CN106477880A - A kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses and preparation method thereof - Google Patents
A kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses and preparation method thereof Download PDFInfo
- Publication number
- CN106477880A CN106477880A CN201610838146.2A CN201610838146A CN106477880A CN 106477880 A CN106477880 A CN 106477880A CN 201610838146 A CN201610838146 A CN 201610838146A CN 106477880 A CN106477880 A CN 106477880A
- Authority
- CN
- China
- Prior art keywords
- glass
- double
- color separation
- containing phosphate
- glasses
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention belongs to laser glass field of material technology is and in particular to a kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses and preparation method thereof.The material composition of this glass is：1.5 10% Li2O, 0 8% Na2O, 0 15% K2O, 1.5 10% MgO, 0 5% CaO, 0 2% SrO, 1 6% BaO, 1 9% Al2O3, 2 10% ZnO, 55 75% P2O5, 1 2% YF3, 0.5 2% LaF3, 0.1 2% Co3O4；The composition proportion of each raw material is molal weight fraction.The present invention solve fluoride glass and high fluorine-containing glass system easy crystallize, become that glass is poor, volatilization is big, be difficult to homogenizing elimination striped and viscosity little cause large scale difficult forming the problems such as.Under equal test condition, its laser damage threshold, apparently higher than fused quartz glass material, can replace fused quartz glass material for improving the laser load ability of system in high energy and power laser instrument.
Description
Technical field
The invention belongs to laser glass field of material technology is and in particular to a kind of low fluorine-containing phosphate two double-frequency laser color separates
Glass and preparation method thereof.
Background technology
Laser Driven inertial confinement fusion (Inertial confinement fusion, ICF) utilizes can be from sea water
The deuterium tritium extracting is fusion fuel, carries out controlled nuclear fusion and produces high-gain fusion energy, be acknowledged as 21 under light laser constraint
Century cleaning new energy dawn, simultaneously to promote Strong-field physics research and high power laser light technology development significant.
2014, the national igniter (National Ignition Facility, NIF) that the U.S. is used for ICF research was realized first
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 of 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 in order 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 the function such as measurement sampling be all whole drive all the time
The weakest link of resisting laser damage and bottleneck unit in dynamic device.In Final optical assembly, harmonic wave separation technology is to determine frequency tripling
The key factor of target practice laser-quality.
Fundamental frequency light is converted into the three of laser-produced fusion experiment by the high-power laser driver such as NIF using frequency conversion crystal
Frequency doubled light, but because conversion efficiency is limited, still remaining certain fundamental frequency and two frequency doubled lights in its output light path.These are remaining
Fundamental frequency, two frequency doubled lights entrance target chambers are all very unfavorable to fusion assay and target chamber diagnostic system.At present, final-optics are mainly passed through
In assembly, fused quartz wedge-shaped lens make fundamental frequency, two frequency doubled lights focus on to retrodeviate with a distance from frequency tripling optical focus very little, and finally only three
Frequency doubled light focuses on target spot.This harmonic wave separation technology based on fused quartz wedge type lens is it is impossible to by fundamental frequency, two multiplied frequency harmonic
Thoroughly remove, in order to avoid the costliness optical element such as fused quartz lens suffers from secondary damage, the structure of existing Final optical assembly
Design is sufficiently complex.Ultraviolet damage threshold plus fused quartz material does not reach the requirement of ICF device high flux operation, causes 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 critical bottleneck problem of restriction ICF device high pass output.Research and development tool
There is the novel optical material that damage threshold is higher compared with fused quartz, design substitutes fused quartz wedge-shaped lens, innovation ICF final-optics system
Harmonic wave separation element in system, opens up new technology way by exporting bottleneck problem for the high flux solving high-power laser driver
Footpath.
NIF technical committee of the U.S. just proposed crystal of fluoride, the fluoride glass developing saturating ultraviolet early in 1999
It is used for substituting conceptual prospect and the conception of fused quartz Deng new pattern laser material.In these materials, fluorphosphate glass is considered
It is that one kind potentially has good ultraviolet diactinic laser glass material.Since the nineties in last century, it has been based primarily upon anti-
The often lenticular application demand of dispersion VUV, researchers carry out to various fluorine phosphorous glass and phosphate-based glass property
Systematic study, including glass composition with preparation, impurity and Study of Defects, ultraviolet, excimer laser and x-ray irradiation effect to material
Material VUV transmitance impact etc..Fluorine phosphorous glass mostly is high fluorine-containing system, is difficult to prepare the heavy caliber of high optical quality
(430mm*430mm) optical element, so fail so far to have applied in ICF Final optical assembly.
Although it is also proposed a kind of high damage threshold two frequency multiplication light absorbing material in patent (ZL201310210092.1)
Preparation method, but this high damage threshold two frequency multiplication light absorbing material is the glass system with fluoride as main component, by master
SiO to be introduced2(19～20mol%) improves one-tenth glass and the physicochemical properties of fluoride, adds a small amount of rare earth oxide
La2O3、Y2O3Improve thermal transition temperature and the devitrification resistance energy of glass.It is important that above-mentioned fluorosilicate glass system and method
The volatilization that still cannot thoroughly solve fluoride basis glass system is big, the problems such as viscosity is little, large scale molding striped removes difficulties,
And found high fluorine-containing fluorosilicate glass to found medium and technological requirement very harsh it is difficult to large scale molding.
Content 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
Technical problem, the present invention provides a kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses and preparation method thereof.
The technical solution of the present invention is：A kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses, its special it
Place is：The material composition of described laser glass is：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 fraction.
Above-mentioned Li2O、Na2O and K2The molal weight fraction sum of O is 8-16%；Described MgO, CaO, SrO and BaO rub
Your mass fraction sum is 9-14%.
Above-mentioned P2O5Molal weight be Al2O39-11 times；In raw material, the molal weight of oxide is the 30- of fluoride
39 times.
The present invention also provides a kind of preparation method of low fluorine-containing phosphate two double-frequency laser color separation of glasses, its special character
It is：Comprise the following steps：
1】Weigh raw material；
Weigh raw material mix homogeneously according to the composition proportion in claim 1；
2】Heating melting；
The raw material of mix homogeneously is heated to after melting keeping glass melting temperature；
3】Clarification homogenizing；
Under reducing atmosphere, the raw material of stirring molten condition, until obtain the high-temperature glass liquid of clarification homogenizing；
4】Casting；
High-temperature glass liquid is slowly injected into the chunk glass obtaining molding in mould；
5】Annealing；
Chunk glass after the demoulding is carried out insulation annealing process at an annealing temperature, obtains low fluorine-containing after being cooled to room temperature
Phosphate two double-frequency laser color separation of glasses.
Step 1】In raw material all using particle diameter for 80-100 mesh the powder that is dried, material purity is specific pure.
Step 2】In glass melting temperature be 1200-1300 DEG C.
Step 3】In stirring be by lifting stirring, eliminate bubble after stir further homogenizing eliminate striped；Described also
Originality atmosphere is H2Or H2With N2Mixed gas.
Step 4】In mould be to be preheated to 280-320 DEG C of copper mould, be provided with refractory cover above copper mould.
Step 5】Further comprising the steps of：
5.1】Annealing device is preheated to the annealing temperature of chunk glass；
5.2】Quickly remove chunk glass and put in annealing device from mould, be incubated 12～24 hours；
5.3】Make 120 DEG C of greenhouse cooling in annealing device with the cooldown rate of -2 DEG C/h；
5.4】The temperature in annealing device is made to be down to 100 DEG C with the cooldown rate of-(3～5) DEG C/h；
5.5】Close annealing device, after naturally cooling to room temperature, obtain low fluorine-containing phosphate two double-frequency laser color separation glass
Glass.
The beneficial effects of the present invention is：
(1) present invention solves the easy crystallize of fluoride glass and high fluorine-containing glass system, becomes that glass is poor, it is big, difficult to volatilize
With homogenizing eliminate striped and viscosity little cause large scale difficult forming the problems such as.Under equal test condition, its damage from laser
Threshold value, apparently higher than fused quartz glass material, can replace fused quartz glass material for improving system in high energy and power laser instrument
Laser load ability, simultaneously replace the detached technology of wedge-shaped mirrors space harmonics, by ionic absorption method remove two frequency multiplication ripples
Long laser is so as to realize being completely separated with frequency tripled laser, thus improving and ICF terminal for the continuation of ICF laser output flow
In optical module, the innovation of harmonic wave separation technology provides two important frequency multiplication color separate optical elements to support.
(2) present invention passes through to regulate and control glass composition and two frequencys multiplication absorb the doping content of ion, can make this glass material
Two frequencys multiplication (2 ω, 527nm) are swashed with light intensity absorption (transmitance τ in 527nm527≤ 2%/cm), simultaneously 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, the damage threshold also slightly above molten stone of two frequency-doubled wavelength (2 ω, 527nm)
English.
(3) the glass material stable chemical performance of the present invention, suitable large scale batch production.
Brief description
Fig. 1 is the interior transmittance curve of the low fluorine-containing phosphate two double-frequency laser color separation of glasses sample of the present invention.
Fig. 2 is the low fluorine-containing phosphate two double-frequency laser color separation of glasses 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 phosphate two double-frequency laser color separation of glasses of the present invention in different capacity density frequency tripling
(351nm) correspond to the transmitance change curve of 351nm wavelength under Irradiation of High.
Fig. 4 is the low fluorine-containing phosphate two double-frequency laser color separation of glasses of the present invention in different capacity density two frequency multiplication
(527nm) correspond to the transmitance change curve of 527nm wavelength under Irradiation of High.
Specific embodiment
The present invention is constituted with alkali metal oxide, alkaline earth oxide, aluminium oxide and phosphorus pentoxide for main composition
Phosphate basis glass system, makes the ultraviolet absorption edge blue shift of glass, improves its one-tenth glass by introducing rare earth fluoride component
Can, introduce viscosity and the processability that zinc oxide adjusts glass；In vitreous humour high temperature clarifying process, in crucible, it is passed through H2Or
H2With N2Mixed gas, manufacture reproducibility glass melting atmosphere, regulation and control glass in absorb ion be in lower valency, realize glass
Ultraviolet absorption edge blue shift；By the ratio of composition each in optimization of C/C composites, obtain and be suitable for large scale molding, stable chemical performance, swash
Light injury threshold is higher than the low fluorine-containing phosphate two double-frequency laser color separation of glasses material of fused quartz.This laser glass material is near
There is good spectral transmission performance ultra-violet (UV) band, has high resisting under frequency tripling (351nm, 355nm) high energy pulse laser irradiation
Laser damage threshold, and stable chemical performance, it is applied to the batch production of large-size glass.The alternative molten stone of this glass material
English material, is processed as ultraviolet lens, two frequencys multiplication (527nm, 532nm) light filter and quadruple (263nm, 266nm) attenuator etc.
Optical component is applied to high energy, high power laser system, the ultraviolet optics such as fused quartz in the existing high energy of solution, high power system
The damage from laser problem of element, improves the load fan-out capability of laser instrument further, and is expected to divide as saturating ultraviolet, two frequency multiplication colors
It is used in the superpower laser of Laser Driven inertial confinement fusion test from optical element.
The present invention is can be improved its UV-permeable characteristic and be become glass by introducing in multicomponent phosphate glass system
The rare earth fluoride component of energy, the zinc oxide of scalable glass viscosity, the new large-sized ultraviolet of acquisition, high damage threshold are low
Fluorine-containing phosphate two double-frequency laser color separation of glasses material.Its preparation method is：With alkali metal oxide, alkaline-earth metal oxide
Thing, aluminium oxide, zinc oxide and phosphorus pentoxide are main composition, add a small amount of rare earth fluoride, control two by reducing atmosphere
Frequency multiplication absorbs the ultraviolet absorption edge of ionic valence condition and glass, high temperature melting, clarification, after homogenizing, prepares glass with leaking note method molding
Blank, then through annealing, obtain the low fluorine-containing phosphate laser glass material of high damage threshold.Specifically include following steps：
(1) calculate the percentage by weight of each composition according to following molal weight fraction, weigh raw material, mix homogeneously：
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) powder of mix homogeneously is added in crucible by several times, melted by siliconits electric smelting stove heat, glass melting temperature control
System, at 1200～1300 DEG C about, is stirred using agitator, the bubble elimination situation that settling time sample according to glass and
Fixed, homogenising time determines according to the refractive index homogeneity of sampling glass.
(3) during glass clarifying, controlled by reducing atmosphere and absorb the valence state of ion and the ultraviolet absorption edge of glass,
Improve the ultraviolet permeability of material while controlling two frequency-doubled wavelength absorbent properties；
(4) after vitreous humour is clarified and eliminated bubble and stir, high-temperature glass liquid is thin via crucible bottom
Long material leakage mouth is slowly injected in the copper mould having been preheated with 280～320 DEG C and carries out chunk glass molding；
(5) chunk glass of cooling and shaping in copper mould is quickly put into and be preheated to annealing temperature and (be arranged on glass
Transition temperature TgNear) Muffle furnace in, be first incubated 12～24 hours, then lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then
It is cooled near 100 DEG C with the cooldown rate of-(3～5) DEG C/h, close Muffle furnace power supply, make glass sample with stove Temperature fall
To room temperature.
Wherein (2nd), (3), (4) step practical operation more crucial, mixed powder add crucible in, siliconits electric smelting
During stove heat high-temperature fusion, lifting stirring is carried out using leaf slurry agitator, successively realizes to high temperature glass in a crucible
The clarification of glass liquid, homogenization process；Particularly during glass clarifying, regulate and control in glass to inhale by reproducibility glass smelting atmosphere
Receive ion to be in lower valency, realize the ultraviolet absorption edge blue shift of glass, improve 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 during glass molding
In preheated good copper mould, above mould with plus refractory cover, prevent forming process high temperature vitreous humour surface with its above
The relatively low air of relative temperature forms convection current, it is to avoid convection current causes in surface layer of glass and is internally formed thin and close glass cord.
Preferably, the powder that is dried that above raw material is all 80～100 mesh using particle diameter, purity is specific pure, that is, lead
Content>99.9%, impurity content Fe<2ppm,Co、Mn、Ni、V、Cr<1ppm.
In step (3), in vitreous humour high temperature clarifying process to crucible in be passed through H2Or H2With N2Mixed gas, manufacture
Reducing atmosphere, on the one hand the three valence state (Co absorbing ion3+) reduction be controlled to divalent state (Co2+), control two times of material
Frequency absorption characteristic；Meanwhile, can be by the trace Fe that may contain in raw material3+Continue to be reduced to Fe2+, reduce foreign ion and cause
Material ultraviolet absorption intensity, improve material frequency tripling transmitance.
In step (4), when the elongated material leakage mouth via crucible bottom is slowly injected in the copper mould having been warmed up,
It is provided with refractory cover above copper mould.
In step (5), the chunk glass of cooling and shaping in copper mould is quickly put into and is preheated to annealing temperature and (is arranged on
The transition temperature T of glassgNear) Muffle furnace in (also can use other annealing devices), first be incubated 12～24 hours, then
Lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then be cooled to 100 DEG C near with the cooldown rate of-(3～5) DEG C/h, closing Muffle
Stove power supply, makes glass sample be naturally cooling to room temperature with stove.
According to GB《GB/T 7962.12 2010 colouless optical glass method of testing the 12nd part：Transmission in spectrum
Than》, using ultraviolet-visible near infrared spectrometer to this low fluorine-containing phosphate two double-frequency laser color separation of glasses material
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:Laser damage threshold is built in requirement 1-on-1test)
Testing system platform, damage at frequency tripling (351nm), two frequencys multiplication (527nm) and fundamental frequency (1053nm) wavelength for the test material
Threshold value.According to GB《GB/T 7962.1 2010 colouless optical glass method of testing part 1：Refractive index and abbe number》
Test obtains refractive index n at 587.6nm, 486.1nm, 656.3nm wavelength for the sampled、nF、nC, byCalculate
To Abbe number υd, field experience formula (1), bring 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) place reaches more than 98.8% (such as
Shown in Fig. 1).This new low fluorine-containing phosphate two double-frequency laser color separation of glasses material is at frequency tripling wavelength (351nm) place
Damage threshold (laser pulse width 8ns) is higher than more than 1 times of quartz material, and at two frequencys multiplication (527nm), fundamental frequency (1053nm) wavelength
Damage threshold be above fused quartz material (as shown in Figure 2)；Meanwhile, this low fluorine-containing phosphate two double-frequency laser color separation of glasses
The nonlinear factor of material is close with fused quartz, and can prepare production large scale (430mm*430mm), the optics of high optical quality
Element.
The composition of each composition and the optical property of respective sample in table 1 specific embodiment
With reference to specific embodiment, technical scheme is described in detail.
Embodiment one：
Formula 1 by table 1#In mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
Mix homogeneously in mixer.The powder joined is sequentially added in 13 liters of crucibles, is melted by carborundum electric smelting stove heat, found
At 1280 DEG C about, melting time is 6～8h to temperature control, using leaf slurry agitator, vitreous humour is stirred in melting process
Mix.In vitreous humour high temperature clarifying process, in crucible, it is passed through H2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
Absorb ionic valence condition, reduce the uv absorption that foreign ion causes.After vitreous humour is clarified and is eliminated bubble and stir,
High-temperature glass liquid is injected in the copper mould have been preheated with 300 DEG C by crucible bottom material leakage mouth and carries out chunk glass one-tenth
Type, and quick warmed up (it is arranged on the transition temperature T of glass to annealing temperature by putting into after the formed glass sample demouldinggNear)
Muffle furnace in, after insulation 12～24h, first lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then the cooling with-(3～5) DEG C/h
Speed is cooled near 100 DEG C, closes Muffle furnace power supply, makes glass sample be naturally cooling to room temperature with stove, takes out chunk glass.
Take the sample after annealing, be processed into the refraction index test sample with an accurate right angle, according to GB《GB/T
7962.1 2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and exists
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCIt is respectively 1.529587,1.535114,1.527188,
It is calculated its Abbe number υdFor 66.82, field experience formula (1), bring n intod、υdIt is calculated the nonlinear coefficient γ of sample
For 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、nCIt is respectively 1.45843,1.6309,1.45634, Abbe number υdFor 67.87, bring n intod、υdTo empirical equation
(1) nonlinear coefficient γ, being calculated sample is 2.5 × 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 GB《GB/T 7962.12 2010 colouless optical glass method of testing the 12nd part：Spectrum internal transmittance》,
Using ultraviolet-visible near infrared spectrometer, the transmitance of sample is measured, obtaining thickness is 10mm sample
Interior transmittance curve, result is as shown in curve 1 in Fig. 1.Table 1 gives this material in frequency tripling light 351nm, two frequency doubled lights
Interior transmitance τ of 527nm wavelength351、τ527With absorptance K351、K527It is respectively 98.83%, 2.93% and 0.0118cm-1、
3.53cm-1.The bubble degree of glass sample, striped degree are respectively A00, B level.
Embodiment two：
Formula 2 by table 1#In mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
Mix homogeneously in mixer.The powder joined is sequentially added in 13 liters of crucibles, is melted by carborundum electric smelting stove heat, found
At 1280 DEG C about, melting time is 6～8h to temperature control, using leaf slurry agitator, vitreous humour is stirred in melting process
Mix.In vitreous humour high temperature clarifying process, in crucible, it is passed through H2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
Absorb ionic valence condition, reduce the uv absorption that foreign ion causes.After vitreous humour is clarified and is eliminated bubble and stir,
High-temperature glass liquid is injected in the copper mould have been preheated with 290 DEG C by crucible bottom material leakage mouth and carries out chunk glass one-tenth
Type, and quick warmed up (it is arranged on the transition temperature T of glass to annealing temperature by putting into after the formed glass sample demouldinggNear)
Muffle furnace in, after insulation 12～24h, first lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then the cooling with-(3～5) DEG C/h
Speed is cooled near 100 DEG C, closes Muffle furnace power supply, makes glass sample be naturally cooling to room temperature with stove, takes out chunk glass.
Take the sample after annealing, be processed into the refraction index test sample with an accurate right angle, according to GB《GB/T
7962.1 2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and exists
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCIt is respectively 1.533827,1.539336,1.531501,
It is calculated its Abbe number υdFor 68.13, bring n intod、υdTo empirical equation (1), the nonlinear coefficient γ being calculated sample is
2.97×10-20esu.
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 GB《GB/T 7962.12 2010 colouless optical glass method of testing the 12nd part：Spectrum internal transmittance》,
Using ultraviolet-visible near infrared spectrometer, the transmitance of sample is measured, obtaining thickness is 10mm sample
Interior transmittance curve, result is as shown in curve 1 in Fig. 1.Table 1 gives this material in frequency tripling light 351nm, two frequency doubled lights
Interior transmitance τ of 527nm wavelength351、τ527With absorptance K351、K527It is respectively 99.19%, 1.24% and 0.0081cm-1、
4.39cm-1.The bubble degree of glass sample, striped degree are respectively A00, B level.
Embodiment three：
Formula 3 by table 1#In mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
Mix homogeneously in mixer.The powder joined is sequentially added in 13 liters of crucibles, is melted by carborundum electric smelting stove heat, found
At 1280 DEG C about, melting time is 6～8h to temperature control, using leaf slurry agitator, vitreous humour is stirred in melting process
Mix.In vitreous humour high temperature clarifying process, in crucible, it is passed through H2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
Absorb ionic valence condition, reduce the uv absorption that foreign ion causes.After vitreous humour is clarified and is eliminated bubble and stir,
High-temperature glass liquid is injected in the copper mould have been preheated with 310 DEG C by crucible bottom material leakage mouth and carries out chunk glass one-tenth
Type, and quick warmed up (it is arranged on the transition temperature T of glass to annealing temperature by putting into after the formed glass sample demouldinggNear)
Muffle furnace in, after insulation 12～24h, first lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then the cooling with-(3～5) DEG C/h
Speed is cooled near 100 DEG C, closes Muffle furnace power supply, makes glass sample be naturally cooling to room temperature with stove, takes out chunk glass.
Take the sample after annealing, be processed into the refraction index test sample with an accurate right angle, according to GB《GB/T
7962.1 2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and exists
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCIt is respectively 1.525149,1.530601,1.522721,
It is calculated its Abbe number υdFor 66.64, bring n intod、υdTo empirical equation (1), the nonlinear coefficient γ being calculated sample is
3.01×10-20esu.
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 GB《GB/T 7962.12 2010 colouless optical glass method of testing the 12nd part：Spectrum internal transmittance》,
Using ultraviolet-visible near infrared spectrometer, the transmitance of sample is measured, obtaining thickness is 10mm sample
Interior transmittance curve, result is as shown in curve 1 in Fig. 1.Table 1 gives this material in frequency tripling light 351nm, two frequency doubled lights
Interior transmitance τ of 527nm wavelength351、τ527With absorptance K351、K527It is respectively 99.59%, 11.14% and 0.0041cm-1、
2.19cm-1.The bubble degree of glass sample, striped degree are respectively A00, B level.
Example IV：
Formula 4 by table 1#In mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
Mix homogeneously in mixer.The powder joined is sequentially added in 13 liters of crucibles, is melted by carborundum electric smelting stove heat, found
At 1280 DEG C about, melting time is 6～8h to temperature control, using leaf slurry agitator, vitreous humour is stirred in melting process
Mix.In vitreous humour high temperature clarifying process, in crucible, it is passed through H2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
Absorb ionic valence condition, reduce the uv absorption that foreign ion causes.After vitreous humour is clarified and is eliminated bubble and stir,
High-temperature glass liquid is injected in the copper mould have been preheated with 310 DEG C by crucible bottom material leakage mouth and carries out chunk glass one-tenth
Type, and quick warmed up (it is arranged on the transition temperature T of glass to annealing temperature by putting into after the formed glass sample demouldinggNear)
Muffle furnace in, after insulation 12～24h, first lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then the cooling with-(3～5) DEG C/h
Speed is cooled near 100 DEG C, closes Muffle furnace power supply, makes glass sample be naturally cooling to room temperature with stove, takes out chunk glass.
Take the sample after annealing, be processed into the refraction index test sample with an accurate right angle, according to GB《GB/T
7962.1 2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and exists
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCIt is respectively 1.53276,1.538233,1.530383,
It is calculated its Abbe number υdFor 67.87, bring n intod、υdTo empirical equation (1), the nonlinear coefficient γ being calculated sample is
2.98×10-20esu.
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 GB《GB/T 7962.12 2010 colouless optical glass method of testing the 12nd part：Spectrum internal transmittance》,
Using ultraviolet-visible near infrared spectrometer, the transmitance of sample is measured, obtaining thickness is 10mm sample
Interior transmittance curve, result is as shown in curve 1 in Fig. 1.Table 1 gives this material in frequency tripling light 351nm, two frequency doubled lights
Interior transmitance τ of 527nm wavelength351、τ527With absorptance K351、K527It is respectively 99.41%, 17.13% and 0.0059cm-1、
1.76cm-1.The bubble degree of glass sample, striped degree are respectively A00, B level.
Embodiment five：
Formula 5 by table 1#In mole composition calculate the percentage by weight of glass, then weigh the common 25Kg of raw material,
Mix homogeneously in mixer.The powder joined is sequentially added in 13 liters of crucibles, is melted by carborundum electric smelting stove heat, found
At 1280 DEG C about, melting time is 6～8h to temperature control, using leaf slurry agitator, vitreous humour is stirred in melting process
Mix.In vitreous humour high temperature clarifying process, in crucible, it is passed through H2Or H2With N2Mixed gas, manufacture reducing atmosphere, control
Absorb ionic valence condition, reduce the uv absorption that foreign ion causes.After vitreous humour is clarified and is eliminated bubble and stir,
High-temperature glass liquid is injected in the copper mould have been preheated with 320 DEG C by crucible bottom material leakage mouth and carries out chunk glass one-tenth
Type, and quick warmed up (it is arranged on the transition temperature T of glass to annealing temperature by putting into after the formed glass sample demouldinggNear)
Muffle furnace in, after insulation 12～24h, first lowered the temperature 120 DEG C with the cooldown rate of -2 DEG C/h, then the cooling with-(3～5) DEG C/h
Speed is cooled near 100 DEG C, closes Muffle furnace power supply, makes glass sample be naturally cooling to room temperature with stove, takes out chunk glass.
Take the sample after annealing, be processed into the refraction index test sample with an accurate right angle, according to GB《GB/T
7962.1 2010 colouless optical glass method of testing part 1s：Refractive index and abbe number》Test obtains sample and exists
Refractive index n at 587.6nm, 486.1nm, 656.3nm wavelengthd、nF、nCIt is respectively 1.526199,1.531651,1.523877,
It is calculated its Abbe number υdFor 67.69, bring n intod、υdTo empirical equation (1), the nonlinear coefficient γ being calculated sample is
2.94×10-20esu.
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 GB《GB/T 7962.12 2010 colouless optical glass method of testing the 12nd part：Spectrum internal transmittance》,
Using ultraviolet-visible near infrared spectrometer, the transmitance of sample is measured, obtaining thickness is 10mm sample
Interior transmittance curve, result is as shown in curve 1 in Fig. 1.Table 1 gives this material in frequency tripling light 351nm, two frequency doubled lights
Interior transmitance τ of 527nm wavelength351、τ527With absorptance K351、K527It is respectively 99.19%, 1.69% and 0.0082cm-1、
4.08cm-1.The bubble degree of glass sample, striped degree are respectively A00, B level.
It is chosen at the interior transmitance (τ of frequency tripling light 351nm wavelength351) higher and 527nm absorptance (K527) larger
2# sample is tested to its laser damage threshold, carries out with the damage threshold of the fused quartz material of test under the same terms simultaneously
Contrast.Test data is as shown in Figure 2.As can be seen that the 351nm damage threshold of this material is fused quartz (Corning 7980)
2 times, and the damage threshold in 527nm, 1053nm wavelength is above fused quartz material, and its damage data is as shown in table 2.
Low fluorine-containing phosphate two frequency multiplication color separation laser glass material sample (1cm thickness, non-plated film) of 2# is in frequency tripling
(351nm), under two frequencys multiplication (527nm) Irradiation of High, with being gradually increased of light laser power density, its corresponding 351nm,
Transmitance change at 527nm wavelength is less:351nm transmitance presents slightly with the increase of frequency tripled laser irradiance power density
Microlitre high trend, its variable quantity near the substantially transmissive rate of 351nm 90% is about ± 0.1%, as shown in Figure 3.And for example Fig. 4 institute
Show, with the increase of basic frequency laser irradiance power density, transmitance at 527nm wavelength for the material slightly increases, but at it
Variable quantity near the substantially transmissive rate of 527nm 1.0% is in the range of ± 0.3%.This explanation high power laser light irradiation is to low fluorine-containing
The bleaching power impact of phosphate two frequency multiplication color separation laser glass material transmitance is less, and this performance makes this material can meet
Application requirement to saturating ultraviolet, high damage threshold two frequency multiplication color resolution element in high energy, high power laser system.
Table 2 damage threshold test data compares
Claims (9)
1. a kind of low fluorine-containing phosphate two double-frequency laser color separation of glasses it is characterised in that：The material composition of glass is：1.5-
10% Li2The 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%, 1-6%'s
The Al of 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%'s
Co3O4；
The composition proportion of each raw material is molal weight fraction.
2. low fluorine-containing phosphate two double-frequency laser color separation of glasses according to claim 1 it is characterised in that：Described Li2O、
Na2O and K2The molal weight fraction sum of O is 8-16%；The molal weight fraction sum of described MgO, CaO, SrO and BaO is 9-
14%.
3. low fluorine-containing phosphate two double-frequency laser color separation of glasses according to claim 2 it is characterised in that：Described P2O5
Molal weight be Al2O39-11 times；In raw material, the molal weight of oxide is 30-39 times of fluoride.
4. a kind of preparation method of low fluorine-containing phosphate two double-frequency laser color separation of glasses it is characterised in that：Comprise the following steps：
1】Weigh raw material；
Weigh raw material mix homogeneously according to the composition proportion in claim 1；
2】Heating melting；
The raw material of mix homogeneously is heated to after melting keeping glass melting temperature；
3】Clarification homogenizing；
Under reducing atmosphere, the raw material of stirring molten condition, until obtain the high-temperature glass liquid of clarification homogenizing；
4】Casting；
High-temperature glass liquid is slowly injected into the chunk glass obtaining molding in mould；
5】Annealing；
Chunk glass after the demoulding is carried out insulation annealing process at an annealing temperature, after being cooled to room temperature, obtains low fluorine-containing phosphoric acid
Salt two double-frequency laser color separation of glasses.
5. the preparation method of low fluorine-containing phosphate two double-frequency laser color separation of glasses according to claim 4, its feature exists
In：Step 1】In raw material all using particle diameter for 80-100 mesh the powder that is dried, material purity is specific pure.
6. the preparation method of low fluorine-containing phosphate two double-frequency laser color separation of glasses according to claim 5, its feature exists
In：Step 2】In glass melting temperature be 1200-1300 DEG C.
7. the preparation method of low fluorine-containing phosphate two double-frequency laser color separation of glasses according to claim 6, its feature exists
In：Step 3】In stirring be by lifting stirring, eliminate bubble after stir further homogenizing eliminate striped；Described reproducibility gas
Atmosphere is H2Or H2With N2Mixed gas.
8. the preparation method of low fluorine-containing phosphate two double-frequency laser color separation of glasses according to claim 7, its feature exists
In：Step 4】In mould be to be preheated to 280-320 DEG C of copper mould, be provided with refractory cover above copper mould.
9. the preparation method according to described low fluorine-containing phosphate two double-frequency laser color separation of glasses arbitrary in claim 4-8,
It is characterized in that：Step 5】Further comprising the steps of：
5.1】Annealing device is preheated to the annealing temperature of chunk glass；
5.2】Quickly remove chunk glass and put in annealing device from mould, be incubated 12～24 hours；
5.3】Make 120 DEG C of greenhouse cooling in annealing device with the cooldown rate of -2 DEG C/h；
5.4】The temperature in annealing device is made to be down to 100 DEG C with the cooldown rate of-(3～5) DEG C/h；
5.5】Close annealing device, after naturally cooling to room temperature, obtain low fluorine-containing phosphate two double-frequency laser color separation of glasses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610838146.2A CN106477880B (en) | 2016-09-21 | 2016-09-21 | Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610838146.2A CN106477880B (en) | 2016-09-21 | 2016-09-21 | Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106477880A true CN106477880A (en) | 2017-03-08 |
| CN106477880B CN106477880B (en) | 2019-03-08 |
Family
ID=58268692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610838146.2A Active CN106477880B (en) | 2016-09-21 | 2016-09-21 | Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106477880B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019142936A1 (en) * | 2018-01-22 | 2019-07-25 | Ａｇｃ株式会社 | Ultraviolet ray-transmitting glass and molded article |
| TWI839128B (en) | 2022-03-24 | 2024-04-11 | 大陸商成都光明光電股份有限公司 | Glass, glass components and filters |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-09-21 CN CN201610838146.2A patent/CN106477880B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| DANDAN FENG ETC.: "Investigations on the photoluminescence spectra and its defect-related nature for the ultraviolet transmitting fluoride-containing phosphate-based glasses", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
| QUANLONG HE ETC.: "Investigations on the photoluminescence of the iron and cobalt doped fluoride-containing phosphate-based glasses and its defects-related nature", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019142936A1 (en) * | 2018-01-22 | 2019-07-25 | Ａｇｃ株式会社 | Ultraviolet ray-transmitting glass and molded article |
| CN111587230A (en) * | 2018-01-22 | 2020-08-25 | Ａｇｃ株式会社 | Ultraviolet-transmitting glass and molded article |
| US20200277220A1 (en) * | 2018-01-22 | 2020-09-03 | AGC Inc. | Uv-transmitting glass and molded products |
| JPWO2019142936A1 (en) * | 2018-01-22 | 2021-01-07 | Ａｇｃ株式会社 | UV transparent glass and molded products |
| JP7268606B2 (en) | 2018-01-22 | 2023-05-08 | Ａｇｃ株式会社 | Method for manufacturing ultraviolet transmitting glass |
| TWI839128B (en) | 2022-03-24 | 2024-04-11 | 大陸商成都光明光電股份有限公司 | Glass, glass components and filters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106477880B (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10106456B2 (en) | Glass and glass ceramic | |
| US5420080A (en) | Wavelength up-conversion transparent glass ceramics | |
| WO2011132786A1 (en) | Uv-transmitting near-infrared cut-off filter glass | |
| KR102551614B1 (en) | Glass composition, glass with low inclusion content, manufacturing method thereof and application thereof | |
| CN1308591A (en) | Tantalum containing glasses and glass ceramics | |
| TW201739712A (en) | Lanthanum flint optical glass | |
| JP2020002010A (en) | Optical glass and optical element | |
| CN105236733B (en) | A kind of preparation method of the low niobium optical glass of high lanthanum of titaniferous | |
| CN104961343A (en) | Rare-earth-doped microcrystalline glass separating out NaYF4 nanocrystalline and manufacturing method thereof | |
| Zmojda et al. | Investigation of upconversion luminescence in Yb3+/Tm3+/Ho3+ triply doped antimony-germanate glass and double-clad optical fiber | |
| CN105000801B (en) | A kind of ultraviolet, high damage threshold fluophosphate laser glass and preparation method thereof | |
| WO2013191270A1 (en) | Glass and optical element production method | |
| JP7003198B2 (en) | Glass, press-molded glass materials, optics blanks, and optics | |
| JP5793164B2 (en) | Glass, optical glass, glass material for press molding and optical element | |
| CN102557430B (en) | Method for preparing high-damage-threshold laser window material | |
| TWI771744B (en) | Optical glass and optical components | |
| CN106477880B (en) | Low fluorine-containing two double-frequency laser color separation glass of phosphate of one kind and preparation method thereof | |
| WO2021171950A1 (en) | Optical glass and optical element | |
| CN106495471B (en) | Low fluorine-containing phosphate basic frequency laser color separation glass of one kind and preparation method thereof | |
| CN101269913B (en) | Yb<3+> doped fluorine phosphorous glass with high crystallization stability and preparing method thereof | |
| JP2018002520A (en) | Optical glass, optical element blank and optical element | |
| Zhou et al. | Influence of CaF2 addition on structure and luminescence properties of the Na2O–CaO–SiO2–Al2O3–ZnO–P2O5 glass co-doped with Ce3+/Yb3+ | |
| Guo et al. | Investigation on local structure surrounding erbium cations in fluoride glasses with TeO2 introduction for 2.7 μm emission | |
| CN110015845B (en) | Optical glass and optical element | |
| Arbuzov et al. | Optical, spectral, and radiation-shielding properties of high-lead phosphate glasses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |