CN105000801A - Ultraviolet-transmittance and high-damage-threshold fluoride phosphate laser glass and preparation method thereof - Google Patents

Ultraviolet-transmittance and high-damage-threshold fluoride phosphate laser glass and preparation method thereof Download PDF

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CN105000801A
CN105000801A CN201510426743.XA CN201510426743A CN105000801A CN 105000801 A CN105000801 A CN 105000801A CN 201510426743 A CN201510426743 A CN 201510426743A CN 105000801 A CN105000801 A CN 105000801A
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王鹏飞
彭波
陆敏
高飞
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XiAn Institute of Optics and Precision Mechanics of CAS
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Abstract

The invention provides high-damage-threshold fluoride phosphate laser glass as a material for preparing an ultraviolet-transmittance window, and a preparation method of the high-damage-threshold fluoride phosphate laser glass. The preparation method comprises the steps of adopting an alkali metal oxide, an alkaline earth metal oxide, alumina, zinc oxide and phosphoric pentoxide as main raw materials, adding a small amount of rare earth fluoride, molding and preparing glass pressing blanks based on the drip injection method after the treatments of high-temperature melting, clarification and homogenizing, and finally obtaining the high-damage-threshold fluoride phosphate laser glass material through the annealing treatment. The fused quartz material can be replaced by the above glass material for preparing lenses, plane windows, prisms and other optical components applied to high-energy and high-power laser systems. In this way, the laser-induced damage problems of ultraviolet optical components made of the fused quartz material in existing high-energy and high-power laser systems can be solved. The load output capability of a laser is further improved. Therefore, the above material can be used for preparing the ultraviolet-transmittance optical components of high-power lasers for laser-driven inertial confinement fusion experiments.

Description

A kind of ultraviolet, high damage threshold fluophosphate laser glass and preparation method thereof thoroughly
Technical field
The invention belongs to laser glass field of material technology, be specifically related to a kind of ultraviolet high damage threshold fluophosphate laser glass material and preparation method thereof thoroughly.
Background technology
Development clean new forms of energy are task of top priority of survival and development of mankind, the top-priority significant problem of Ye Shi China the Implement of sustainable development strategy.Laser Driven inertial confinement fusion is the important means realizing controlled nuclear fusion; can be the energy that the mankind provide inexhaustible; be solve the energy dilemma in the whole world at present, a potential important channel of alleviation Greenhouse effect, be acknowledged as the dawn of 21 century cleaning new energy.Meanwhile, Laser Driven inertial confinement fusion has most important theories meaning and practical value to fundamental researchs such as Strong-field physics, laser-(produced)plasma, high energy trauma, laser fusion physics.
Device of high power laser is a kind of driving mechanism ideal, ripe in current inertial confinement fusion (Inertial confinement fusion, ICF) drive source technology, has become the main direction in ICF field in world wide.The maximum efflux of large-scale fusion level laser device is limited to the damage of optical elements of large caliber.Along with the development of superpower laser, the national portfire (NIF) of the such as U.S., the megajoule device (LMJ) of France, God Light III device (SG III) of China and the GEKKO of Japan, the harm that optic element damage brings manifests further.Fused quartz optical component is the optical material be most widely used in high power solid-state laser system, and it is in great demand.The laser-induced damage of fused quartz optical component is key restraining factors of development high energy, high power laser system.
Defect in fused quartz material cause the damage threshold of optical element to reduce and surface damage threshold value far below bulk damage threshold value, thus the complex damage threshold value of material is reduced.The internal structural defects such as the microstructural flaws produced after the native defect of cause the defect of fused quartz material initial damage mainly the to comprise System of Detecting Surface Defects For Materials such as sub microcrack that the cut of material surface, impression, earlier damage splash pollutent and processing produces and material and laser irradiation.The surface imperfection of fused quartz material effectively can be reduced by techniques such as MRF, ultrasonic cleaning technology, surface acid etching.Native defect is mainly relevant with microtexture with the composition of fused quartz material, preparation technology; Diverse microcosmic structure and defect be atarting material performance variation to irradiation response.For high-purity optical material, extraneous irradiation forms the defect such as optics, electricity, and defect increases fast breeding with irradiation and causes dielectric failure, directly affects the critical natures such as optical, electrical of material, causes initial damage to produce.Although, by improving raw materials purity, improving the uv-absorbing coefficient that preparation technology reduces material, adopt super smooth surface processing to reduce surface imperfection and CO 2the techniques such as laser pre-treated promote suface processing quality, and these measures can only improve the damage threshold of fused quartz material to a certain extent, fundamentally can not solve the low problem of its laser-induced damage threshold value.
In addition, the damage under post laser irradiation of the initial damage of fused quartz under frequency tripled laser (0.35 μm) irradiation and initial damage point continues to increase, this not only can cause the damage of element self to aggravate further, also can reduce transmitance and the beam quality of element, produce wavefront distortion, affect focal spot quality, even modulation is produced to light field, cause optical intensity local to strengthen, very easily causing the appearance of the serious conditions such as " downstream " optic element damage, is a vicious cycle.In general, fused quartz element is once damage, and its mechanics, optics and thermal property all can be weakened, and its resisting laser damage ability has become one of key factor that restriction high powered laser system energy promotes further at present, belongs to " bottleneck " problem.
As far back as latter stage in 20th century, America NI F Technical Committee just points out that the catastrophic failure of fused quartz element under high-throughput should cause material supply section scholar and engineering staff to note, how far can fused quartz move ahead on current technological line? can it continue reliable use at the full flux of NIF apparatus design or more under high-throughput? so, research and develop new, have compared with fused quartz that more the importance of the optical material of high damage threshold and urgency show especially day by day.U.S. Lao Lunsi-livre More National Laboratory (Lawrence Livermore National Laboratory) also proposes the better laser glass material of exploitation simultaneously, makes it meet at 8-9J/cm 2flux under engineer applied, such as adopt crystal of fluoride, fluoride glass etc. to have the conceptual surrogate of good UV-permeable performance and higher resisting laser damage performance at ultraviolet band.But crystal of fluoride exists the intrinsic deficiency of poor chemical stability, face again the Technology predicament etc. being difficult to make large size (430mm × 430mm) crystal simultaneously; Then very easily there is crystallization, become glass poor in fluoride glass; in melting process, fluoride components volatilization greatly, not easily keeps composition stable simultaneously; need again preparation condition harsh especially; as the protection of inert gas atmosphere such as airtight plumbago crucible, argon gas must be adopted and be difficult to use agitator to promote homogenization of glass etc., be therefore difficult to eliminate striped that the uneven and component volatilization of component in glass produces, glass viscosity is little, large size is shaping extremely difficult.
Although it is also proposed a kind of preparation method of high damage threshold window material in patent (CN 102557430 B), this high damage threshold window material take fluorochemical as the glass system of main component, by mainly introducing SiO 2(19-20mol%) improve one-tenth glass and the physicochemical property of fluorochemical, add a small amount of rare earth oxide La 2o 3, Y 2o 3improve thermal transition temperature and the devitrification resistance energy of glass.The importantly above-mentioned fluorosilicate glass system and way problem that still thoroughly cannot solve that the volatilization of fluorochemical basis glass system is large, viscosity is little, the shaping striped of large size removes difficulties etc.
Therefore, develop a kind of spectrum property meets ultraviolet region frequency tripling light (0.35 μm) transmitance high, there is laser damage threshold higher than fused quartz material, and chemical stability is higher, melting technology technical elements is applicable to again the new pattern laser glass material of large size, batch production, with the satisfied carrying capacity of lifting high energy and power Optical Maser System and the engineering demand of efflux, its scientific meaning and engineer applied are worth very great.
Summary of the invention
Low for current silica glass frequency tripling damage threshold, and the easy crystallization of fluoride glass, be difficult to the problems such as large size production, the present invention proposes a kind of novel ultraviolet, high damage threshold fluophosphate laser glass composition and preparation method thereof.This laser glass material near ultraviolet region, there is good spectral transmission performance visible region, under frequency tripling (0.35 μm) high energy pulse laser irradiation, have high threshold for resisting laser damage, and stable chemical performance, be applicable to produce in enormous quantities.
To achieve these goals, technology disclosed by the invention can improve the fluoride components of its UV-permeable characteristic and nonlinear factor, the zinc oxide of adjustable glass viscosity on a small quantity by introducing in phosphate glass system, obtains novel large-sized ultraviolet high damage threshold fluophosphate laser glass material.
Material composition and the proportioning of the fluophosphate laser glass material of ultraviolet high damage threshold of the present invention are as follows:
Each proportioning components sum is 100%, calculates its weight percentage according to the molar basis of each component, takes raw material and mixes.
Based on above proportioning, alkalimetal oxide (R 2o) summation optimum is 6 ~ 20% (mol), alkaline earth metal oxide (R 'o) summation optimum is 7 ~ 15% (mol), P 2o 5with Al 2o 3ratio optimum be 7 ~ 12, the ratio optimum of oxide compound and fluorochemical is 15 ~ 22; Described alkalimetal oxide comprises the Li in material composition 2o, Na 2o, K 2o, described alkaline earth metal oxide comprises MgO, CaO, SrO, BaO in material composition.
The preparation method of the fluophosphate laser glass material of this saturating ultraviolet high damage threshold, according to above material composition and proportioning, take raw material to mix, after high-temperature fusion, stirring clarification, homogenizing, adopt and leak the shaping large-size glass blank of note method, through anneal, the described fluophosphate laser glass material of final acquisition.Specifically can realize according to following steps:
(1) according to the mol ratio of above material composition and each composition, calculate the weight percent of each composition, take raw material, mix;
(2) the powder gradation mixed is added in platinum crucible, heating and melting, glass melting temperature controls at about 1280 DEG C, and carry out lifting stirring with platinum leaf slurry agitator, high temp glass liquid is clarified and eliminates bubble, stir further homogenizing after sampling bubble-free and eliminate striped, thus the composition of glass metal upper and lower in whole crucible is all consistent, namely component is even; In actually operating, settling time can be eliminated situation according to the bubble of glass sampling and determine, and homogenising time can be determined according to the refractive index homogeneity of sampling glass;
(3) eliminate bubble after stirring until glass metal clarification, via elongated leakages of crucible bottom, high temp glass liquid is expected that mouth is slowly injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping;
(4) by copper mould the chunk glass of cooling and shaping put into the retort furnace of preheating fast, through insulation, annealing, finally naturally cool to room temperature, obtain the fluorophosphate laser window glass material of high damage threshold.
Based on above-mentioned preparation technology's flow process, the present invention also does following optimization further:
In step (4), by copper mould the chunk glass of cooling and shaping put into fast and be preheated to annealing temperature and (be arranged on the transition temperature T of glass gnear) retort furnace in, be first incubated 12 hours, then lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature.
Raw material uses particle diameter to be the dry powders of 80 ~ 100 objects, and purity is specific pure, i.e. main content >99.9%, foreign matter content Fe<2ppm, Co, Mn, Ni, V, Cr<1ppm.
(3), (4) actually operating of step is comparatively crucial, mixed powder adds in platinum crucible, in globars electric smelter heating high-temperature fusion process, adopt platinum leaf slurry agitator to carry out lifting to stir, the clarification to high temp glass liquid is successively realized in a crucible, homogenization process, particularly during glass ware forming, via the elongated leakage of crucible bottom, high temp glass liquid expects that mouth is slowly injected in preheated copper mould, with adding refractory cover above mould, prevent high temp glass liquid surface in moulding process from forming convection current with ambient air, avoid convection current to cause and form thin and close striped at inside glass.
The present invention has following technique effect:
This laser glass material near ultraviolet region, there is good spectral transmission performance visible region.
Under equal conditions, when standing frequency tripling (0.35 μm of@8ns) High Power Laser Pulses irradiation, the laser damage threshold of this material is about the twice of fused quartz.
The invention solves the easy crystallization of fluoride glass, one-tenth glass is poor, volatilization is large, be difficult to problem such as homogenizing elimination striped and the little large size difficult forming caused of viscosity etc., the alternative fused quartz material of this glass material, be processed as the optical components such as lens, plane window and prism and be applied to the carrying capacity improving system in high energy, high power laser system, be expected to for ICF Laser output flux continuation improve and ICF research carry out to provide important optical element support in a deep going way.
Glass material stable chemical performance of the present invention, applicable large size batch production.
Accompanying drawing explanation
The interior transmittance curve of the thick sample of Fig. 1 fluorophosphate laser window glass material 1cm.
Fig. 2 fluorophosphate laser window glass material, the damage threshold test data of fused quartz at 351nm, 527nm, 1053nm wavelength place.
Specific embodiments:
The present invention is that main composition is formed phosphoric acid salt basis glass system with alkalimetal oxide, alkaline earth metal oxide, aluminum oxide and Vanadium Pentoxide in FLAKES, making its ultraviolet absorption edge blue shift by introducing a small amount of fluoride components, improving its UV-permeable characteristic, reduce the nonlinear factor of material simultaneously, introduce viscosity and the processability of zinc oxide adjustment glass; By the ratio of composition each in optimization of C/C composites, obtain be applicable to that large size is shaping, stable chemical performance, laser damage threshold be higher than the fluophosphate laser glass material of fused quartz.
According to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", use the transmitance of ultraviolet visible light-near infrared spectrometer to this fluophosphate laser glass material sample to measure, obtain the interior transmittance curve of the thick sample of 1cm.Build laser damage threshold testing system platform according to the requirement of international standard ISO11254-1:2000 (E) (Laser andlaser-related equipment-Determination of laser-induced damage threshold of opticalsurfaces – Part 1:1-on-1test), test material is at the damage threshold at frequency tripling wavelength (0.351 μm) place.The refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place is obtained according to GB " GB/T 7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n c, by calculate Abbe number υ d, field experience formula (1), brings n into d, υ dthe nonlinear factor γ of sample can be calculated, wherein, K=2.8 × 10 -10m 2/ W.
&gamma; = K ( n d - 1 ) ( n d 2 + 1 ) 2 n d &upsi; &lsqb; 1.52 + ( n d 2 + 2 ) ( n d + 1 ) &upsi; / 6 n d &rsqb; 1 / 2 - - - ( 1 )
Test result shows: the interior transmitance at 1cm thick sample frequency tripling wavelength (0.351 μm) place reached for more than 98.0% (as shown in Figure 1).The damage threshold (laser pulse width 8ns) of this novel fluophosphate laser glass material at frequency tripling wavelength (0.351 μm) place is higher than quartz material more than 1 times, and the damage threshold at 527nm, 1053nm wavelength place is all higher than fused quartz material (as shown in Figure 2); Meanwhile, nonlinear factor and the fused quartz of this fluophosphate laser glass material are close, and can prepare the glass print of production large size (430mm*430mm), high optical quality.
The composition of each composition and the optical property of respective sample in table 1 specific embodiment
Embodiment one:
By above-mentioned formula 1 #in mole composition calculate the weight percent of glass, then take raw material 25Kg altogether, mix in mixer.Added by joined powder in 11 liters of platinum crucibles successively, by silicon carbide electric smelter heating and melting, glass melting temperature controls at about 1280 DEG C, and melting time is 6h, uses platinum leaf to starch agitator and stir glass metal in melting process.Bubble after stirring is eliminated until glass metal clarification, high temp glass liquid is leaked material mouth by crucible bottom and is injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping, and be warmed up to annealing temperature (be arranged on the transition temperature T of glass by putting into after the demoulding of formed glass sample fast gnear) retort furnace in, after insulation 12h, first lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature, take out chunk glass.
Get the sample after annealing, be processed into the refraction index test sample with an accurate right angle, obtain the refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place according to GB " GB/T7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n cbe respectively 1.526555,1.531934,1.524138, calculate its Abbe number υ dbe 67.52, field experience formula (1), brings n into d, υ dthe nonlinear factor γ calculating sample is 2.96 × 10 -20esu.
For fused quartz material, check in its n according to Xiao Te opticglass handbook (Schott Optical Glass catalogue) d, n f, n cbe respectively 1.45843,1.6309,1.45634, Abbe number υ dbe 67.87, bring n into d, υ dto experimental formula (1), the nonlinear factor γ calculating sample is 2.5 × 10 -20esu.
Sample after annealing is processed into the sample that thickness is respectively the two logical light mirror polish of 5mm ± 0.05mm and 15mm ± 0.05mm, according to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", the transmitance of ultraviolet visible light-near infrared spectrometer to sample is used to measure, obtain the interior transmittance curve that thickness is 10mm sample, result is as shown in curve in Fig. 11.Table 1 gives this material transmitance τ in frequency tripling light 351nm wavelength 351with uptake factor K 351be respectively 99.66% and 0.0034cm -1.
Embodiment two:
By above-mentioned formula 2 #in mole composition calculate the weight percent of glass, then take raw material 25Kg altogether, mix in mixer.Added by joined powder in 11 liters of platinum crucibles successively, by silicon carbide electric smelter heating and melting, glass melting temperature controls at about 1280 DEG C, and melting time is 6h, uses platinum leaf to starch agitator and stir glass metal in melting process.Bubble after stirring is eliminated until glass metal clarification, high temp glass liquid is leaked material mouth by crucible bottom and is injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping, and be warmed up to annealing temperature (be arranged on the transition temperature T of glass by putting into after the demoulding of formed glass sample fast gnear) retort furnace in, after insulation 12h, first lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature, take out chunk glass.
Get the sample after annealing, be processed into the refraction index test sample with an accurate right angle, obtain the refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place according to GB " GB/T7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n cbe respectively 1.535772,1.541463,1.533275, calculate its Abbe number υ dbe 65.43, bring n into d, υ dto experimental formula (1), the nonlinear factor γ calculating sample is 3.17 × 10 -20esu.
Sample after annealing is processed into the sample that thickness is respectively the two logical light mirror polish of 5mm ± 0.05mm and 15mm ± 0.05mm, according to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", the transmitance of ultraviolet visible light-near infrared spectrometer to sample is used to measure, obtain the interior transmittance curve that thickness is 10mm sample, result is as shown in curve in Fig. 12.Table 1 gives this material transmitance τ in frequency tripling light 351nm wavelength 351with uptake factor K 351be respectively 98.57% and 0.0143cm -1.
Embodiment three:
By above-mentioned formula 3 #in mole composition calculate the weight percent of glass, then take raw material 25Kg altogether, mix in mixer.Added by joined powder in 11 liters of platinum crucibles successively, by silicon carbide electric smelter heating and melting, glass melting temperature controls at about 1280 DEG C, and melting time is 6h, uses platinum leaf to starch agitator and stir glass metal in melting process.Bubble after stirring is eliminated until glass metal clarification, high temp glass liquid is leaked material mouth by crucible bottom and is injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping, and be warmed up to annealing temperature (be arranged on the transition temperature T of glass by putting into after the demoulding of formed glass sample fast gnear) retort furnace in, after insulation 12h, first lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature, take out chunk glass.
Get the sample after annealing, be processed into the refraction index test sample with an accurate right angle, obtain the refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place according to GB " GB/T7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n cbe respectively 1.536268,1.541800,1.533797, calculate its Abbe number υ dbe 67.00, bring n into d, υ dto experimental formula (1), the nonlinear factor γ calculating sample is 3.06 × 10 -20esu.
Sample after annealing is processed into the sample that thickness is respectively the two logical light mirror polish of 5mm ± 0.05mm and 15mm ± 0.05mm, according to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", the transmitance of ultraviolet visible light-near infrared spectrometer to sample is used to measure, obtain the interior transmittance curve that thickness is 10mm sample, result is as shown in curve in Fig. 13.Table 1 gives this material transmitance τ in frequency tripling light 351nm wavelength 351with uptake factor K 351be respectively 98.95% and 0.0105cm -1.
Embodiment four:
By above-mentioned formula 4 #in mole composition calculate the weight percent of glass, then take raw material 25Kg altogether, mix in mixer.Added by joined powder in 11 liters of platinum crucibles successively, by silicon carbide electric smelter heating and melting, glass melting temperature controls at about 1280 DEG C, and melting time is 6h, uses platinum leaf to starch agitator and stir glass metal in melting process.Bubble after stirring is eliminated until glass metal clarification, high temp glass liquid is leaked material mouth by crucible bottom and is injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping, and be warmed up to annealing temperature (be arranged on the transition temperature T of glass by putting into after the demoulding of formed glass sample fast gnear) retort furnace in, after insulation 12h, first lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature, take out chunk glass.
Get the sample after annealing, be processed into the refraction index test sample with an accurate right angle, obtain the refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place according to GB " GB/T7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n cbe respectively 1.529395,1.534938,1.526994, calculate its Abbe number υ dbe 66.64, bring n into d, υ dto experimental formula (1), the nonlinear factor γ calculating sample is 3.04 × 10 -20esu.
Sample after annealing is processed into the sample that thickness is respectively the two logical light mirror polish of 5mm ± 0.05mm and 15mm ± 0.05mm, according to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", the transmitance of ultraviolet visible light-near infrared spectrometer to sample is used to measure, obtain the interior transmittance curve that thickness is 10mm sample, result is as shown in curve in Fig. 14.Table 1 gives this material transmitance τ in frequency tripling light 351nm wavelength 351with uptake factor K 351be respectively 99.49% and 0.0051cm -1.
Embodiment five:
By above-mentioned formula 5 #in mole composition calculate the weight percent of glass, then take raw material 25Kg altogether, mix in mixer.Added by joined powder in 11 liters of platinum crucibles successively, by silicon carbide electric smelter heating and melting, glass melting temperature controls at about 1280 DEG C, and melting time is 6h, uses platinum leaf to starch agitator and stir glass metal in melting process.Bubble after stirring is eliminated until glass metal clarification, high temp glass liquid is leaked material mouth by crucible bottom and is injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping, and be warmed up to annealing temperature (be arranged on the transition temperature T of glass by putting into after the demoulding of formed glass sample fast gnear) retort furnace in, after insulation 12h, first lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature, take out chunk glass.
Get the sample after annealing, be processed into the refraction index test sample with an accurate right angle, obtain the refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place according to GB " GB/T7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n cbe respectively 1.528638,1.534153,1.526174, calculate its Abbe number υ dbe 66.24, bring n into d, υ dto experimental formula (1), the nonlinear factor γ calculating sample is 3.06 × 10 -20esu.
Sample after annealing is processed into the sample that thickness is respectively the two logical light mirror polish of 5mm ± 0.05mm and 15mm ± 0.05mm, according to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", the transmitance of ultraviolet visible light-near infrared spectrometer to sample is used to measure, obtain the interior transmittance curve that thickness is 10mm sample, result is as shown in curve in Fig. 15.Table 1 gives this material transmitance τ in frequency tripling light 351nm wavelength 351with uptake factor K 351be respectively 98.65% and 0.0135cm -1.
Embodiment six:
By above-mentioned 6 #in mole composition calculate the weight percent of glass, then take raw material 25Kg altogether, mix in mixer.Added by joined powder in 11 liters of platinum crucibles successively, by silicon carbide electric smelter heating and melting, glass melting temperature controls at about 1280 DEG C, and melting time is 6h, uses platinum leaf to starch agitator and stir glass metal in melting process.Bubble after stirring is eliminated until glass metal clarification, high temp glass liquid is leaked material mouth by crucible bottom and is injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping, and be warmed up to annealing temperature (be arranged on the transition temperature T of glass by putting into after the demoulding of formed glass sample fast gnear) retort furnace in, after insulation 12h, first lower the temperature 100 DEG C with the rate of cooling of-2 DEG C/h, then be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature, take out chunk glass.
Get the sample after annealing, be processed into the refraction index test sample with an accurate right angle, obtain the refractive index n of sample at 587.6nm, 486.1nm, 656.3nm wavelength place according to GB " GB/T7962.1-2010 colouless optical glass testing method part 1: specific refractory power and abbe number " test d, n f, n cbe respectively 1.527200,1.532651,1.524752, calculate its Abbe number υ dbe 66.67, bring n into d, υ dto experimental formula (1), the nonlinear factor γ calculating sample is 3.02 × 10 -20esu.
Sample after annealing is processed into the sample that thickness is respectively the two logical light mirror polish of 5mm ± 0.05mm and 15mm ± 0.05mm, according to GB " GB/T 7962.12-2010 colouless optical glass testing method the 12nd part: spectrum internal transmittance ", the transmitance of ultraviolet visible light-near infrared spectrometer to sample is used to measure, obtain the interior transmittance curve that thickness is 10mm sample, result is as shown in curve in Fig. 16.Table 1 gives this material transmitance τ in frequency tripling light 351nm wavelength 351with uptake factor K 351be respectively 98.85% and 0.0115cm -1.
Be chosen at the interior transmitance (τ of frequency tripling light 351nm wavelength 351) higher and uptake factor (K 351) less sample 1 tests its laser damage threshold, contrast with the damage threshold of fused quartz material tested under the same terms simultaneously.Test data as shown in Figure 2.Can find out, the damage threshold of this window material is at 351nm, 527nm, 1053nm all higher than quartz material, and its damage data is as shown in table 2.
Table 2 fused quartz and fluophosphate laser glass material damage threshold testing data compare

Claims (7)

1. a fluophosphate laser glass material for saturating ultraviolet high damage threshold, is characterized in that: material composition and proportioning as follows
Each proportioning components sum is 100%.
2. the fluophosphate laser glass material of ultraviolet high damage threshold according to claim 1, is characterized in that:
Alkalimetal oxide summation is 6 ~ 20% (mol), and alkaline earth metal oxide summation is 7 ~ 15% (mol), P 2o 5with Al 2o 3ratio be 7 ~ 12, the ratio of all oxides sum and all fluorochemical sums is 15 ~ 22; Described alkalimetal oxide comprises the Li in material composition 2o, Na 2o and K 2o, described alkaline earth metal oxide comprises MgO, CaO, SrO and BaO in material composition.
3. the preparation method of the fluophosphate laser glass material of a saturating ultraviolet high damage threshold, it is characterized in that: the material composition established according to claim 1 and proportioning, take raw material to mix, after high-temperature fusion, stirring clarification, homogenizing, adopt and leak the shaping large-size glass blank of note method, through anneal, the described fluophosphate laser glass material of final acquisition.
4. preparation method according to claim 3, is characterized in that, specifically comprises the following steps:
(1) material composition listed according to claim 1 and the mol ratio of each composition, calculate the weight percent of each composition, take raw material, mix;
(2) the powder gradation mixed is added in platinum crucible, heating and melting, glass melting temperature controls at about 1280 DEG C, and carries out lifting stirring with platinum leaf slurry agitator, high temp glass liquid is clarified and eliminates bubble, stir homogenizing after sampling bubble-free further and eliminate striped;
(3) eliminate bubble after stirring until glass metal clarification, via elongated leakages of crucible bottom, high temp glass liquid is expected that mouth is slowly injected in the copper mould being preheating to 300 DEG C that to carry out chunk glass shaping;
(4) by copper mould the chunk glass of cooling and shaping put into the retort furnace of preheating fast, through insulation, annealing, finally naturally cool to room temperature, obtain the fluorophosphate laser window glass material of high damage threshold.
5. preparation method according to claim 4, is characterized in that:
In step (4), by in copper mould the chunk glass of cooling and shaping put into the retort furnace being preheated to annealing temperature fast, first be incubated 12 hours, then 100 DEG C are lowered the temperature with the rate of cooling of-2 DEG C/h, be cooled near 100 DEG C with the rate of cooling of-5 DEG C/h again, close retort furnace power supply, make glass sample with stove Temperature fall to room temperature.
6. preparation method according to claim 4, it is characterized in that: raw material uses particle diameter to be the dry powders of 80 ~ 100 objects, purity is specific pure, i.e. main content >99.9%, foreign matter content Fe<2ppm, Co, Mn, Ni, V, Cr<1ppm.
7. preparation method according to claim 4, is characterized in that: in step (3), when the elongated leakage material mouth via crucible bottom is slowly injected in preheated copper mould, is provided with refractory cover above copper mould.
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CN106477880A (en) * 2016-09-21 2017-03-08 中国科学院西安光学精密机械研究所 A kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses and preparation method thereof
CN106495471A (en) * 2016-09-21 2017-03-15 中国科学院西安光学精密机械研究所 A kind of low fluorine-containing phosphate basic frequency laser color separation of glasses and preparation method thereof
CN108227047A (en) * 2018-01-24 2018-06-29 四川大学 A kind of optical element slowed down or eliminate the damage of laser induced optical element rear surface
CN114573231A (en) * 2022-03-24 2022-06-03 中国科学院西安光学精密机械研究所 AgI-AgPO3-MpOqPreparation method of system transparent conductive glass and electromagnetic shielding application

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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 Method for preparing high-damage-threshold laser window material

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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 Method for preparing high-damage-threshold laser window material

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Publication number Priority date Publication date Assignee Title
CN106477880A (en) * 2016-09-21 2017-03-08 中国科学院西安光学精密机械研究所 A kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses and preparation method thereof
CN106495471A (en) * 2016-09-21 2017-03-15 中国科学院西安光学精密机械研究所 A kind of low fluorine-containing phosphate basic frequency laser color separation of glasses and preparation method thereof
CN106477880B (en) * 2016-09-21 2019-03-08 中国科学院西安光学精密机械研究所 Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof
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 basic frequency laser color separation glass of one kind and preparation method thereof
CN108227047A (en) * 2018-01-24 2018-06-29 四川大学 A kind of optical element slowed down or eliminate the damage of laser induced optical element rear surface
CN114573231A (en) * 2022-03-24 2022-06-03 中国科学院西安光学精密机械研究所 AgI-AgPO3-MpOqPreparation method of system transparent conductive glass and electromagnetic shielding application
CN114573231B (en) * 2022-03-24 2023-01-31 中国科学院西安光学精密机械研究所 AgI-AgPO 3 -M p O q Preparation method of system transparent conductive glass and electromagnetic shielding application

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