CN106477880B - Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof - Google Patents
Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof Download PDFInfo
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- CN106477880B CN106477880B CN201610838146.2A CN201610838146A CN106477880B CN 106477880 B CN106477880 B CN 106477880B CN 201610838146 A CN201610838146 A CN 201610838146A CN 106477880 B CN106477880 B CN 106477880B
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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
- C03C4/0071—Compositions for glass with special properties for laserable glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
- C03B5/027—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by passing an electric current between electrodes immersed in the glass bath, i.e. by direct resistance heating
- C03B5/0272—Pot furnaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
- C03B5/187—Stirring devices; Homogenisation with moving elements
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
Abstract
The invention belongs to laser glass field of material technology, and in particular to low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof.The material composition of the glass are as follows: the Li of 1.5-10%2The Na of O, 0-8%2The K of O, 0-15%2The Al of the BaO of the SrO of the CaO of the MgO of O, 1.5-10%, 0-5%, 0-2%, 1-6%, 1-9%2O3, the P of the ZnO of 2-10%, 55-75%2O5, the YF of 1-2%3, the LaF of 0.5-2%3, the Co of 0.1-2%3O4；The composition proportion of each raw material is molal weight score.The present invention solves the problems such as easy crystallization of fluoride glass and high fluorine-containing glass system, poor at glass, volatilization is big, is difficult to be homogenized elimination striped and large scale difficult forming caused by viscosity is small.Under same test condition, laser damage threshold is apparently higher than fused quartz glass material, fused quartz glass material can be replaced for improving the laser load ability of system in high energy and power laser.
Description
Technical field
The invention belongs to laser glass field of material technology, and in particular to a kind of low fluorine-containing two double-frequency laser color separation of phosphate
Glass and preparation method thereof.
Background technique
Laser Driven inertial confinement fusion (Inertial confinement fusion, ICF) utilizes can be from seawater
The deuterium tritium of extraction is fusion fuel, carries out controlled nuclear fusion under light laser constraint and generates high-gain fusion energy, is acknowledged as 21
Century cleaning new energy dawn, while to push Strong-field physics research and high power laser light technology development be of great significance.
2014, national igniter (National Ignition Facility, NIF) of the U.S. for ICF research was realized for the first time
The postiive gain output of laser-driven inertial confinement fusion experiment makes the mankind to nuclear fusion energy source using again across going a step further.For state, the U.S.
Family's igniter, French megajoule laser aid (Laser Mega Joule, LMJ) and Chinese God Light III large scientific facilities etc.
Similar ICF high-power laser driver, wherein to realize frequency conversion, focusing, harmonic wave separation (by fundamental frequency light (1 ω), two times
Frequency light (2 ω) is separated with frequency tripling light (3 ω)) and the Final optical assembly of functions such as measurement sampling be all entirely to drive all the time
The weakest link and bottleneck unit of resisting laser damage in dynamic device.Harmonic wave separation technology is to determine frequency tripling in Final optical assembly
The key factor of target practice laser-quality.
The high-power laser drivers such as NIF convert the three of laser-produced fusion experiment for fundamental frequency light using frequency conversion crystal
Frequency doubled light, but since transfer efficiency is limited, still remaining certain fundamental frequency and two frequency doubled lights in output light path.These are remaining
It is all very unfavorable to fusion assay and target chamber diagnostic system that fundamental frequency, two frequency doubled lights enter target chamber.Currently, mainly passing through final-optics
Fused quartz wedge-shaped lens retrodeviate fundamental frequency, the focusing of two frequency doubled lights with a distance from frequency tripling optical focus very little in component, and finally only three
Frequency doubled light focuses on target spot.This harmonic wave separation technology based on fused quartz wedge type lens, cannot be by fundamental frequency, two multiplied frequency harmonics
It completely removes, in order to avoid the expensive optical element such as fused quartz lens is by secondary damage, the structure of existing Final optical assembly
It designs sufficiently complex.In addition the requirement of ICF device high throughput operation is not achieved in the ultraviolet damage threshold of fused quartz material, cause to swash
Light constraint nuclear fusion is pushed slowly.Therefore, in Final optical assembly the ultraviolet damage problem of fused quartz element and be based on fused quartz
The harmonic wave separation problem of wedge-shaped lens has become one of the critical bottleneck problem for restricting the output of ICF device high pass.Research and development tool
Threshold value is had damage compared with the higher novel optical material of fused quartz, design substitution fused quartz wedge-shaped lens, innovation ICF final-optics system
Harmonic wave separation element in system will open up new technology way for the high-throughput output bottleneck problem for solving high-power laser driver
Diameter.
NIF technical committee, the U.S. just proposed the saturating ultraviolet crystal of fluoride of exploitation, fluoride glass early in 1999
Equal new pattern lasers material is used to substitute the conceptual prospect and conception of fused quartz.In these materials, fluorphosphate glass is considered
It is a kind of potentially with the diactinic laser glass material of good ultraviolet.Since the nineties in last century, it has been based primarily upon anti-
The application demand of normal dispersion vacuum ultraviolet lenticule, researchers carry out various fluorine phosphorous glass and phosphate-based glass property
System research, including glass composition and preparation, impurity and Study of Defects, ultraviolet, excimer laser and x-ray irradiation effect are to material
Expect vacuum ultraviolet transmitance influence etc..Fluorine phosphorous glass is mostly high fluorine-containing system, is difficult to prepare the heavy caliber of high optical quality
(430mm*430mm) optical element, so failing to be applied in ICF Final optical assembly so far.
Although also proposed a kind of two frequency multiplication light absorbing material of high damage threshold in patent (ZL201310210092.1)
Preparation method, but the two frequency multiplication light absorbing material of high damage threshold is to pass through master with fluoride glass system as main component
Introduce SiO2(19~20mol%) improve fluoride at glass and physicochemical properties, a small amount of rare earth oxide is added
La2O3、Y2O3Improve the thermal transition temperature and devitrification resistance energy of glass.It is important that above-mentioned fluorosilicate glass system and method
The problems such as volatilization that still can not thoroughly solve fluoride basis glass system is big, viscosity is small, large scale molding striped removes difficulties,
And high fluorine-containing fluorosilicate glass is melted, very harshness is required to melted medium and technique, it is difficult to large scale molding.
Summary of the invention
It is difficult to prepare large scale, high optical quality optical element to solve existing fluoride and high fluorine-containing glass system
The technical issues of, the present invention provides low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof.
The technical solution of the invention is as follows: a kind of low fluorine-containing two double-frequency laser color separation glass of phosphate, it is special it
It is in the material composition of the laser glass are as follows: the Li of 1.5-10%2The Na of O, 0-8%2The K of O, 0-15%2O, 1.5-
The Al of the BaO of the SrO of the CaO of 10% MgO, 0-5%, 0-2%, 1-6%, 1-9%2O3, the ZnO of 2-10%, 55-75%'s
P2O5, the YF of 1-2%3, the LaF of 0.5-2%3, the Co of 0.1-2%3O4；
The composition proportion of each raw material is molal weight score.
Above-mentioned Li2O、Na2O and K2The sum of molal weight score of O is 8-16%；Described MgO, CaO, SrO and BaO's rubs
The sum of your mass fraction is 9-14%.
Above-mentioned P2O5Molal weight be Al2O39-11 times；The molal weight of oxide is the 30- of fluoride in raw material
39 times.
The present invention also provides a kind of preparation method of low fluorine-containing two double-frequency laser color separation glass of phosphate, special characters
It is: the following steps are included:
1] raw material is weighed；
Raw material is weighed according to the composition proportion in claim 1 and is uniformly mixed；
2] heating melting；
Glass melting temperature is kept after uniformly mixed raw material is heated to melting；
3] clarifying and homogenizing；
Under reducing atmosphere, the raw material of molten condition is stirred, until obtaining the high-temperature glass liquid of clarifying and homogenizing；
4] casting；
High-temperature glass liquid is slowly injected into mold and obtains molding chunk glass；
5] it makes annealing treatment；
Chunk glass after demoulding is subjected to insulation annealing processing at an annealing temperature, is obtained after being cooled to room temperature low fluorine-containing
Two double-frequency laser color separation glass of phosphate.
Step 1] in raw material use partial size be 80-100 mesh dry powder, material purity is specific pure.
Step 2] in glass melting temperature be 1200-1300 DEG C.
Step 3] in stirring be to carry out promotion stirring, eliminate bubble after futher stir homogenizing eliminate striped；It is described to go back
Originality atmosphere is H2Or H2With N2Mixed gas.
Step 4] in mold be the copper mould for being preheated to 280-320 DEG C, be provided with refractory cover above copper mould.
Step 5] further comprising the steps of:
Annealing device 5.1] is preheated to the annealing temperature of chunk glass；
5.2] from quickly removing chunk glass in mold and being put into annealing device, 12~24 hours are kept the temperature；
5.3] make 120 DEG C of the greenhouse cooling in annealing device with the cooling rate of -2 DEG C/h；
5.4] temperature in annealing device is made to be down to 100 DEG C with the cooling rate of-(3~5) DEG C/h；
5.5] annealing device is closed, obtains low two double-frequency laser color separation glass of fluorine-containing phosphate after cooled to room temperature
Glass.
The beneficial effects of the present invention are:
(1) present invention solves the easy crystallization of fluoride glass and high fluorine-containing glass system, volatilize big, hardly possible poor at glass
With homogenizing eliminate striped and viscosity it is small caused by large scale difficult forming the problems such as.Under same test condition, damage from laser
Threshold value is apparently higher than fused quartz glass material, fused quartz glass material can be replaced for improving system in high energy and power laser
Laser load ability, while replace wedge-shaped mirrors space harmonics separation technology, pass through Ions Absorption method remove two frequency multiplication waves
Long laser is completely separated it with frequency tripled laser realization, to continue raising and ICF terminal for ICF laser output flow
The innovation of harmonic wave separation technology provides two important frequency multiplication color separation optical elements and supports in optical module.
(2) present invention absorbs the doping concentration of ion by regulation glass composition and two frequencys multiplication, can make the glass material
Light intensity absorption (transmitance τ in 527nm is swashed to two frequencys multiplication (2 ω, 527nm)527≤ 2%/cm), while but also with to frequency tripling (3
ω) ultraviolet light high transmission (transmitance τ in 351nm351>=99.0%/cm) spectral characteristic, and its frequency tripling (3 ω,
351nm) laser damage threshold is about 2 times of fused quartz, and the damage threshold of two frequency-doubled wavelengths (2 ω, 527nm) also slightly above melts stone
English.
(3) glass material stable chemical performance of the invention, suitable large scale batch production.
Detailed description of the invention
Fig. 1 is the interior transmittance curve of the low fluorine-containing two double-frequency laser color separation glass sample of phosphate of the present invention.
Fig. 2 is the low fluorine-containing two double-frequency laser color separation glass of phosphate of the present invention and fused quartz glass (Corning7980)
Damage threshold test data at frequency tripling (351nm), two frequencys multiplication (527nm) and fundamental frequency (1053nm) wavelength.
Fig. 3 is the low fluorine-containing two double-frequency laser color separation glass of phosphate of the present invention in different capacity density frequency tripling
The transmitance change curve of 351nm wavelength is corresponded under (351nm) Irradiation of High.
Fig. 4 is the low fluorine-containing two double-frequency laser color separation glass of phosphate of the present invention in two frequency multiplication of different capacity density
The transmitance change curve of 527nm wavelength is corresponded under (527nm) Irradiation of High.
Specific embodiment
The present invention is mainly to form to be constituted with alkali metal oxide, alkaline earth oxide, aluminium oxide and phosphorus pentoxide
Phosphate basis glass system makes the ultraviolet absorption edge blue shift of glass by introducing rare earth fluoride component, improves it into glass
Can, introduce the viscosity and processability of zinc oxide adjustment glass；In glass metal high temperature clarifying process, H is passed through into crucible2Or
H2With N2Mixed gas, manufacture reproducibility glass melting atmosphere, regulate and control to absorb in glass ion in lower valency, realize glass
Ultraviolet absorption edge blue shift；By the ratio respectively formed in optimization of C/C composites, obtains and be suitble to large scale molding, stable chemical performance, swash
Light injury threshold is higher than the low fluorine-containing two double-frequency laser color separation glass material of phosphate of fused quartz.The laser glass material is close
There is good spectral transmission performance in ultra-violet (UV) band, resists under frequency tripling (351nm, 355nm) high energy pulse laser irradiation with high
Laser damage threshold, and stable chemical performance, the batch production suitable for large-size glass.The alternative molten stone of the glass material
English material is processed as ultraviolet lens, two frequencys multiplication (527nm, 532nm) colour filter and quadruple (263nm, 266nm) attenuator etc.
Optical component is applied to high energy, high power laser system, solves existing high energy, the ultraviolet optics such as fused quartz in high power system
The damage from laser problem of element, further increases the load fan-out capability of laser, and is expected to as saturating ultraviolet, two frequency multiplication colors point
From in superpower laser of the optical element for the test of Laser Driven inertial confinement fusion.
The present invention is can to improve its UV transmission characteristic and at glass by introducing in multicomponent phosphate glass system
Can rare earth fluoride component, adjustable glass viscosity zinc oxide, obtain it is novel it is large-sized it is ultraviolet, high damage threshold is low
Fluorine-containing two double-frequency laser color separation glass material of phosphate.Preparation method are as follows: with alkali metal oxide, alkaline-earth metal oxide
Object, aluminium oxide, zinc oxide and phosphorus pentoxide are main composition, add a small amount of rare earth fluoride, pass through reducing atmosphere control two
Frequency multiplication absorbs the ultraviolet absorption edge of ionic valence condition and glass, after high temperature melting, clarification, homogenizing, prepares glass with leakage note method molding
Blank obtains the low fluorine-containing phosphate laser glass material of high damage threshold using annealing.Specifically includes the following steps:
(1) weight percent that each ingredient is calculated according to following molal weight score weighs raw material, is uniformly mixed:
The Li of 1.5-10%2The Na of O, 0-8%2The K of O, 0-15%2The SrO of the CaO of the MgO of O, 1.5-10%, 0-5%, 0-2%, 1-
The Al of 6% BaO, 1-9%2O3, the P of the ZnO of 2-10%, 55-75%2O5, the YF of 1-2%3, the LaF of 0.5-2%3, 0.1-
2% Co3O4。
(2) uniformly mixed powder is added in crucible by several times, passes through Elema electric smelter heating melting, glass melting temperature control
System is stirred at 1200~1300 DEG C or so using blender, the bubble elimination situation that settling time sample according to glass and
Fixed, homogenising time is determined according to the refractive index homogeneity of sampling glass.
(3) during glass clarifying, the ultraviolet absorption edge of the valence state and glass that absorb ion is controlled by reducing atmosphere,
The ultraviolet permeability of material is improved while controlling two frequency-doubled wavelength absorbent properties；
(4) after glass metal is clarified and eliminates bubble and stir, by high-temperature glass liquid via the thin of crucible bottom
Long material leakage mouth is slowly injected into progress chunk glass molding in the copper mould for have been preheated with 280~320 DEG C；
(5) by the chunk glass of cooling and shaping is quickly put into and is preheated to annealing temperature and (glass is arranged in copper mould
Transition temperature TgNear) Muffle furnace in, first keep the temperature 12~24 hours, then cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then
It is cooled near 100 DEG C with the cooling rate of-(3~5) DEG C/h, closes Muffle furnace power supply, make glass sample with furnace Temperature fall
To room temperature.
Wherein (2), (3), the practical operation of (4) step are more crucial, and mixed powder is added in crucible, Elema electric smelting
During stove heating high-temperature fusion, promotion stirring is carried out using leaf slurry blender, is successively realized in a crucible to high temperature glass
The clarification of glass liquid, homogenization process；Especially during glass clarifying, is regulated and controled in glass by reproducibility glass smelting atmosphere and inhaled
Ion is received in lower valency, the ultraviolet absorption edge blue shift of realization glass, improves material while controlling two frequency-doubled wavelength absorbent properties
The ultraviolet permeability of material；In addition, high-temperature glass liquid is slowly injected into via the elongated material leakage mouth of crucible bottom when glass forms
In preheated good copper mould, with refractory cover is added above mold, forming process high temperature glass metal surface and its top are prevented
The lower air of relative temperature forms convection current, and convection current is avoided to cause the glass cord thin and close in surface layer of glass and internal formation.
Preferably, it is the dry powder of 80~100 mesh that the above raw material, which all uses partial size, purity be it is specific pure, i.e., it is main
Content>99.9%, impurity content Fe<2ppm, Co, Mn, Ni, V, Cr<1ppm.
In step (3), H is passed through into crucible in glass metal high temperature clarifying process2Or H2With N2Mixed gas, manufacture
Reducing atmosphere, on the one hand three valence state (Co of absorption ion3+) control is restored as divalent state (Co2+), control two times of material
Frequency absorption characteristic；Meanwhile the trace Fe that can will may contain in raw material3+Continue to be reduced to Fe2+, reduce foreign ion and cause
Material in ultraviolet absorption intensity, improve the frequency tripling transmitance of material.
In step (4), when being slowly injected into the copper mould having had been warmed up via the elongated material leakage mouth of crucible bottom,
Refractory cover is provided with above copper mould.
In step (5), by copper mould the chunk glass of cooling and shaping be quickly put into be preheated to annealing temperature (setting exist
The transition temperature T of glassgNear) Muffle furnace in (other annealing devices can also be used), first keep the temperature 12~24 hours, then
Cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then is cooled to 100 DEG C near with the cooling rate of-(3~5) DEG C/h, closing Muffle
Furnace power supply, makes glass sample be naturally cooling to room temperature with furnace.
According to national standard " the 12nd part of 7962.12-2010 colouless optical glass test method of GB/T: transmission in spectrum
Than ", using ultraviolet visible light-near infrared spectrometer to the low fluorine-containing two double-frequency laser color separation glass material of phosphate
The transmitance of material sample measures, and obtains the interior transmittance curve of 1cm thickness sample.According to international standard ISO11254-1:
2000(E)(Laser and laser-related equipment—Determination of laser-induced
Damage threshold of optical surfaces-Part 1:1-on-1test) requirement build laser damage threshold
Testing system platform, damage of the test material at frequency tripling (351nm), two frequencys multiplication (527nm) and fundamental frequency (1053nm) wavelength
Threshold value.According to national standard " 7962.1-2010 colouless optical glass test method part 1 of GB/T: refractive index and abbe number "
Test obtains refractive index n of the sample at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nC, byIt calculates
To Abbe number υd, field experience formula (1) brings n intod、υdThe nonlinear coefficient γ of sample can be calculated, wherein K=2.8 ×
10-10m2/W。
Test result shows: the interior transmitance at 1cm thickness sample frequency tripling wavelength (351nm) reaches 98.8% or more (such as
Shown in Fig. 1).This novel low fluorine-containing two double-frequency laser color separation glass material of phosphate is at frequency tripling wavelength (351nm)
Damage threshold (laser pulse width 8ns) is higher than 1 times of quartz material or more, and at two frequencys multiplication (527nm), fundamental frequency (1053nm) wavelength
Damage threshold be above fused quartz material (as shown in Figure 2)；Meanwhile the low fluorine-containing two double-frequency laser color separation glass of phosphate
The nonlinear factor and fused quartz of material are close, and can prepare the optics of production large scale (430mm*430mm), high optical quality
Element.
The composition of each ingredient and the optical property of respective sample in 1 specific embodiment of table
Technical solution of the present invention is described in detail combined with specific embodiments below.
Embodiment one:
By the formula 1 of table 1#In a mole composition calculate the weight percent of glass, then weigh the total 25Kg of raw material,
It is uniformly mixed in mixer.The powder matched is sequentially added in 13 liters of crucibles, by silicon carbide electric smelter heating melting, is melted
At 1280 DEG C or so, melting time is 6~8h for temperature control, is stirred using leaf slurry blender glass metal in melting process
It mixes.In glass metal high temperature clarifying process, H is passed through into crucible2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
It absorbs ionic valence condition, reduce UV absorption caused by foreign ion.After glass metal is clarified and eliminates bubble and stir,
By high-temperature glass liquid by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 300 DEG C carry out chunk glass at
Type, and will quickly be put into after the demoulding of formed glass sample and have warmed up annealing temperature (the transition temperature T of glass is setgNear)
Muffle furnace in, after heat preservation 12~for 24 hours, first cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then with the cooling of-(3~5) DEG C/h
Rate is cooled near 100 DEG C, closes Muffle furnace power supply, and glass sample is made to be naturally cooling to room temperature with furnace, takes out chunk glass.
Sample after taking annealing, is processed into the refraction index test sample with an accurate right angle, according to national standard " GB/T
7962.1-2010 colouless optical glass test method part 1s: refractive index and abbe number " test obtain sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.529587,1.535114,1.527188,
Its Abbe number υ is calculateddIt is 66.82, field experience formula (1) brings n intod、υdThe nonlinear coefficient γ of sample is calculated
It is 3.02 × 10-20esu。
For fused quartz material, according to healthy and free from worry optical glass handbook (Corning Optical Glass catalogue)
Check in its nd、nF、nCRespectively 1.45843,1.6309,1.45634, Abbe number υdIt is 67.87, brings n intod、υdTo empirical equation
(1), the nonlinear coefficient γ that sample is calculated is 2.5 × 10-20esu。
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, as a result as shown in figure 1 shown in curve 1.Table 1 gives the material in frequency tripling light 351nm, two frequency doubled lights
The interior transmitance τ of 527nm wavelength351、τ527With absorption coefficient K351、K527Respectively 98.83%, 2.93% and 0.0118cm-1、
3.53cm-1.Bubble degree, the striped degree of glass sample are respectively A00, B grades.
Embodiment two:
By the formula 2 of table 1#In a mole composition calculate the weight percent of glass, then weigh the total 25Kg of raw material,
It is uniformly mixed in mixer.The powder matched is sequentially added in 13 liters of crucibles, by silicon carbide electric smelter heating melting, is melted
At 1280 DEG C or so, melting time is 6~8h for temperature control, is stirred using leaf slurry blender glass metal in melting process
It mixes.In glass metal high temperature clarifying process, H is passed through into crucible2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
It absorbs ionic valence condition, reduce UV absorption caused by foreign ion.After glass metal is clarified and eliminates bubble and stir,
By high-temperature glass liquid by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 290 DEG C carry out chunk glass at
Type, and will quickly be put into after the demoulding of formed glass sample and have warmed up annealing temperature (the transition temperature T of glass is setgNear)
Muffle furnace in, after heat preservation 12~for 24 hours, first cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then with the cooling of-(3~5) DEG C/h
Rate is cooled near 100 DEG C, closes Muffle furnace power supply, and glass sample is made to be naturally cooling to room temperature with furnace, takes out chunk glass.
Sample after taking annealing, is processed into the refraction index test sample with an accurate right angle, according to national standard " GB/T
7962.1-2010 colouless optical glass test method part 1s: refractive index and abbe number " test obtain sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.533827,1.539336,1.531501,
Its Abbe number υ is calculateddIt is 68.13, brings n intod、υdTo empirical equation (1), the nonlinear coefficient γ that sample is calculated is
2.97×10-20esu。
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, as a result as shown in figure 1 shown in curve 1.Table 1 gives the material in frequency tripling light 351nm, two frequency doubled lights
The interior transmitance τ of 527nm wavelength351、τ527With absorption coefficient K351、K527Respectively 99.19%, 1.24% and 0.0081cm-1、
4.39cm-1.Bubble degree, the striped degree of glass sample are respectively A00, B grades.
Embodiment three:
By the formula 3 of table 1#In a mole composition calculate the weight percent of glass, then weigh the total 25Kg of raw material,
It is uniformly mixed in mixer.The powder matched is sequentially added in 13 liters of crucibles, by silicon carbide electric smelter heating melting, is melted
At 1280 DEG C or so, melting time is 6~8h for temperature control, is stirred using leaf slurry blender glass metal in melting process
It mixes.In glass metal high temperature clarifying process, H is passed through into crucible2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
It absorbs ionic valence condition, reduce UV absorption caused by foreign ion.After glass metal is clarified and eliminates bubble and stir,
By high-temperature glass liquid by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 310 DEG C carry out chunk glass at
Type, and will quickly be put into after the demoulding of formed glass sample and have warmed up annealing temperature (the transition temperature T of glass is setgNear)
Muffle furnace in, after heat preservation 12~for 24 hours, first cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then with the cooling of-(3~5) DEG C/h
Rate is cooled near 100 DEG C, closes Muffle furnace power supply, and glass sample is made to be naturally cooling to room temperature with furnace, takes out chunk glass.
Sample after taking annealing, is processed into the refraction index test sample with an accurate right angle, according to national standard " GB/T
7962.1-2010 colouless optical glass test method part 1s: refractive index and abbe number " test obtain sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.525149,1.530601,1.522721,
Its Abbe number υ is calculateddIt is 66.64, brings n intod、υdTo empirical equation (1), the nonlinear coefficient γ that sample is calculated is
3.01×10-20esu。
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, as a result as shown in figure 1 shown in curve 1.Table 1 gives the material in frequency tripling light 351nm, two frequency doubled lights
The interior transmitance τ of 527nm wavelength351、τ527With absorption coefficient K351、K527Respectively 99.59%, 11.14% and 0.0041cm-1、
2.19cm-1.Bubble degree, the striped degree of glass sample are respectively A00, B grades.
Example IV:
By the formula 4 of table 1#In a mole composition calculate the weight percent of glass, then weigh the total 25Kg of raw material,
It is uniformly mixed in mixer.The powder matched is sequentially added in 13 liters of crucibles, by silicon carbide electric smelter heating melting, is melted
At 1280 DEG C or so, melting time is 6~8h for temperature control, is stirred using leaf slurry blender glass metal in melting process
It mixes.In glass metal high temperature clarifying process, H is passed through into crucible2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
It absorbs ionic valence condition, reduce UV absorption caused by foreign ion.After glass metal is clarified and eliminates bubble and stir,
By high-temperature glass liquid by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 310 DEG C carry out chunk glass at
Type, and will quickly be put into after the demoulding of formed glass sample and have warmed up annealing temperature (the transition temperature T of glass is setgNear)
Muffle furnace in, after heat preservation 12~for 24 hours, first cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then with the cooling of-(3~5) DEG C/h
Rate is cooled near 100 DEG C, closes Muffle furnace power supply, and glass sample is made to be naturally cooling to room temperature with furnace, takes out chunk glass.
Sample after taking annealing, is processed into the refraction index test sample with an accurate right angle, according to national standard " GB/T
7962.1-2010 colouless optical glass test method part 1s: refractive index and abbe number " test obtain sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.53276,1.538233,1.530383,
Its Abbe number υ is calculateddIt is 67.87, brings n intod、υdTo empirical equation (1), the nonlinear coefficient γ that sample is calculated is
2.98×10-20esu。
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, as a result as shown in figure 1 shown in curve 1.Table 1 gives the material in frequency tripling light 351nm, two frequency doubled lights
The interior transmitance τ of 527nm wavelength351、τ527With absorption coefficient K351、K527Respectively 99.41%, 17.13% and 0.0059cm-1、
1.76cm-1.Bubble degree, the striped degree of glass sample are respectively A00, B grades.
Embodiment five:
By the formula 5 of table 1#In a mole composition calculate the weight percent of glass, then weigh the total 25Kg of raw material,
It is uniformly mixed in mixer.The powder matched is sequentially added in 13 liters of crucibles, by silicon carbide electric smelter heating melting, is melted
At 1280 DEG C or so, melting time is 6~8h for temperature control, is stirred using leaf slurry blender glass metal in melting process
It mixes.In glass metal high temperature clarifying process, H is passed through into crucible2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
It absorbs ionic valence condition, reduce UV absorption caused by foreign ion.After glass metal is clarified and eliminates bubble and stir,
By high-temperature glass liquid by crucible bottom material leakage mouth be injected into the copper mould for have been preheated with 320 DEG C carry out chunk glass at
Type, and will quickly be put into after the demoulding of formed glass sample and have warmed up annealing temperature (the transition temperature T of glass is setgNear)
Muffle furnace in, after heat preservation 12~for 24 hours, first cooled down 120 DEG C with the cooling rate of -2 DEG C/h, then with the cooling of-(3~5) DEG C/h
Rate is cooled near 100 DEG C, closes Muffle furnace power supply, and glass sample is made to be naturally cooling to room temperature with furnace, takes out chunk glass.
Sample after taking annealing, is processed into the refraction index test sample with an accurate right angle, according to national standard " GB/T
7962.1-2010 colouless optical glass test method part 1s: refractive index and abbe number " test obtain sample exist
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCRespectively 1.526199,1.531651,1.523877,
Its Abbe number υ is calculateddIt is 67.69, brings n intod、υdTo empirical equation (1), the nonlinear coefficient γ that sample is calculated is
2.94×10-20esu。
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, as a result as shown in figure 1 shown in curve 1.Table 1 gives the material in frequency tripling light 351nm, two frequency doubled lights
The interior transmitance τ of 527nm wavelength351、τ527With absorption coefficient K351、K527Respectively 99.19%, 1.69% and 0.0082cm-1、
4.08cm-1.Bubble degree, the striped degree of glass sample are respectively A00, B grades.
It is chosen at the interior transmitance (τ of frequency tripling light 351nm wavelength351) higher and 527nm absorption coefficient (K527) biggish
2# sample tests its laser damage threshold, while carrying out with the damage threshold for the fused quartz material tested under the same terms
Comparison.Test data is as shown in Figure 2.As can be seen that the 351nm damage threshold of the material is fused quartz (Corning's 7980)
2 times, and it is above fused quartz material in the damage threshold of 527nm, 1053nm wavelength, damage data is as shown in table 2.
The low fluorine-containing two frequency multiplication color separation laser glass material sample (1cm thickness, non-plated film) of phosphate of 2# is in frequency tripling
Under (351nm), two frequencys multiplication (527nm) Irradiation of High, with being gradually increased for light laser power density, correspond to 351nm,
Transmitance variation at 527nm wavelength is smaller: 351nm transmitance is omited as the increase of frequency tripled laser irradiance power density is presented
Micro- raised trend, variable quantity is about ± 0.1% near the substantially transmissive rate 90% of 351nm, as shown in Figure 3.For another example Fig. 4 institute
Show, with the increase of basic frequency laser irradiance power density, transmitance of the material at 527nm wavelength slightly increases, but at it
Variable quantity near the substantially transmissive rate 1.0% of 527nm is in ± 0.3% range.This illustrates high power laser light irradiation to low fluorine-containing
The bleaching power influence of two frequency multiplication color separation laser glass material transmitance of phosphate is smaller, which can satisfy the material
To saturating ultraviolet, two frequency multiplication color separation element of high damage threshold application requirement in high energy, high power laser system.
2 damage threshold test data of table compares
Claims (9)
1. a kind of low fluorine-containing two double-frequency laser color separation glass of phosphate, it is characterised in that: the material composition of glass are as follows: 1.5-
7.5% Li2The Na of O, 0.3-4.4%2The K of O, 1.3-7%2The CaO of the MgO of O, 3-7.6%, 2.7-4.1%, 0.5-1.9%
SrO, the Al of the BaO of 2.7-5.1%, 1-9%2O3, the P of the ZnO of 2.5-7.2%, 55-75%2O5, the YF of 1.1-2%3,
The LaF of 0.6-1.9%3, the Co of 0.18-1.42%3O4；
The composition proportion of each raw material is molal weight score.
2. low fluorine-containing two double-frequency laser color separation glass of phosphate according to claim 1, it is characterised in that: the Li2O、
Na2O and K2The sum of molal weight score of O is 8-16%；The sum of molal weight score of described MgO, CaO, SrO and BaO is 9-
14%.
3. low fluorine-containing two double-frequency laser color separation glass of phosphate according to claim 2, it is characterised in that: the P2O5
Molal weight be Al2O39-11 times；The molal weight of oxide is 30-39 times of fluoride in raw material.
4. a kind of preparation method of low fluorine-containing two double-frequency laser color separation glass of phosphate, it is characterised in that: the following steps are included:
1] raw material is weighed；
Raw material is weighed according to the composition proportion in claim 1 and is uniformly mixed；
2] heating melting；
Glass melting temperature is kept after uniformly mixed raw material is heated to melting；
3] clarifying and homogenizing；
Under reducing atmosphere, the raw material of molten condition is stirred by the way of promoting stirring, until obtaining the height of clarifying and homogenizing
Warm glass metal；
4] casting；
High-temperature glass liquid is slowly injected into mold and obtains molding chunk glass；
5] it makes annealing treatment；
Chunk glass after demoulding is subjected to insulation annealing processing at an annealing temperature, low fluorine-containing phosphoric acid is obtained after being cooled to room temperature
Two double-frequency laser color separation glass of salt.
5. the preparation method of low fluorine-containing two double-frequency laser color separation glass of phosphate according to claim 4, feature exist
In step 1] in raw material to use partial size be the dry powder of 80-100 mesh, material purity is specific pure.
6. the preparation method of low fluorine-containing two double-frequency laser color separation glass of phosphate according to claim 5, feature exist
In step 2] in glass melting temperature be 1200-1300 DEG C.
7. the preparation method of low fluorine-containing two double-frequency laser color separation glass of phosphate according to claim 6, feature exist
In step 3] in eliminate and futher stir homogenizing after bubble and eliminate striped；The reducing atmosphere is H2Or H2With N2Mixing
Gas.
8. the preparation method of low fluorine-containing two double-frequency laser color separation glass of phosphate according to claim 7, feature exist
In step 4] in mold be the copper mould that is preheated to 280-320 DEG C, be provided with refractory cover above copper mould.
9. according to the preparation method of the low fluorine-containing two double-frequency laser color separation glass of phosphate any in claim 4-8,
It is characterized by: step 5] further comprising the steps of:
Annealing device 5.1] is preheated to the annealing temperature of chunk glass；
5.2] from quickly removing chunk glass in mold and being put into annealing device, 12~24 hours are kept the temperature；
5.3] make 120 DEG C of the greenhouse cooling in annealing device with the cooling rate of -2 DEG C/h；
5.4] temperature in annealing device is made to be down to 100 DEG C with the cooling rate of-(3~5) DEG C/h；
5.5] annealing device is closed, obtains low two double-frequency laser color separation glass of fluorine-containing phosphate after cooled to room temperature.
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| US5526369A (en) * | 1992-10-07 | 1996-06-11 | Schott Glass Technologies, Inc. | Phosphate glass useful in high energy lasers |
| 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 |
| CN103265173A (en) * | 2013-05-30 | 2013-08-28 | 中国科学院西安光学精密机械研究所 | Preparation method of second harmonic light absorbing material with high damage threshold |
| CN105000801A (en) * | 2015-07-20 | 2015-10-28 | 中国科学院西安光学精密机械研究所 | Ultraviolet-transmittance and high-damage-threshold fluoride phosphate laser glass and preparation method thereof |
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2016
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|---|---|---|---|---|
| US5526369A (en) * | 1992-10-07 | 1996-06-11 | Schott Glass Technologies, Inc. | Phosphate glass useful in high energy lasers |
| 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 |
| CN103265173A (en) * | 2013-05-30 | 2013-08-28 | 中国科学院西安光学精密机械研究所 | Preparation method of second harmonic light absorbing material with high damage threshold |
| CN105000801A (en) * | 2015-07-20 | 2015-10-28 | 中国科学院西安光学精密机械研究所 | Ultraviolet-transmittance and high-damage-threshold fluoride phosphate laser glass and preparation method thereof |
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| Investigations on the photoluminescence of the iron and cobalt doped fluoride-containing phosphate-based glasses and its defects-related nature;Quanlong He etc.;《Journal of Alloys and Compounds》;20160526;第685卷;第154页第2节 * |
| Investigations on the photoluminescence spectra and its defect-related nature for the ultraviolet transmitting fluoride-containing phosphate-based glasses;Dandan Feng etc.;《Journal of Non-Crystalline Solids》;20150613;第425卷;第130-137页 * |
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