CN106830672B - Lanthanum flint LaF3 series space radiation resistance optical glass and preparation method thereof - Google Patents
Lanthanum flint LaF3 series space radiation resistance optical glass and preparation method thereof Download PDFInfo
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- CN106830672B CN106830672B CN201611256405.7A CN201611256405A CN106830672B CN 106830672 B CN106830672 B CN 106830672B CN 201611256405 A CN201611256405 A CN 201611256405A CN 106830672 B CN106830672 B CN 106830672B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
- C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
- C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
Abstract
The present invention relates to a kind of lanthanum flint LaF3 series space radiation resistance optical glass and preparation method thereof for being mainly used for the spaceborne optical system of star sensor of aerospace.The material composition and quality proportioning of the series space radiation resistance optical glass are as follows: the SiO of 13-16%2, 14-16% B2O3, 8-13% Al2O3, 39-42% La2O3, 11-16% PbO, 1-3% ZnO, 0-2% CaO, 0.5-2.5% ZrO2, 1-2% Y2O3, 0.2-1.5% CeO2.Lanthanum flint LaF3 series provided by the invention space radiation resistance optical glass has high radiation-resistant property, it can satisfy the tolerance high dose accumulation irradiation for a long time in the space environment of space optics optical system of star sensor, it can be met in space high orbit, the requirement of 10~25 years service life.
Description
Technical field
The present invention relates to a kind of lanthanum flint LaF3 series for being mainly used for the spaceborne optical system of star sensor of aerospace is empty
Between 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, optical system
Image 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 Space Radiation Effects of high-energy rays and particle are tired out for a long time
Product will lead to the similar transmission type optical system transmitance such as star sensor of common designations optical glass structure and quickly decline
Reduce to opaque, system imaging quality, which reduces, not to be available even.The domestic anti-spoke because lacking space optical system of star sensor
According to performance innovation design and high-quality radiation resistance optical glass material needed for reinforcing, it there is no such long-life (in space before
High orbit, 15 to 25 years service life) optical system.
Domestic radiation resistance optical glass material single variety, so that middle high orbit, long-life aerospace load transmission-type
The Radiation hardness design of optical system is limited by the available optics of optical system with the promotion of spaceborne star sensor key performance
Glass material, thus the design difficulty of the spaceborne optical system of star sensor of aerospace greatly increases, and constrains China in middle height
The development of track, long-life Space Optical System and load technical aspect.
To flint class optical glass, PbO content increases greatly the melted technical difficulty of optical glass in glass system.From glass
Glass composition considers that the leaded shortwave transmitance for making optical glass declines, and the higher decline of lead content is more obvious；It needs to pass through glass
The optimization of glass adjustment of formula and material purity, impurity content and melting control climate reduce the UV absorption of material, and it is saturating to improve shortwave
Cross rate.In melted technical aspect, in order to reduce erosion of the direct melting flint class flint glass to noble metal crucible, flint glass
Clay pot is mostly used directly to be melted greatly before, it is more difficult to obtain the optical glass product of high optical-grade, especially optical glass
The middle more difficult thorough elimination of bubble, bubble degree grade is lower, and yield rate is low.And leaded optical glass is in crucible high temperature melting
It is particularly easy to volatilize and be layered, therefore be difficult to obtain the leaded optical glass of high optical quality using existing preparation method.
Summary of the invention
In order to solve the skill of domestic radiation resistance optical glass material single variety at present and leaded optical glass preparation difficulty
Art problem, the present invention provide a kind of lanthanum flint LaF3 series space radiation resistance optical glass and preparation method thereof.
The technical solution of the invention is as follows: a kind of lanthanum flint LaF3 series space radiation resistance optical glass, feature exist
In: material composition and quality proportioning are as follows: the SiO of 13-16%2, 14-16% B2O3, 8-13% Al2O3, 39-42%
La2O3, 11-16% PbO, 1-3% ZnO, 0-2% CaO, 0.5-2.5% ZrO2, 1-2% Y2O3, 0.2-1.5%
CeO2。
Preferably, SiO2Mass fraction be 13.6-15.1%；B2O3Mass fraction be 14.2-15.7%；Al2O3's
Mass fraction is 9.2-9.9%；La2O3Mass fraction be 39.8-41.2%；The mass fraction of PbO is 13.5-15.2%；
ZnO、CaO、Y2O3And ZrO2The sum of mass fraction be 4.3-6.7%.
The present invention also provides a kind of preparation method of lanthanum flint LaF3 series space radiation resistance optical glass, special characters
It is: 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 flint LaF3 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 heated to 1250 DEG C of pre- fusings；
2.2] after keeping the temperature 2h, 1380 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 1.7369 ± 0.0003 ranges；If so, executing step after continuing stirring promotion 5h
3]；If it is not, thening follow the steps 2.7]；
2.7] if ndLower than 1.7366, then lead silicate is added into glass metal in the ratio of 0.53g/kg glass metal；If ndIt is high
In 1.7372, then boric acid is added into glass metal in the ratio of 0.44g/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 1210 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 440 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 650 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 650 DEG C；After keeping the temperature 48h, with the rate of temperature fall cooling 100 of 0.1~1.0 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 flint LaF3 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 80-100 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 LaF503 is passed through
It is 1 × 10 by accumulated dose5Optical density increment Delta D≤0.11 after rad (Si) gamma-ray irradiation on thickness per cm, can satisfy
The tolerance high dose accumulation irradiation for a long time in the space environment of space optics optical system of star sensor, can meet it in the high rail in space
The requirement in road, 10~25 years service life.
2, device for Optical Properties of Materials is excellent.Mixed powder in the present invention is molten into clinker, platinum crucible through ceramic crucible in advance
The method of high-temperature fusion preparation series LaF3 radiation resistance optical glass is easier to obtain no platinum granule foreign, excellent in optical properties
Radiation resistance optical glass material, bubble degree can reach A0 grades, striped degree it is double up to 1 class, stress up to A grades, optical homogeneity
It reflecting up to 1 class, the refractive index of same batch material and the consistency of abbe number are A grades, acid resistance, moisture resistivity be respectively 2,
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 sufficiently eliminates the stress in glass material to 1.7440 ± 0.0002, and radiation resistance light can be effectively controlled
Learning glass and LaF3 common designations optical glass has comparable optical constant, the refringence (± 2 × 10 of the two-4) and dispersion system
Number difference (± 0.3%) can be controlled simultaneously in 0 class, low reachable 1 class (< 2nm/cm) of stress birfringence.
4, material series.By optimizing and revising radiation resistance optical glass composition and radiation stabilized agent content, realize visible
The balance of light shortwave transmitance and resistance to high-energy ray irradiation ability takes into account Space Optical System design and is resistant to different spaces to material
The difference of total radiation dose and shortwave transmitance height stresses to require, can prepare LaF303 with close dispersion properties,
The series radiation resistance optical glass material such as LaF403, LaF503, LaF603, LaF703, it is different resistance to meet high and low track etc.
Protection observation light under irradiation ability, the space in different designs service life projection/refractive optical system design and strong nuclear radiation environment
Learn the requirement of window.
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 (LaF303, LaF403, LaF503, LaF603, LaF703,10mm) 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)) LaF503 does not plate the optical transmission spectra curve of membrane sample (Ф 20mm × 2mm) after gamma-rays irradiates respectively.
Specific embodiment
Development and production high orbit, long-life space optics load LaF3 series radiation resistance optical glass material, enrich me
The glass trade mark type in state, radiation resistance optical glass material library, space, can fundamentally solve Space Optical System radiation resistance
Reinforce the materials for support problem of design, the development of the deep space exploration in power-assisted China and high orbit satellite navigation cause.In addition, tolerance
The radiation resistance optical glass material of high irradiation dose, also can be used as observation optical window protective materials under strong nuclear radiation environment or
Imaging optical system is constituted as system important Parts, is applied to the key areas such as atomic energy industry, high-energy physics 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 protecting under design and strong nuclear radiation environment and imaging optical system is to radiation resistance optical glass material series
The requirement of change, the invention discloses a kind of lanthanum flint LaF3 series radiation resistance optical glass material and its crucial preparation processes
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 LaF3 series radiation resistance optical glass material essence is annealedd) in 1.7440 ± 0.0002 ranges
It is interior, Abbe number (υd) in 44.9 ± 0.13 ranges.
Lanthanum flint LaF3 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 13~16%, it is optimal be 14~
15% (wt), it can reduce the thermal expansion coefficient of glass, improve the thermal stability of glass, chemical stability, softening temperature, heat-resisting
Property, hardness and mechanical strength etc..B2O3Total content is 14~16%, and optimal is 14.2-15.7% (wt), can reduce glass smelting
Temperature, while improving the above-mentioned performance of glass, but when its content is more than 16%, will increase the tendency towards devitrification of this kind of glass, it reduces
The chemical stability of glass.
ZrO is added2, ZnO, CaO and Al2O3、Y2O3For adjusting the refractive index and thermal expansion coefficient of glass, glass is improved
Chemical stability and machining property.Meanwhile ZrO2、Al2O3、Y2O3Addition can improve the crystallization property of glass, improve glass
Glass, at glass stability, thermal stability and chemical stability, can effectively extend the material of glass, prevent large scale leakage injection forming
Chunk glass is burst in cooling procedure in a mold；Again can the refractive index to glass effectively adjusted.But ZrO2, ZnO and Y2O3
Otherwise total content can make this kind of glass be easy to devitrification no more than 15%, dwindle into glass range, while will increase the viscous of glass
Degree improves glass smelting and forming temperature, prepares more difficult；ZrO2, CaO, ZnO and Y2O3Summation it is optimal be 4.3~
6.7% (wt).Network intermediate oxide Al2O3Optimal is 9.2~9.9% (wt).
It introduces PbO and is remarkably improved glass refraction, but dispersion increases less；But glass metal high temperature when PbO too high levels
Viscosity is smaller, glass is easy layering, and micro-bubble is more in glass, is unfavorable for glass photosensitiveness state modulator, while PbO content mistake
Height will increase the hot, aggressive of corundum-mullite ceramics crucible and platinum crucible.Take into account the refractive index of lanthanum flint glass with
The design of dispersion parameters is modulated, and for PbO content no more than 16%, optimal is 13.5~15.2% (wt) in this kind of glass.
(2) uniformly mixed powder is added in corundum-mullite ceramics crucible by several times, 1250 DEG C by mixed powder fritting
Change, after keeping the temperature 2h, be put into 1350 DEG C of platinum crucibles, glass smelting temperature is on 1380 DEG C of left sides in the control platinum crucible that slowly heats up
The right side, and constant speed promotion and high-speed stirred are carried out with platinum leaf slurry blender, keep glass liquid stirring uniform；After clarification starts 2h, use
Sample spoon carries out stokehold sampling, the right angle refractive index test sample that cooling post-processing angle is 90 ° ± 1 ', and measurement sample exists
Refractive index n at 587.6nm wavelengthd；Stokehold samples refractive index ndControl is in 1.7369 ± 0.0003 ranges, if ndIt is relatively low, to
Lead silicate (0.53g/kg glass metal) is added in glass metal to be turned up 0.0001 for refractive index；If ndIt is higher, add into glass metal
Enter boric acid (0.44g/kg glass metal) and refractive index is turned down 0.0001；ndAfter the value that makes it, continues clarification and eliminates bubble,
Homogenizing is futher stirred after sampling bubble-free, and elimination 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 1210 DEG C, is slowly injected into the copper mould for having been preheated with 440 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 650 DEG C of annealing temperature after the demoulding of molding glass and slightly moved back
Fire: 650 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: 650 DEG C of heat preservation 48h, elder generation is with-(0.1~1.0) 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 mixed powder is through corundum-mullite crucible fritting
It is transferred to clarifying and homogenizing in platinum crucible again after turning to glassy state, can effectively reduce and platinum crucible is invaded under PbO component high temperature
Erosion, avoids bringing platinum particle into and enters in glass；During Elema electric smelting stove heating high temperature molten glass, starched using platinum leaf
Blender carries out promotion stirring, and clarification to high-temperature glass liquid, homogenization process, high-temperature glass liquid are successively realized in a crucible
It is sampled after mixing evenly by stokehold refractive index and additional high/low refractive index component adjusts the refractive index of glass in crucible, accurately
Control ndThe value that makes it 1.7369 ± 0.0003 is that subsequent handle by fine annealing makes glass ndNumerical value is modulated to
1.7440 ± 0.0002 premise guarantee.High-temperature glass liquid is slowly injected into via the elongated material leakage mouth of crucible bottom when glass forms
Into the copper mould having had been warmed up；It is cooling that casting starts rear mold bottom ventilation, during preventing glass to be poured and copper mould
It sticks together and causes demoulding difficult；Stainless steel cover board is covered above mold, 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, byAbbe number υ is calculatedd.According to GB/T 7962 respectively to the light of radiation resistance optical glass sample
Uniformity, stress birfringence, striped degree, bubble degree, acid resistance, moisture resistivity are tested, according to " GB 903-87 non-colored light
Learn 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, determine that test accumulated dose corresponds to irradiation time；
5) irradiation dose (or time) is added up, and reaches test plan accumulated dose or dose point 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 corundum-mullite ceramics crucible to be melted for 1250 DEG C in advance, and 1350 DEG C of platinum earthenware is put into after heat preservation
In crucible, by silicon carbide electric smelter heating melting, for the control of glass smelting temperature at 1380 DEG C or so, melting time is 5~7h,
Homogenizing is stirred to glass metal using platinum leaf slurry blender in melting process.High-temperature glass liquid after mixing evenly, passes through furnace
Preceding refractive index modulation, accurately controls ndThe value that makes it 1.7369.After continuing clarification elimination bubble and stirring,
By high-temperature glass liquid slow cooling to 1210 DEG C or so, it is injected by crucible bottom material leakage mouth and has been preheated with 400 DEG C of copper
Chunk glass molding is carried out in mold, and will be quickly put into and had warmed up to 650 DEG C of annealing temperatures after the demoulding of formed glass sample
It carries out black annealing in Muffle 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 drop of -5 DEG C/h
Warm rate is cooled to room temperature.Black annealing chunk glass is subjected to fine annealing processing: being embedded in stainless steel with glass sand
In matter Muffle cabinet, 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 -2
DEG C/h, -4 DEG C/h rate of temperature fall be cooled near 300 DEG C, 100 DEG C, close power supply so that glass sample is naturally cooling to room with furnace
Temperature.
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 LaF303 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7439, refractive index after fine annealing
Increment 0.0070；Its Abbe number υ is calculateddIt is 45.00.
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 LaF303 material in 470nm wavelength470It is 97.0%；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 × 103It is right on thickness per cm after rad (Si) gamma-ray irradiation
Answering the optical density increment Delta D of 470nm is 0.06.
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 corundum-mullite ceramics crucible to be melted for 1250 DEG C in advance, and 1350 DEG C of platinum earthenware is put into after heat preservation
In crucible, by silicon carbide electric smelter heating melting, at 1380 DEG C or so, melting time is 5~7h for glass melting temperature control, is being melted
Glass metal is stirred using platinum leaf slurry blender in the process.High-temperature glass liquid after mixing evenly, passes through stokehold refractive index
High/low refractive index component is sampled and be added, n is accurately controlleddThe value that makes it 1.7371.Continue clarification to eliminate bubble and fill
Divide after mixing evenly, by high-temperature glass liquid slow cooling to 1210 DEG C or so, is injected into advance by crucible bottom material leakage mouth
Heat carries out chunk glass molding into 400 DEG C of copper mould, and will quickly be put into and had warmed up to 650 after the demoulding of formed glass sample
Black annealing is carried out in the Muffle furnace of DEG C annealing temperature: 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
It is cooled to room temperature with the rate of temperature fall of -5 DEG C/h.Black annealing chunk glass is subjected to fine annealing processing: being buried with glass sand
It sets in stainless steel material Muffle cabinet, in smart annealing furnace, keeps the temperature 48h, first with the rate of temperature fall cooling 100 of -0.5 DEG C/h
DEG C, then be cooled near 300 DEG C, 100 DEG C with the rate of temperature fall of -2 DEG C/h, -4 DEG C/h respectively, close power supply make glass sample with
Furnace is naturally cooling to room temperature.
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 LaF403 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7442, refractive index after fine annealing
Increment 0.0071；Its Abbe number υ is calculateddIt is 44.79.
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 LaF403 material in 470nm wavelength470It is 95.6%；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 0.08.
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 corundum-mullite ceramics crucible to be melted for 1250 DEG C in advance, and 1350 DEG C of platinum earthenware is put into after heat preservation
In crucible, by silicon carbide electric smelter heating melting, at 1380 DEG C or so, melting time is 5~7h for glass melting temperature control, is being melted
Glass metal is stirred using platinum leaf slurry blender in the process.High-temperature glass liquid after mixing evenly, passes through stokehold refractive index
Modulation, accurately controls ndThe value that makes it 1.7370.After continuing clarification elimination bubble and stirring, by high temperature glass
Glass liquid slow cooling to 1210 DEG C or so, by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 380 DEG C into
The molding of row chunk glass, and will quickly be put into and had warmed up into the Muffle furnace of 650 DEG C of annealing temperatures after the demoulding of formed glass sample
It carries out black annealing: 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 cold with the rate of temperature fall of -5 DEG C/h
But to room temperature.Black annealing chunk glass is subjected to fine annealing processing: being embedded in stainless steel material Muffle case with glass sand
In body, in smart annealing furnace, keep the temperature 48h, first cooled down 100 DEG C with the rate of temperature fall of -1.0 DEG C/h, then respectively with -2 DEG C/h, -4
DEG C/rate of temperature fall of h is cooled near 300 DEG C, 100 DEG C, 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 LaF503 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7440, refractive index after fine annealing
Increment 0.0070；Its Abbe number υ is calculateddIt is 44.82.
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 LaF503 material in 470nm wavelength470It is 94.2%；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 0.11.
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 corundum-mullite ceramics crucible to be melted for 1250 DEG C in advance, and 1350 DEG C of platinum earthenware is put into after heat preservation
In crucible, by silicon carbide electric smelter heating melting, at 1380 DEG C or so, melting time is 5~7h for glass melting temperature control, is being melted
Glass metal is stirred using platinum leaf slurry blender in the process.High-temperature glass liquid after mixing evenly, passes through stokehold refractive index
Modulation, accurately controls ndThe value that makes it 1.7368.After continuing clarification elimination bubble and stirring, by high temperature glass
Glass liquid slow cooling to 1210 DEG C or so, by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 390 DEG C into
The molding of row chunk glass, and will quickly be put into and had warmed up into the Muffle furnace of 650 DEG C of annealing temperatures after the demoulding of formed glass sample
It carries out black annealing: 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 cold with the rate of temperature fall of -5 DEG C/h
But to room temperature.Black annealing chunk glass is subjected to fine annealing processing: being embedded in stainless steel material Muffle case with glass sand
In body, in smart annealing furnace, keep the temperature 48h, first cooled down 100 DEG C with the rate of temperature fall of -0.2 DEG C/h, then respectively with -2 DEG C/h, -4
DEG C/rate of temperature fall of h is cooled near 300 DEG C, 100 DEG C, 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 LaF603 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7440, refractive index after fine annealing
Increment 0.0072；Its Abbe number υ is calculateddIt is 44.93.
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 LaF603 material in 470nm wavelength470It is 89.5%；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 0.15.
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 corundum-mullite ceramics crucible to be melted for 1250 DEG C in advance, and 1350 DEG C of platinum earthenware is put into after heat preservation
In crucible, by silicon carbide electric smelter heating melting, at 1380 DEG C or so, melting time is 5~7h for glass melting temperature control, is being melted
Glass metal is stirred using platinum leaf slurry blender in the process.High-temperature glass liquid after mixing evenly, passes through stokehold refractive index
Modulation, accurately controls ndThe value that makes it 1.7370.After continuing clarification elimination bubble and stirring, by high temperature glass
Glass liquid slow cooling to 1210 DEG C or so, by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 370 DEG C into
The molding of row chunk glass, and will quickly be put into and had warmed up into the Muffle furnace of 650 DEG C of annealing temperatures after the demoulding of formed glass sample
It carries out black annealing: 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 cold with the rate of temperature fall of -5 DEG C/h
But to room temperature.Black annealing chunk glass is subjected to fine annealing processing: being embedded in stainless steel material Muffle case with glass sand
In body, 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, -4
DEG C/rate of temperature fall of h is cooled near 300 DEG C, 100 DEG C, 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 LaF703 sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, wherein ndIt is 1.7441, refractive index after fine annealing
Increment 0.0071；Its Abbe number υ is calculateddIt is 44.86.
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 LaF703 material in 470nm wavelength470It is 84.8%；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 0.18.
The space optics optical system of star sensor that selection can meet space high orbit, 15 to 25 years service life requires is set
With the LaF503 radiation resistance optical glass of use in meter, the interior transmittance curve of material is as shown in Figure 1, LaF503 glass material exists
The interior transmitance τ of 470nm wavelength470It is 94.2%.LaF503 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, with
Non-irradiated LaF503 glass material is compared, the optical density increment Delta D that 470nm is corresponded on thickness per cm is respectively 0.003,
0.011,0.10 and 0.49.
As can be seen from the above embodiments, lanthanum flint LaF3 series radiation resistance optical glass of the present invention the preparation method comprises the following steps:
It is mainly to form with glass sand, boric acid, aluminium oxide, lanthana and lead oxide, addition small amounts zirconium, yttrium oxide and irradiation
Stabilizer cerium oxide passes through the pre- melt raw material mixture of ceramic crucible, the clarification of platinum crucible high temperature melting and homogenizing, melting process
In accurate control glass refraction finely tuned by extraneous component, form large-size glass blank with material leakage method, moved back using precision
Fire process finally realizes accurate control value-added to glass refraction, obtains high optical quality, lanthanum flint LaF3 series radiation resistance
Optical glass material.The LaF3 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 >=94.2% of the LaF503 glass material predose (with a thickness of 10mm) at 470nm, be subjected to accumulated dose be 1 ×
105Optical density increment Delta D≤0.11 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, space high orbit, 15 to 25 can be met
Year service life requirement.The refractive index and abbe number of radiation resistance optical glass and common not radiotolerant LaF3 trade mark optics
The refractive index and abbe number difference of the standard of glass can be controlled in 0 class, and the two has comparable optical constant；The radiation resistance of preparation
Optical glass material stable chemical performance is suitable for producing in enormous quantities.Contained by optimizing and revising glass composition and radiation stabilized agent
Amount can get the adjustable serial radiation resistance optical glass material with identical dispersion properties of visible light shortwave transmitance height, can
Meet the Star-Sensor Design application demand of the different radiation-resistant property requirements such as high and low track, different service lifes.It greatly enriches
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 flint LaF3 series space radiation resistance optical glass, it is characterised in that: material composition and quality proportioning are as follows:
The SiO of 13-16%2, 14-16% B2O3, 8-13% Al2O3, 39-42% La2O3, 11-16% PbO, 1-3%
The ZrO of CaO, 0.5-2.5% of ZnO, 0-2%2, 1-2% Y2O3, 0.2-1.5% CeO2。
2. lanthanum flint LaF3 series according to claim 1 space radiation resistance optical glass, it is characterised in that: SiO2Matter
Amount score is 13.6-15.1%；B2O3Mass fraction be 14.2-15.7%；Al2O3Mass fraction be 9.2-9.9%；
La2O3Mass fraction be 39.8-41.2%；The mass fraction of PbO is 13.5-15.2%；ZnO,CaO,Y2O3And ZrO2Matter
Measuring the sum of score is 4.3-6.7%.
3. a kind of preparation method of lanthanum flint LaF3 series space radiation resistance optical glass, it is characterised in that: the following steps are included:
1] it according to the material composition and quality proportioning precise raw material in claim 1 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 flint LaF3 series radiation resistance optical glass is obtained after annealing to chunk glass.
4. the preparation method of lanthanum flint LaF3 series according to claim 3 space radiation resistance optical glass, feature exist
In: step 2] the following steps are included:
2.1] raw material after mixing is heated to 1250 DEG C of pre- fusings；
2.2] after keeping the temperature 2h, 1380 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 flint LaF3 series according to claim 4 space radiation resistance optical glass, feature exist
In step 2] in further include the steps that refractive index adjusts:
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 1.7369 ± 0.0003 ranges；If so, executing step 3 after continuing stirring promotion 5h]；If
It is no, then follow the steps 2.7]；
2.7] if ndLower than 1.7366, then lead silicate is added into glass metal in the ratio of 0.53g/kg glass metal；If ndIt is higher than
1.7372, then boric acid is added into glass metal in the ratio of 0.44g/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 flint LaF3 series according to claim 4 or 5 space radiation resistance optical glass, feature
It is: step 3] the following steps are included:
3.1] high-temperature glass liquid is cooled to 1210 DEG C under 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 440 DEG C, carries out the molding of large-size glass blank.
7. the preparation method of lanthanum flint LaF3 series according to claim 6 space radiation resistance optical glass, feature exist
In: step 4] the following steps are included:
4.1] it will be transferred to have warmed up into 650 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 650 DEG C；After keeping the temperature 48h, cooled down 100 DEG C with the rate of temperature fall of 0.1~1.0 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 flint LaF3 series radiation resistance optical glass after room temperature with furnace.
8. the preparation method of lanthanum flint LaF3 series according to claim 7 space radiation resistance optical glass, feature exist
In step 1] used in raw material be partial size in the specific pure dry powder of 80-100 purpose.
9. the preparation method of lanthanum flint LaF3 series according to claim 8 space radiation resistance optical glass, feature exist
In step 3.2] in mold above be provided with cover board.
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| 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 |
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| 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 |
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Application publication date: 20170613 Assignee: FEMTO TECHNOLOGY (XI'AN) Co.,Ltd. Assignor: Xi'an Institute of Optics and precision machinery, Chinese Academy of Sciences Contract record no.: X2021610000010 Denomination of invention: Lanthanum flint LaF3 series space radiation resistant optical glass and its preparation method Granted publication date: 20190531 License type: Exclusive License Record date: 20210811 |
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