical glass sample, stress birfringence, striped degree, bubble degree are tested, grade is respectively 1,
1、A、A0Grade, acid resistance, moisture resistivity are respectively 2 grades, 1 grade；Through 1 × 107It is right on thickness per cm after rad (Si) gamma-ray irradiation
Answering the optical density increment Delta D of 470nm is 0.035.
Choose the space optics optical system of star sensor that can meet high orbit in space, service life requirement in 15 to 25 years
With the LaK503 radiation resistance optical glass of use in design, the interior transmittance curve of material is as shown in Figure 1, LaK503 glass material
In the interior transmitance τ of 470nm wavelength470It is 92.1%.LaK503 glass material is respectively 1 × 10 by accumulated dose3rad(Si)、
1×104rad(Si)、1×105rad(Si)、1×106Transmittance curve after the gamma-ray irradiation of rad (Si) as shown in Fig. 2,
Compared with non-irradiated LaK503 glass material, the optical density increment Delta D that 470nm is corresponded on thickness per cm is respectively 0.003,
0.004,0.011 and 0.044.
As can be seen from the above embodiments, lanthanum crown LaK3 series radiation resistance optical glass of the present invention the preparation method comprises the following steps: with
Glass sand, boric acid, aluminium hydroxide and lanthana are main composition, addition small amounts zinc, zirconium oxide, yttrium oxide and irradiation
Stabilizer is melted, the clarification of platinum crucible high temperature melting and homogenizing in advance by raw material mixture, passes through extraneous component in melting process
The accurate control glass refraction of fine tuning, forms large-size glass blank with material leakage method, finally realizes using fine annealing technique
Accurate control value-added to glass refraction obtains the lanthanum crown LaK3 series radiation resistance of high optical quality, high-refractivity and low-dispersion
Optical glass material.The LaK3 series stabilized glass material bubble degree of this method preparation is A0 grades, and A grades of striped degree, optics is equal
Even 1 class of property, up to 1 class, the refractive index of same batch material and the consistency of abbe number are A grades for stress birfringence, wherein
Interior transmitance >=92% of the LaK503 glass material predose (with a thickness of 10mm) at 470nm, be subjected to accumulated dose be 1 ×
105Optical density increment Delta D≤0.015 after rad (Si) gamma-ray irradiation on thickness per cm；The glass material can satisfy sky
Between optics optical system of star sensor be resistant to high dosage irradiation for a long time in space environment, can meet high orbit in space, 15 to
Service life requirement in 25 years.The refractive index and abbe number of radiation resistance optical glass and common not radiotolerant LaK3 trade mark light
The refractive index and abbe number difference for learning the standard of glass can be controlled in 0 class, and the two has comparable optical constant；The resistance to spoke of preparation
According to optical glass material stable chemical performance, it is suitable for producing in enormous quantities.By optimizing and revising glass composition and radiation stabilized agent
Content can get the adjustable serial radiation resistance optical glass material with identical dispersion properties of visible light shortwave transmitance height,
The Star-Sensor Design application demand of the different radiation-resistant property requirements such as high and low track, different service lifes can be met.It is significantly rich
Rich China's radiation resistance optical glass material trade mark designs for Space Optical System and increases more more options.
Claims (9)
1. a kind of lanthanum crown LaK3 series space radiation resistance optical glass, it is characterised in that: material composition and mass fraction are as follows: 10-
13% SiO2, 13-17% B2O3, 11-14% Al2O3, 0.5-4% ZnO, 0.5-3% ZrO2, 51-55%
La2O3, 1.5-6% Y2O3, 0.3-1.5% CeO2。
2. lanthanum crown LaK3 series according to claim 1 space radiation resistance optical glass, it is characterised in that: SiO2Quality
Score is 10.5-11.8%；B2O3Mass fraction be 14.7-15.7%；Al2O3Mass fraction be 11-12.5%；La2O3
Mass fraction be 52.6-54%；ZrO2, ZnO and Y2O3The sum of mass fraction be 5-10.5%；CeO2Mass fraction be
0.4-1%.
3. a kind of preparation method of lanthanum crown LaK3 series space radiation resistance optical glass, it is characterised in that: the following steps are included:
1] according to the quality proportioning of oxide raw material ingredient and mass percent calculating glass raw material in claim 1, accurately
It weighs raw material and is uniformly mixed；
2] the high temperature glass of bubble-free and striped is obtained after raw material after mixing being carried out high-temperature fusion, stirring clarification and homogenizing
Glass liquid；
3] large-size glass blank is formed using leakage note method；
4] lanthanum crown LaK3 series radiation resistance optical glass is obtained after annealing to chunk glass.
4. the preparation method of lanthanum crown LaK3 series according to claim 3 space radiation resistance optical glass, it is characterised in that:
Step 2] the following steps are included:
2.1] raw material after mixing is added portionwise in the platinum crucible for be heated to 1230 DEG C and is melted in advance；
2.2] after keeping the temperature 2h, 1400 DEG C is warming up to and carries out constant speed promotion and stirring with blender；
2.3] glass metal of bubble-free and striped is obtained after 5~7h of clarifying and homogenizing.
5. the preparation method of lanthanum crown LaK3 series according to claim 4 space radiation resistance optical glass, it is characterised in that:
Step 2] in further include the steps that refractive index adjust:
2.4] post-processing refraction index test sample is sampled；
2.5] refractive index n of the measurement sample at 587.6nm wavelengthd；
2.6] judge ndWhether in 1.7397 ± 0.0003 ranges；If so, executing step 3 after continuing stirring promotion 4h]；If
It is no, then follow the steps 2.7]；
2.7] if ndLower than 1.7394, then lanthana is added into glass metal in the ratio of 0.35g/kg glass metal；If ndIt is higher than
1.7400, then boric acid is added into glass metal in the ratio of 0.42g/kg glass metal and carries out refractive index adjustment；
2.8] after stirring evenly and clarify, return step 2.4].
6. the preparation method of lanthanum crown LaK3 series according to claim 4 or 5 space radiation resistance optical glass, feature exist
In: step 3] the following steps are included:
3.1] high-temperature glass liquid is cooled to 1220 DEG C with the rate of temperature fall of 1 DEG C/min；
3.2] high-temperature glass liquid after cooling is injected into the mold for being preheating to 420 DEG C, carries out the molding of large-size glass blank.
7. the preparation method of lanthanum crown LaK3 series according to claim 6 space radiation resistance optical glass, it is characterised in that:
Step 4] the following steps are included:
4.1] it will be transferred to have warmed up into 710 DEG C of Muffle furnace after the demoulding of molding chunk glass and carry out black annealing, heat preservation 12~
Cooled down 100 DEG C after for 24 hours with the rate of temperature fall of 2 DEG C/h, then be cooled to 100 DEG C with the rate of temperature fall of 5 DEG C/h, closing Muffle furnace makes glass
Glass sample obtains black annealing chunk glass after being naturally cooling to room temperature with furnace；
4.2] black annealing chunk glass is embedded in the Muffle cabinet of stainless steel material with fine granularity glass sand, then will
Muffle cabinet, which is placed in annealing furnace, is warming up to 710 DEG C；After keeping the temperature 48h, cooled down 100 DEG C with the rate of temperature fall of 0.2~1.0 DEG C/h,
300 DEG C are cooled to the rate of temperature fall of 2 DEG C/h again, is then cooled to 100 DEG C with the rate of temperature fall of 4 DEG C/h；Closing annealing furnace makes
Glass sample is naturally cooling to obtain lanthanum crown LaK3 series radiation resistance optical glass after room temperature with furnace.
8. the preparation method of lanthanum crown LaK3 series according to claim 7 space radiation resistance optical glass, it is characterised in that:
Step 1] used in raw material be partial size in the specific pure dry powder of 100-120 purpose.
9. the preparation method of lanthanum crown LaK3 series according to claim 8 space radiation resistance optical glass, it is characterised in that:
Step 3.2] in mold above be provided with cover board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611260938.2A CN106830670B (en) | 2016-12-30 | 2016-12-30 | Lanthanum crown LaK3 series space radiation-resistant optical glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611260938.2A CN106830670B (en) | 2016-12-30 | 2016-12-30 | Lanthanum crown LaK3 series space radiation-resistant optical glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106830670A CN106830670A (en) | 2017-06-13 |
| CN106830670B true CN106830670B (en) | 2019-05-31 |
Family
ID=59114175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611260938.2A Active CN106830670B (en) | 2016-12-30 | 2016-12-30 | Lanthanum crown LaK3 series space radiation-resistant optical glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106830670B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI795418B (en) * | 2017-07-21 | 2023-03-11 | 日商小原股份有限公司 | Optical glass, preforms and optical components |
| CN107759074A (en) * | 2017-11-07 | 2018-03-06 | 柳州市奥康眼镜有限公司 | A kind of high refraction lanthanum crown optical glass and optical element |
| CN112250298B (en) * | 2020-10-28 | 2022-08-12 | 中国建筑材料科学研究总院有限公司 | Radiation-proof glass and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215503A (en) * | 2002-12-27 | 2010-09-30 | Hoya Corp | Optical glass, press-molding glass gob and optical element |
| JP2015074572A (en) * | 2013-10-08 | 2015-04-20 | 日本電気硝子株式会社 | Optical glass |
| CN105967514A (en) * | 2016-05-10 | 2016-09-28 | 成都光明光电股份有限公司 | Lanthanum flint optical glass |
-
2016
- 2016-12-30 CN CN201611260938.2A patent/CN106830670B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215503A (en) * | 2002-12-27 | 2010-09-30 | Hoya Corp | Optical glass, press-molding glass gob and optical element |
| JP2015074572A (en) * | 2013-10-08 | 2015-04-20 | 日本電気硝子株式会社 | Optical glass |
| CN105967514A (en) * | 2016-05-10 | 2016-09-28 | 成都光明光电股份有限公司 | Lanthanum flint optical glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106830670A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106587596B (en) | Heavy flint ZF series space radiation-resistant optical glass and preparation method thereof | |
| US9416047B2 (en) | Optical glass, glass material for press molding, and optical element | |
| CN101492247B (en) | Optic glass | |
| US8158541B2 (en) | Optical glass, precision press-molding preform and optical element | |
| JP4322217B2 (en) | Optical glass, glass gob for press molding, optical component, method for manufacturing glass molded body, and method for manufacturing optical component | |
| CN106830670B (en) | Lanthanum crown LaK3 series space radiation-resistant optical glass and preparation method thereof | |
| JP5867507B2 (en) | Optical glass | |
| JP4562041B2 (en) | Optical glass, glass gob for press molding, and optical element | |
| CN104981439A (en) | Optical glass, optical glass blank, glass material for press molding use, optical element, and methods respectively for producing said products | |
| TWI666188B (en) | Glass, glass materials for press molding, blanks for optical elements, and optical elements | |
| Liao et al. | FTIR spectra and properties of iron borophosphate glasses containing simulated nuclear wastes | |
| CN106477881B (en) | Dense crown ZK9 series space radiation-resistant optical glass and preparation method thereof | |
| CN105461219B (en) | Glass, compression moulding glass material, optical element blank and optical element | |
| CN101012103A (en) | Optical glass, press-molding glass gob and optical element | |
| CN105693087B (en) | Glass, compression moulding glass material, optical element blank and optical element | |
| WO2014196523A1 (en) | Optical glass, optical element blank, glass material for press forming, optical element, and processes for producing these | |
| JP2009203135A (en) | Optical glass, optical element and preform for precision press molding | |
| CN102745894A (en) | Optical glass | |
| CN106966589A (en) | Glass, compressing use glass material, optical element blank and optical element | |
| Wang et al. | Immobilization of a simulated HLW in phosphate based glasses/glass-ceramics by melt-quenching process | |
| CN108623146A (en) | Environmentally friendly special type protection glass | |
| CN106830672B (en) | Lanthanum flint LaF3 series space radiation-resistant optical glass and preparation method thereof | |
| CN104995144A (en) | Optical glass, hot-formed article and method for manufacturing same, and optical element and method for manufacturing same | |
| CN107207320B (en) | Glass, compression moulding glass material, optical element blank and optical element | |
| CN103833219B (en) | Opticglass |
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 |