CN105000801B - Ultraviolet-transmitting high-damage-threshold fluorophosphate laser glass and preparation method thereof - Google Patents
Ultraviolet-transmitting high-damage-threshold fluorophosphate laser glass and preparation method thereof Download PDFInfo
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- 239000000087 laser glass Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 105
- 239000000463 material Substances 0.000 claims abstract description 83
- 230000006378 damage Effects 0.000 claims abstract description 54
- 238000000137 annealing Methods 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000005352 clarification Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000004927 fusion Effects 0.000 claims abstract description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 238000007493 shaping process Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- 239000005357 flat glass Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 29
- 239000005350 fused silica glass Substances 0.000 abstract description 22
- 238000012360 testing method Methods 0.000 abstract description 21
- 230000003287 optical effect Effects 0.000 abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000265 homogenisation Methods 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- -1 rare earth fluoride Chemical class 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 239000005304 optical glass Substances 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 14
- 238000010998 test method Methods 0.000 description 13
- 230000007547 defect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000010309 melting process Methods 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005383 fluoride glass Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000009738 saturating Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 241000931526 Acer campestre Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000270288 Gekko Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006132 parent glass Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Glass Compositions (AREA)
Abstract
The invention provides high damage threshold fluorophosphate laser glass capable of being used as an ultraviolet transmitting window material and a preparation method thereof. The preparation method comprises the steps of taking alkali metal oxide, alkaline earth metal oxide, aluminum oxide, zinc oxide and phosphorus pentoxide as main raw material components, adding a small amount of rare earth fluoride, preparing a glass blank by a leakage injection method after high-temperature melting, clarification and homogenization, and obtaining the high damage threshold fluorophosphate laser glass material by annealing treatment. The glass material can replace fused quartz materials, is processed into optical components such as lenses, plane windows, prisms and the like to be applied to high-energy and high-power laser systems, solves the problem of laser damage of fused quartz and other ultraviolet optical elements in the existing high-energy and high-power systems, further improves the load output capacity of the laser, and is expected to be used as an ultraviolet transmitting optical element in a high-power laser for laser-driven inertial confinement nuclear fusion tests.
Description
Technical field
The invention belongs to laser glass field of material technology, and in particular to a kind of ultraviolet high damage threshold fluorophosphate laser
Glass material and preparation method thereof.
Background technology
Development clean type new energy is the task of top priority of survival and development of mankind, is also that China's the Implement of sustainable development strategy is excellent
The significant problem first considered.Laser Driven inertial confinement fusion is the important means for realizing controlled nuclear fusion, can be carried for the mankind
It is to solve the energy crisis in the whole world, a potential important channel of alleviation greenhouse effects at present for the inexhaustible energy, it is public
Think the dawn of 21 century cleaning new energy.Meanwhile, Laser Driven inertial confinement fusion is to Strong-field physics, laser plasma
The basic research such as body, high energy trauma, laser fusion physics have most important theories meaning and practical value.
Device of high power laser is that current inertial confinement fusion (Inertial confinement fusion, ICF) drives
A kind of ideal, ripe driver in dynamic source technology, it has also become the main direction in ICF fields in world wide.It is large-scale poly-
The maximum output flux for becoming level laser aid is limited to the damage of optical elements of large caliber.With the development of superpower laser,
National igniter (NIF), megajoule device (LMJ) of France, the device of God Light III (SG III) of China and the day in the such as U.S.
This GEKKO, the harm that optic element damage is brought further shows.Fused quartz optical component is high power solid-state laser system
The optical material being most widely used in system, it is in great demand.The laser -induced damage of fused quartz optical component is that development is high
Energy, a key restraining factors of high power laser system.
Defect in fused quartz material causes the damage threshold reduction of optical element and its surface damage threshold value to be far below body
Damage threshold, so that the complex damage threshold value reduction of material.Causing the defect of fused quartz material initial damage mainly includes material
Expect System of Detecting Surface Defects For Material and the materials such as the sub-microcrack that cut, impression, earlier damage splash pollutant and the processing on surface are produced
The internal structural defects such as the microstructural flaws produced after intrinsic defect and the laser irradiation of material.By MRF, surpass
The techniques such as sound wave cleaning technique, surface acid etching are effectively reduced the surface defect of fused quartz material.Intrinsic defect is mainly with melting
The composition of quartz material, preparation technology are relevant with microstructure；Diverse microcosmic structure and defect trigger material to irradiation response
Performance change.For high-purity optical material, external world's irradiation forms the defects such as optics, electricity, and defect increases with irradiation increase is quick
Growing causes dielectric failure, directly affects the critical natures such as light, the electricity of material, causes initial damage to produce.Although, by improving
Preparing raw material purity, improve preparation technology and reduce the UV absorption coefficient of material, surface is reduced using super smooth surface processing
Defect and CO2The techniques such as laser pre-treated lift suface processing quality, and these measures can only improve fused quartz to a certain extent
The damage threshold of material, can not fundamentally solve the problem of its laser -induced damage threshold value is low.
In addition, initial damage and initial damage point of the fused quartz under (0.35 μm) irradiation of frequency tripled laser are subsequently swashing
Damage under light irradiation continues to increase, and this not only can cause the damage of element itself to be further exacerbated by, and can also reduce the saturating of element
Rate and beam quality are crossed, wavefront distortion, influence focal spot quality is produced, or even modulation is produced to light field, causes optical intensity local to strengthen,
Easily cause the appearance of the serious conditions such as " downstream " optic element damage, be a vicious circle.In general, fused quartz element
Once damage, its mechanics, optically and thermally performance all can be weakened, and its resisting laser damage ability has turned into limitation high power at present
One of key factor that Optical Maser System energy is further lifted, has belonged to " bottleneck " problem.
Early in latter stage in 20th century, disaster of the fused quartz element under high flux is just already indicated above in NIF technical committees of the U.S.
Property damage material supply section scholar and engineering staff should be caused to note, how far fused quartz can also move ahead on current technology route
Whether it can continue reliably to use under the full flux of NIF devices design or more high fluxSo, research and development it is new, have
Importance and urgency compared with the optical material of fused quartz more high damage threshold are increasingly shown especially.U.S. Lao Lunsi-livre More state
Family laboratory (Lawrence Livermore National Laboratory) is while it is also proposed that develop more preferable laser glass
Material, makes it meet in 8-9J/cm2Flux under engineer applied, for example with crystal of fluoride, fluoride glass etc. in purple
Wave section has the conceptual substitute of good UV-permeable performance and higher resisting laser damage performance.But, fluoride is brilliant
There is the intrinsic deficiency of poor chemical stability in body, while facing the technique for being difficult to make large scale (430mm × 430mm) crystal again
Technological fix etc.；Then easily there is crystallization in fluoride glass, poor into glass, at the same in melting process fluoride components volatilization it is big,
It is difficult to keep composition stable, particularly harsh preparation condition is needed again, closed graphite crucible, argon gas inertia must be such as used
Gas shield atmosphere and it is difficult with agitator and promotes homogenization of glass etc., component in glass is uneven and component therefore, it is difficult to eliminate
The striped produced, the glass viscosity of volatilizing are small, large scale shaping is extremely difficult.
Although it is also proposed a kind of preparation method of high damage threshold window material in patent (CN 102557430B),
The high damage threshold window material is the glass system using fluoride as main component, by being introduced primarily into SiO2(19-
20mol%) improve fluoride into glass and physicochemical properties, add a small amount of rare earth oxide La2O3、Y2O3Improve glass
Thermal transition temperature and devitrification resistance energy.It is important that above-mentioned fluorosilicate glass system and method still can not thoroughly solve fluorination
The problems such as volatilization of thing parent glass system is big, viscosity is small, large scale shaping striped removes difficulties.
Therefore, develop and ultra-violet (UV) band frequency tripling light (0.35 μm) transmitance height is met on a kind of spectrum property, with higher than molten
The laser damage threshold of quartz material, and chemical stability is higher, melting technology technical elements are adapted to large scale, batch production again
New pattern laser glass material, with meet lifting high energy and power Optical Maser System load capacity and output flow engineering need
Ask, its scientific meaning and engineering application value are very great.
The content of the invention
It is low for current quartz glass frequency tripling damage threshold, and the easy crystallization of fluoride glass, be difficult to large scale production etc.
Problem, the present invention proposes a kind of new ultraviolet, high damage threshold fluophosphate laser glass composition and preparation method thereof.Should
Laser glass material has good spectral transmission performance near ultraviolet band, visible region, in frequency tripling (0.35 μm) high energy pulse
Laser irradiation is lower to have a high threshold for resisting laser damage, and stable chemical performance, suitable for producing in enormous quantities.
To achieve these goals, technology disclosed by the invention can be changed on a small quantity by being introduced in phosphate glass system
It is apt to fluoride components, the zinc oxide of adjustable glass viscosity of its UV-permeable characteristic and nonlinear factor, obtains new big chi
Very little saturating ultraviolet high damage threshold fluophosphate laser glass material.
The material composition and proportioning of the fluophosphate laser glass material of the saturating ultraviolet high damage threshold of the present invention are as follows：
Each proportioning components sum is 100%, and its percetage by weight is calculated according to the molal quantity of each component, weighs raw material and mixes
Close uniform.
Matched based on more than, alkali metal oxide (R2O it is 6~20mol%, alkaline earth oxide (R ' that) summation is optimal
O it is 7~15mol%, P that) summation is optimal2O5With Al2O3Ratio it is optimal be 7~12, the ratio of oxide and fluoride is optimal to be
15~22；The alkali metal oxide includes the Li in material composition2O、Na2O、K2O, the alkaline earth oxide includes original
Expect MgO, CaO, SrO, BaO in composition.
The preparation method of the fluophosphate laser glass material of the saturating ultraviolet high damage threshold, is according to above material composition
And proportioning, weigh raw material and be well mixed, after high-temperature fusion, stirring clarification, homogenizing, using leakage note method shaping large-size glass
Blank, annealed processing finally obtains the fluophosphate laser glass material.It can specifically be realized according to following steps：
(1) according to the mol ratio of above material composition and each composition, the percentage by weight of each composition is calculated, original is weighed
Expect, be well mixed；
(2) well mixed powder is added in platinum crucible by several times, heating melting, glass melting temperature is controlled on 1280 DEG C of left sides
The right side, and lifting stirring is carried out with platinum leaf slurry agitator, high-temperature glass liquid clarification is eliminated after bubble, sampling bubble-free further
Stirring homogenizing eliminates striped, so that the composition of the glass metal upper and lower in whole crucible is all consistent, i.e., component is uniform；Actual behaviour
In work, depending on the bubble elimination situation that settling time can be sampled according to glass, homogenising time can be according to the refractive index for sampling glass
Homogeneity is determined；
(3) after glass metal clarification eliminates bubble and stirs, by high-temperature glass liquid via the thin of crucible bottom
Long material leakage mouth is slowly injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C；
(4) by the chunk glass of cooling and shaping is quickly put into the Muffle furnace of preheating in copper mould, by being incubated, moving back
Fire, finally naturally cools to room temperature, obtains the fluorophosphate laser window glass material of high damage threshold.
Based on above-mentioned preparation technology flow, the present invention also further makees following optimization：
In step (4), by the chunk glass of cooling and shaping is quickly put into and is preheated to annealing temperature and (is arranged in copper mould
The transition temperature T of glassgNear) Muffle furnace in, be first incubated 12 hours, then cooled 100 DEG C with -2 DEG C/h cooldown rate,
It is cooled to again with -5 DEG C/h cooldown rate near 100 DEG C, closes Muffle furnace power supply, glass sample is naturally cooling to room with stove
Temperature.
The practical operation of (3), (4) step is more crucial, and mixed powder is added in platinum crucible, and Elema electric smelter adds
During hot high-temperature fusion, lifting stirring is carried out using platinum leaf slurry agitator, successively realized to high temperature glass in a crucible
High-temperature glass liquid is slowly noted via the elongated material leakage mouth of crucible bottom when the clarification of glass liquid, homogenization process, particularly glass are molded
Enter into the copper mould having had been warmed up, above mould with plus refractory cover, prevent forming process high temperature glass metal surface with
Surrounding air formation convection current, it is to avoid convection current causes to form thin and close striped in inside glass.
The present invention has following technique effect：
The laser glass material has good spectral transmission performance near ultraviolet band, visible region.
Under equal conditions, when being subjected to the irradiation of frequency tripling (0.35 μm of@8ns) High Power Laser Pulses, the laser of the material is damaged
Hinder twice that threshold value is about fused quartz.
The present invention solves the easy crystallization of fluoride glass, eliminates striped and viscosity into glass is poor, volatilization is big, be difficult to homogenizing
It is small cause large scale difficult forming the problems such as, the alternative fused quartz material of the glass material, be processed as lens, plane window and
The optical components such as prism be applied to high energy, high power laser system in improve system load capacity, be expected to for ICF laser it is defeated
The important optical element of offer of carrying out in a deep going way for going out continuation raising and the ICF researchs of flux is supported.
The glass material stable chemical performance of the present invention, suitable large scale batch production.
Brief description of the drawings
The interior transmittance curve of Fig. 1 fluorophosphate laser window glass materials 1cm thickness samples.
Fig. 2 fluorophosphate laser windows glass material, damage threshold of the fused quartz at 351nm, 527nm, 1053nm wavelength
It is worth test data.
Specific embodiment：
The present invention is constituted by main composition of alkali metal oxide, alkaline earth oxide, aluminum oxide and phosphorus pentoxide
Phosphate basis glass system, makes its ultraviolet absorption edge blue shift by introducing a small amount of fluoride components, improves its UV-permeable spy
Property, while reducing the nonlinear factor of material, introduce viscosity and processability that zinc oxide adjusts glass；By in optimization of C/C composites
The ratio respectively constituted, obtain be adapted to large scale shaping, stable chemical performance, laser damage threshold higher than fused quartz fluorophosphate
Laser glass material.
According to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Transmitted in spectrum
Than》, the transmitance of the fluophosphate laser glass material sample is entered using ultraviolet visible light-near infrared spectrometer
Row measurement, obtains the interior transmittance curve of the thick samples of 1cm.According to international standard ISO11254-1:2000(E)(Laser and
laser-related equipment—Determination of laser-induced damage threshold of
optical surfaces–Part 1:Laser damage threshold testing system platform is built in requirement 1-on-1test), tests material
Expect the damage threshold at frequency tripling wavelength (0.351 μm) place.According to national standard《The colouless optical glasses of GB/T 7962.1-2010 are surveyed
Method for testing part 1：Refractive index and abbe number》Test obtains sample at 587.6nm, 486.1nm, 656.3nm wavelength
Refractive index nd、nF、nC, byCalculating obtains Abbe number υd, field experience formula (1) brings n intod、υdIt can calculate and obtain
The nonlinear coefficient γ of sample, wherein, K=2.8 × 10-10m2/W。
Test result shows：The interior transmitance at 1cm thickness sample frequency tripling wavelength (0.351 μm) place reaches more than 98.0%
(as shown in Figure 1).Damage threshold of this new fluophosphate laser glass material at frequency tripling wavelength (0.351 μm) place (swashs
Light pulsewidth 8ns) it is higher than quartz material more than 1 times, and the damage threshold at 527nm, 1053nm wavelength is above fused quartz material
Expect (as shown in Figure 2)；Meanwhile, nonlinear factor and the fused quartz of the fluophosphate laser glass material are approached, and can prepare life
Produce large scale (430mm*430mm), the glass print of high optical quality.
The composition and the optical property of respective sample of each composition in the specific embodiment of table 1
Embodiment one：
By above-mentioned formula 1#In a mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
It is well mixed in mixer.The powder matched somebody with somebody is sequentially added in 11 liters of platinum crucibles, melted by carborundum electric smelting stove heat,
Glass melting temperature is controlled at 1280 DEG C or so, and melting time is 6h, and agitator is starched to glass metal using platinum leaf in melting process
It is stirred.After glass metal clarification eliminates bubble and stirs, high-temperature glass liquid is passed through into crucible bottom material leakage mouth
Put after being injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C, and the quick demoulding by formed glass sample
Enter to have warmed up annealing temperature and (be arranged on the transition temperature T of glassgNear) Muffle furnace in, insulation 12h after, first with -2 DEG C/h
Cooldown rate cool 100 DEG C, then be cooled to -5 DEG C/h cooldown rate 100 DEG C near, closing Muffle furnace power supply makes glass
Sample is naturally cooling to room temperature with stove, takes out chunk glass.
The sample after annealing is taken, the refraction index test sample with an accurate right angle is processed into, according to national standard《GB/T
7962.1-2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and existed
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.526555,1.531934,1.524138,
Calculating obtains its Abbe number υdFor 67.52, field experience formula (1) brings n intod、υdCalculate the nonlinear coefficient γ for obtaining sample
For 2.96 × 10-20esu。
For fused quartz material, looked into according to Xiao Te optical glass handbook (Schott Optical Glass catalogue)
Obtain its nd、nF、nCRespectively 1.45843,1.6309,1.45634, Abbe number υdFor 67.87, n is brought intod、υdTo empirical equation
(1) it is 2.5 × 10, to calculate and obtain the nonlinear coefficient γ of sample-20esu。
Sample after annealing is processed into the two thang-kng mirror polish that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Spectrum internal transmittance》,
The transmitance of sample is measured using ultraviolet visible light-near infrared spectrometer, it is 10mm samples to obtain thickness
Interior transmittance curve, as a result as shown in curve 1 in Fig. 1.Table 1 gives interior transmission of the material in frequency tripling light 351nm wavelength
Rate τ351With absorption coefficient K351Respectively 99.66% and 0.0034cm-1。
Embodiment two：
By above-mentioned formula 2#In a mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
It is well mixed in mixer.The powder matched somebody with somebody is sequentially added in 11 liters of platinum crucibles, melted by carborundum electric smelting stove heat,
Glass melting temperature is controlled at 1280 DEG C or so, and melting time is 6h, and agitator is starched to glass metal using platinum leaf in melting process
It is stirred.After glass metal clarification eliminates bubble and stirs, high-temperature glass liquid is passed through into crucible bottom material leakage mouth
Put after being injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C, and the quick demoulding by formed glass sample
Enter to have warmed up annealing temperature and (be arranged on the transition temperature T of glassgNear) Muffle furnace in, insulation 12h after, first with -2 DEG C/h
Cooldown rate cool 100 DEG C, then be cooled to -5 DEG C/h cooldown rate 100 DEG C near, closing Muffle furnace power supply makes glass
Sample is naturally cooling to room temperature with stove, takes out chunk glass.
The sample after annealing is taken, the refraction index test sample with an accurate right angle is processed into, according to national standard《GB/
The colouless optical glass method of testing part 1s of T7962.1-2010：Refractive index and abbe number》Test obtains sample and existed
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.535772,1.541463,1.533275,
Calculating obtains its Abbe number υdFor 65.43, n is brought intod、υdTo empirical equation (1), the nonlinear coefficient γ that calculating obtains sample is
3.17×10-20esu。
Sample after annealing is processed into the two thang-kng mirror polish that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Spectrum internal transmittance》,
The transmitance of sample is measured using ultraviolet visible light-near infrared spectrometer, it is 10mm samples to obtain thickness
Interior transmittance curve, as a result as shown in curve 2 in Fig. 1.Table 1 gives interior transmission of the material in frequency tripling light 351nm wavelength
Rate τ351With absorption coefficient K351Respectively 98.57% and 0.0143cm-1。
Embodiment three：
By above-mentioned formula 3#In a mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
It is well mixed in mixer.The powder matched somebody with somebody is sequentially added in 11 liters of platinum crucibles, melted by carborundum electric smelting stove heat,
Glass melting temperature is controlled at 1280 DEG C or so, and melting time is 6h, and agitator is starched to glass metal using platinum leaf in melting process
It is stirred.After glass metal clarification eliminates bubble and stirs, high-temperature glass liquid is passed through into crucible bottom material leakage mouth
Put after being injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C, and the quick demoulding by formed glass sample
Enter to have warmed up annealing temperature and (be arranged on the transition temperature T of glassgNear) Muffle furnace in, insulation 12h after, first with -2 DEG C/h
Cooldown rate cool 100 DEG C, then be cooled to -5 DEG C/h cooldown rate 100 DEG C near, closing Muffle furnace power supply makes glass
Sample is naturally cooling to room temperature with stove, takes out chunk glass.
The sample after annealing is taken, the refraction index test sample with an accurate right angle is processed into, according to national standard《GB/
The colouless optical glass method of testing part 1s of T7962.1-2010：Refractive index and abbe number》Test obtains sample and existed
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.536268,1.541800,1.533797,
Calculating obtains its Abbe number υdFor 67.00, n is brought intod、υdTo empirical equation (1), the nonlinear coefficient γ that calculating obtains sample is
3.06×10-20esu。
Sample after annealing is processed into the two thang-kng mirror polish that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Spectrum internal transmittance》,
The transmitance of sample is measured using ultraviolet visible light-near infrared spectrometer, it is 10mm samples to obtain thickness
Interior transmittance curve, as a result as shown in curve 3 in Fig. 1.Table 1 gives interior transmission of the material in frequency tripling light 351nm wavelength
Rate τ351With absorption coefficient K351Respectively 98.95% and 0.0105cm-1。
Example IV：
By above-mentioned formula 4#In a mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
It is well mixed in mixer.The powder matched somebody with somebody is sequentially added in 11 liters of platinum crucibles, melted by carborundum electric smelting stove heat,
Glass melting temperature is controlled at 1280 DEG C or so, and melting time is 6h, and agitator is starched to glass metal using platinum leaf in melting process
It is stirred.After glass metal clarification eliminates bubble and stirs, high-temperature glass liquid is passed through into crucible bottom material leakage mouth
Put after being injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C, and the quick demoulding by formed glass sample
Enter to have warmed up annealing temperature and (be arranged on the transition temperature T of glassgNear) Muffle furnace in, insulation 12h after, first with -2 DEG C/h
Cooldown rate cool 100 DEG C, then be cooled to -5 DEG C/h cooldown rate 100 DEG C near, closing Muffle furnace power supply makes glass
Sample is naturally cooling to room temperature with stove, takes out chunk glass.
The sample after annealing is taken, the refraction index test sample with an accurate right angle is processed into, according to national standard《GB/T
7962.1-2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and existed
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.529395,1.534938,1.526994,
Calculating obtains its Abbe number υdFor 66.64, n is brought intod、υdTo empirical equation (1), the nonlinear coefficient γ that calculating obtains sample is
3.04×10-20esu。
Sample after annealing is processed into the two thang-kng mirror polish that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Spectrum internal transmittance》,
The transmitance of sample is measured using ultraviolet visible light-near infrared spectrometer, it is 10mm samples to obtain thickness
Interior transmittance curve, as a result as shown in curve 4 in Fig. 1.Table 1 gives interior transmission of the material in frequency tripling light 351nm wavelength
Rate τ351With absorption coefficient K351Respectively 99.49% and 0.0051cm-1。
Embodiment five：
By above-mentioned formula 5#In a mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
It is well mixed in mixer.The powder matched somebody with somebody is sequentially added in 11 liters of platinum crucibles, melted by carborundum electric smelting stove heat,
Glass melting temperature is controlled at 1280 DEG C or so, and melting time is 6h, and agitator is starched to glass metal using platinum leaf in melting process
It is stirred.After glass metal clarification eliminates bubble and stirs, high-temperature glass liquid is passed through into crucible bottom material leakage mouth
Put after being injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C, and the quick demoulding by formed glass sample
Enter to have warmed up annealing temperature and (be arranged on the transition temperature T of glassgNear) Muffle furnace in, insulation 12h after, first with -2 DEG C/h
Cooldown rate cool 100 DEG C, then be cooled to -5 DEG C/h cooldown rate 100 DEG C near, closing Muffle furnace power supply makes glass
Sample is naturally cooling to room temperature with stove, takes out chunk glass.
The sample after annealing is taken, the refraction index test sample with an accurate right angle is processed into, according to national standard《GB/
The colouless optical glass method of testing part 1s of T7962.1-2010：Refractive index and abbe number》Test obtains sample and existed
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.528638,1.534153,1.526174,
Calculating obtains its Abbe number υdFor 66.24, n is brought intod、υdTo empirical equation (1), the nonlinear coefficient γ that calculating obtains sample is
3.06×10-20esu。
Sample after annealing is processed into the two thang-kng mirror polish that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Spectrum internal transmittance》,
The transmitance of sample is measured using ultraviolet visible light-near infrared spectrometer, it is 10mm samples to obtain thickness
Interior transmittance curve, as a result as shown in curve 5 in Fig. 1.Table 1 gives interior transmission of the material in frequency tripling light 351nm wavelength
Rate τ351With absorption coefficient K351Respectively 98.65% and 0.0135cm-1。
Embodiment six：
By above-mentioned 6#In a mole composition calculate the percentage by weight of glass, the common 25Kg of raw material is then weighed, in batch mixing
It is well mixed in case.The powder matched somebody with somebody is sequentially added in 11 liters of platinum crucibles, is melted, founded by carborundum electric smelting stove heat
Temperature control is at 1280 DEG C or so, and melting time is 6h, and starch agitator using platinum leaf in melting process is carried out to glass metal
Stirring.After glass metal clarification eliminates bubble and stirs, high-temperature glass liquid is injected by crucible bottom material leakage mouth
It is put into after chunk glass shaping, and the quick demoulding by formed glass sample are carried out into the copper mould for have been preheated with 300 DEG C
It is warming up to annealing temperature and (is arranged on the transition temperature T of glassgNear) Muffle furnace in, insulation 12h after, first with the cold of -2 DEG C/h
But speed cools 100 DEG C, then is cooled to -5 DEG C/h cooldown rate near 100 DEG C, closes Muffle furnace power supply, makes glass sample
Room temperature is naturally cooling to stove, chunk glass is taken out.
The sample after annealing is taken, the refraction index test sample with an accurate right angle is processed into, according to national standard《GB/
The colouless optical glass method of testing part 1s of T7962.1-2010：Refractive index and abbe number》Test obtains sample and existed
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.527200,1.532651,1.524752,
Calculating obtains its Abbe number υdFor 66.67, n is brought intod、υdTo empirical equation (1), the nonlinear coefficient γ that calculating obtains sample is
3.02×10-20esu。
Sample after annealing is processed into the two thang-kng mirror polish that thickness is respectively 5mm ± 0.05mm and 15mm ± 0.05mm
Sample, according to national standard《The part of the colouless optical glasses of GB/T 7962.12-2010 method of testing the 12nd：Spectrum internal transmittance》,
The transmitance of sample is measured using ultraviolet visible light-near infrared spectrometer, it is 10mm samples to obtain thickness
Interior transmittance curve, as a result as shown in curve 6 in Fig. 1.Table 1 gives interior transmission of the material in frequency tripling light 351nm wavelength
Rate τ351With absorption coefficient K351Respectively 98.85% and 0.0115cm-1。
It is chosen at the interior transmitance (τ of frequency tripling light 351nm wavelength351) higher and absorption coefficient (K351) less sample 1
Its laser damage threshold is tested, while the damage threshold of the fused quartz material with being tested under the same terms is contrasted.
Test data is as shown in Figure 2.As can be seen that the damage threshold of the window material is above quartz in 351nm, 527nm, 1053nm
Material, its damage data is as shown in table 2.
The fused quartz of table 2 and fluophosphate laser glass material damage threshold testing data compare
Claims (6)
1. a kind of fluophosphate laser glass material of ultraviolet high damage threshold, it is characterised in that：Material composition and with such as
Under
Each proportioning components sum is 100%.
2. the fluophosphate laser glass material of ultraviolet high damage threshold according to claim 1, it is characterised in that：
Alkali metal oxide summation is 6~20mol%, and alkaline earth oxide summation is 7~15mol%, P2O5With Al2O3Ratio
Example is 7~12, and the ratio of all oxides sum and all fluoride sums is 15~22；The alkali metal oxide includes original
Expect the Li in composition2O、Na2O and K2O, the alkaline earth oxide includes MgO, CaO, SrO and BaO in material composition.
3. a kind of preparation method of the fluophosphate laser glass material of ultraviolet high damage threshold, it is characterised in that：According to power
Profit requires the material composition and proportioning of 1 establishment, weighs raw material and is well mixed, and after high-temperature fusion, stirring clarification, homogenizing, adopts
With leakage note method shaping large-size glass blank, annealed processing finally obtains the fluophosphate laser glass material.
4. preparation method according to claim 3, it is characterised in that specifically include following steps：
(1) material composition and the mol ratio of each composition listed according to claim 1, calculate the percentage by weight of each composition,
Weigh raw material, be well mixed；
(2) well mixed powder is added in platinum crucible by several times, heating melting, glass melting temperature is controlled at 1280 DEG C or so,
And lifting stirring is carried out with platinum leaf slurry agitator, high-temperature glass liquid clarification is further stirred after eliminating bubble, sampling bubble-free
Mix homogenizing and eliminate striped；
(3) after glass metal clarification eliminates bubble and stirs, by elongated leakage of the high-temperature glass liquid via crucible bottom
Material mouth is slowly injected into progress chunk glass shaping in the copper mould for have been preheated with 300 DEG C；
(4) by the chunk glass of cooling and shaping is quickly put into the Muffle furnace of preheating in copper mould, by insulation, annealing, most
After naturally cool to room temperature, obtain the fluorophosphate laser window glass material of high damage threshold.
5. preparation method according to claim 4, it is characterised in that：
In step (4), by the chunk glass of cooling and shaping is quickly put into the Muffle furnace for being preheated to annealing temperature in copper mould,
12 hours first are incubated, is then cooled 100 DEG C with -2 DEG C/h cooldown rate, then 100 DEG C are cooled to -5 DEG C/h cooldown rate
Near, Muffle furnace power supply is closed, glass sample is naturally cooling to room temperature with stove.
6. preparation method according to claim 4, it is characterised in that：In step (3), in the elongated leakage via crucible bottom
When material mouth is slowly injected into the copper mould having had been warmed up, refractory cover is provided with above copper mould.
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| CN106495471B (en) * | 2016-09-21 | 2019-04-02 | 中国科学院西安光学精密机械研究所 | Low-fluorine-containing phosphate fundamental frequency laser color separation glass and preparation method thereof |
| CN108227047B (en) * | 2018-01-24 | 2019-08-13 | 四川大学 | A kind of optical element slowed down or eliminate the damage of laser induced optical element rear surface |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239645A (en) * | 1975-03-18 | 1980-12-16 | Hoya Glass Works, Ltd. | Phosphate base laser glasses |
| CN101293737A (en) * | 2008-05-27 | 2008-10-29 | 中国计量学院 | Ytterbium fluorine phosphate doped laser glass with high transmission section and preparation method thereof |
| CN102557430A (en) * | 2011-12-16 | 2012-07-11 | 中国科学院西安光学精密机械研究所 | Preparation method of high damage threshold laser window material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239645A (en) * | 1975-03-18 | 1980-12-16 | Hoya Glass Works, Ltd. | Phosphate base laser glasses |
| CN101293737A (en) * | 2008-05-27 | 2008-10-29 | 中国计量学院 | Ytterbium fluorine phosphate doped laser glass with high transmission section and preparation method thereof |
| CN102557430A (en) * | 2011-12-16 | 2012-07-11 | 中国科学院西安光学精密机械研究所 | Preparation method of high damage threshold laser window material |
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