CN105601106A - Neodymium-doped fluorophosphate glass and preparation method thereof - Google Patents

Neodymium-doped fluorophosphate glass and preparation method thereof Download PDF

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Publication number
CN105601106A
CN105601106A CN201610021399.0A CN201610021399A CN105601106A CN 105601106 A CN105601106 A CN 105601106A CN 201610021399 A CN201610021399 A CN 201610021399A CN 105601106 A CN105601106 A CN 105601106A
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glass
neodymium
doped
speed
preparation
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CN105601106B (en
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张丽艳
薛天峰
胡丽丽
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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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
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/80—Non-oxide glasses or glass-type compositions
    • C03B2201/82—Fluoride glasses, e.g. ZBLAN glass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to neodymium-doped fluorophosphate laser glass and a preparation method thereof. The glass mainly comprises low-content phosphate and high-content divalent and trivalent metal fluoride. The positive ions of the glass include, by mole percentage, 12.0-12.1% of P<5+>, 28.2-28.6% of Al<3+>, 7.7-7.8% of Mg<2+>, 18.8-19.1% of Ca<2+>, 18.8-19.1% of Sr<2+>, 9.4-9.5% of Ba<2+>, 3.4-3.5% of Y<3+>, 0.2-1.6% of Nd<3+> and 82.49-82.59% of F<->/(F<->+O<2->). Compared with existing neodymium-doped fluorophosphate laser glass, the neodymium-doped fluorophosphate glass is excellent in glass forming performance, long in fluorescence lifetime, low in nonlinear coefficient, free of alkali and applicable to solid-state laser amplification.

Description

Neodymium-doped fluorphosphate glass and preparation method thereof
Technical field
The present invention relates to laser glass, particularly a kind of neodymium-doped fluorphosphate glass and preparation method thereof,This neodymium-doped fluorphosphate glass has that good one-tenth glass properties, high fluorescence, life-span are low, nonlinear systemThe feature of number and alkali-free, is applicable to solid-state laser and amplifies.
Background technology
Neodymium doped phosphate glass is that bigger device superlaser fusion system is unique extensively in the world at presentThe operation material using, Main Function is to provide enough energy storage and increasings for laser aid laser amplifierBenefit. Wherein Nd3+The ion fluorescence life-span is one of important gain performance parameter, and nonlinear refractionRate n2Also be one of important output performance parameter. Than neodymium doped phosphate glass, neodymium-doped fluorine phosphorusSilicate glass has refractive index and nonlinear refractive index is low and fluorescence lifetime is high feature, wherein, lowRefractive index is conducive to suppress the inner amplified spontaneous emission effect of neodymium glass (ASE); Low nonlinearity refractionRate and high fluorescence lifetime are conducive to improve by a relatively large margin device output performance. United States Patent (USP) 4,120,814And 4,225,459 reported serial low n2Neodymium-doped fluorine phosphorous glass, is characterized by n2=0.6-0.7, containsThe alkali metal fluoride of 2-15wt% is to reduce nonlinear refractive index. The existence meeting of alkali metal fluorideReduce transition temperature and the thermal stability of glass, not only cause glass easy under high power stateDestroy, and make glass time prepared by the equal large scale of high light, face very large preparation difficulty.
Summary of the invention
The object of this invention is to provide a kind of neodymium-doped fluophosphate laser glass and preparation method thereof, shouldThe feature of glass is to have low nonlinearity coefficient, high fluorescence lifetime, easily carries out large scale preparation,There is good one-tenth glass properties and good crystallization stability energy. Meet high energy laser system energy storageWith the instructions for use of amplifying.
Technical solution of the present invention is as follows:
A kind of neodymium-doped fluophosphate laser glass, its feature is that this glass is mainly by the phosphorus of low contentThe divalence of hydrochlorate and high-load and trivalent metal fluoride composition, cationic mole hundred of this glassGrouping becomes: P5+：12.0～12.1，Al3+：28.2～28.6，Mg2+：7.7～7.8，Ca2+：18.8～19.1，Sr2+：18.8～19.1，Ba2+：9.4～9.5，Y3+：3.4～3.5，Nd3+：0.2～1.6，F-/(F-+O2-) mol ratio is 82.49～82.59%.
The preparation method of described neodymium-doped fluophosphate laser glass, its feature is that the method comprisesThe following step:
1) first with Al (PO3)3、Sr(H2PO4)2、Ba(PO3)3、MgF2、CaF2、SrF2、BaF2、AlF3、YF3And NdF3As the raw material of introducing described ion, selected neodymium-doped fluorophosphateThe cationic molar percentage that laser glass composition is described the selected raw material of introducing ion, takeGlass powder, stirs formation glass batch;
2) described batch is added and in platinum crucible, carry out grog and found, melt temperature is1050 DEG C, the glass metal melting pours in the large scale platinum crucible of sealing, and metal level leads to nitrogenGas protection, glass metal clarification, after 60 minutes, is cooled to 730 DEG C and stirs 6 hours, and mixing speed is80 revs/min; After be at the uniform velocity cooled to 680 DEG C of insulations 30 minutes, simultaneously leaf oar rotating speed is down to 20 and is turned/ minute, then on the cast iron die that is preheated to 350 DEG C, leak material moulding;
3) poured into a mould glass is put into the Muffle furnace that is warming up to 450 DEG C, is incubated 8 hours,Be annealed to 300 DEG C with the speed of 1 DEG C/h, be then annealed to room temperature with the speed of 5 DEG C/h.
Experiment shows, the feature of glass system of the present invention is to keep high fluorescence lifetime and low non-Linear time, glass has good one-tenth glass properties, outstanding crystallization stability energy and than mixingThe higher transition temperature of neodymium phosphate glass. When sample cast thickness is 6cm, found and mouldingIn process, all occur without crystallization.
Beneficial effect of the present invention is:
Nd3+The fluorescence lifetime of ion in body series is 336-530 μ s, nonlinear refractive index n2For0.58-0.6×1013Esu. Glass transformation temperature is 457-459 DEG C, and crystallization property is outstanding, viscographShow that it has good viscosity characteristics.
Brief description of the drawings
Fig. 1 is the DSC curve of alkali-free neodymium-doped fluophosphate laser glass of the present invention
Fig. 2 is the viscograph of alkali-free neodymium-doped fluophosphate laser glass of the present invention
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated.
The cation mole percentage group of 5 embodiment glass of neodymium-doped fluophosphate laser glass of the present inventionBecome and F-/(F-+O2-) mol ratio is as shown in table 1. In table, give the Nd of corresponding glass3+IonConcentration, fluorescence lifetime, n2And transition temperature.
Cation mole percentage composition and the character of table 1 neodymium-doped fluorphosphate glass embodiment
Component (mol%) 1# 2# 3# 4#4 5#
P5+ 12.1 12.1 12.1 12.03 12.0
Al3+ 28.6 28.5 28.5 28.3 28.2
Mg2+ 7.8 7.8 7.8 7.7 7.7
Ca2+ 19.1 19.0 19.0 18.9 18.8
Sr2+ 19.1 19.0 19.0 18.9 18.8
Ba2+ 9.5 9.5 9.5 9.4 9.4
Y3+ 3.5 3.5 3.5 3.4 3.4
Nd3+ 0.2 0.5 0.8 1.3 1.6
F-/(F-+O2-) 82.49 82.51 82.54 82.57 82.59
Nd3+Ion concentration ions/cm3 0.54 1.24 2.0 3.12 3.5
Fluorescence lifetime/μ s 530 505 475 394 336
nd 1.45826 1.45829 1.45833 1.45842 1.45844
n2/1013esu 0.58 0.58 0.59 0.59 0.60
Transition temperature Tg/ DEG C 457 457 458 459 459
Embodiment 1:
The first step, chooses 1# glass formula according to table 1, and according to cation, mole percentage composition is usedThe raw material of following molfraction takes 8kg powder: 1Al (PO3)3,1Ba(PO3)3,3.05Sr(H2PO4)2，27.6AlF3,7.8MgF2，19.1CaF2，16.05SrF2，8.5BaF2，3.5YF3，0.2NdF3, batch is stirred.
Second step, adds batch in platinum crucible, to carry out grog and found, and melt temperature is1050 DEG C. The glass metal melting pours in the large scale platinum crucible of sealing, and metal level leads to nitrogenGas protection. Glass metal clarification, after 60 minutes, is cooled to 730 DEG C and stirs 6 hours, and mixing speed is80 revs/min; After be at the uniform velocity cooled to 680 DEG C of insulations 30 minutes, simultaneously leaf oar rotating speed is down to 20 and is turned/ minute, then on the cast iron die that is preheated to 350 DEG C, leak material moulding;
The 3rd step, puts into poured into a mould glass the Muffle furnace that is warming up to 450 DEG C, is incubated 8 hours,Be annealed to 300 DEG C with the speed of 1 DEG C/h, be then annealed to room temperature with the speed of 5 DEG C/h.
Embodiment 2:
The first step, chooses 3# glass formula according to table 1, and according to cation, mole percentage composition is usedThe raw material of following molfraction takes 8kg powder: 1Al (PO3)3,1Ba(PO3)3,3.05Sr(H2PO4)2，27.5AlF3,7.8MgF2，19.0CaF2，15.95SrF2，8.5BaF2，3.5YF3，0.8NdF3, batch is stirred.
Second step, adds batch in platinum crucible, to carry out grog and found, and melt temperature is1050 DEG C. The glass metal melting pours in the large scale platinum crucible of sealing, and metal level leads to nitrogenGas protection. Glass metal clarification, after 60 minutes, is cooled to 730 DEG C and stirs 6 hours, and mixing speed is80 revs/min; After be at the uniform velocity cooled to 680 DEG C of insulations 30 minutes, simultaneously leaf oar rotating speed is down to 20 and is turned/ minute, then on the cast iron die that is preheated to 350 DEG C, leak material moulding;
The 3rd step, puts into poured into a mould glass the Muffle furnace that is warming up to 450 DEG C, insulation 8Hour, be annealed to 300 DEG C with the speed of 1 DEG C/h, be then annealed to the speed of 5 DEG C/hRoom temperature.
Embodiment 3:
The first step, chooses 5# glass formula according to table 1, and according to cation, mole percentage composition is usedThe raw material of following molfraction takes 8kg powder: 1Al (PO3)3,1Ba(PO3)3,3Sr(H2PO4)2，27.2AlF3,7.7MgF2，18.8CaF2，15.8SrF2，8.4BaF2，3.4YF3，1.6NdF3, willBatch stirs.
Second step, adds batch in platinum crucible, to carry out grog and found, and melt temperature is1050 DEG C. The glass metal melting pours in the large scale platinum crucible of sealing, and metal level leads to nitrogenGas protection. Glass metal clarification, after 60 minutes, is cooled to 730 DEG C and stirs 6 hours, and mixing speed is80 revs/min; After be at the uniform velocity cooled to 680 DEG C of insulations 30 minutes, simultaneously leaf oar rotating speed is down to 20 and is turned/ minute, then on the cast iron die that is preheated to 350 DEG C, leak material moulding;
The 3rd step, puts into poured into a mould glass the Muffle furnace that is warming up to 450 DEG C, insulation 8Hour, be annealed to 300 DEG C with the speed of 1 DEG C/h, be then annealed to the speed of 5 DEG C/hRoom temperature.
After tested, the Nd of glass3+Ion concentration, fluorescence lifetime, n2And transition temperature is as table 1Show. Experiment shows, neodymium-doped fluorphosphate glass of the present invention have good one-tenth glass properties, high fluorescence,The feature of low, nonlinear factor of life-span and alkali-free, is applicable to solid-state laser and amplifies.

Claims (2)

1. a neodymium-doped fluophosphate laser glass, is characterized in that this glass is mainly by a small amount of phosphoric acidSalt and divalence and trivalent metal fluoride composition, the cationic molar percentage of this glass consists of:
P5+：12.0～12.1，Al3+：28.2～28.6，Mg2+：7.7～7.8，Ca2+：18.8～19.1，Sr2+：18.8～19.1，Ba2+：9.4～9.5，Y3+：3.4～3.5，Nd3+：0.2～1.6，F-/(F-+O2-) mol ratio is 82.49～82.59%
2. the preparation method of neodymium-doped fluophosphate laser glass claimed in claim 1, its feature existsComprise the following steps: in the method
1) first with Al (PO3)3、Sr(H2PO4)2、Ba(PO3)3、MgF2、CaF2、SrF2、BaF2、AlF3、YF3And NdF3As the raw material of introducing described ion, in selected claim 1The cationic molar percentage that neodymium-doped fluophosphate laser glass composition is described the selected ion of introducingRaw material, take glass powder, stir formation glass batch;
2) described batch is added and in platinum crucible, carry out grog and found, melt temperature is1050 DEG C, the glass metal melting pours in the large scale platinum crucible of sealing, and metal level leads to nitrogenGas protection, glass metal clarification, after 60 minutes, is cooled to 730 DEG C and stirs 6 hours, and mixing speed is80 revs/min; After be at the uniform velocity cooled to 680 DEG C of insulations 30 minutes, simultaneously leaf oar rotating speed is down to 20 and is turned/ minute, then on the cast iron die that is preheated to 350 DEG C, leak material moulding;
3) poured into a mould glass is put into the Muffle furnace that is warming up to 450 DEG C, is incubated 8 hours,Be annealed to 300 DEG C with the speed of 1 DEG C/h, be then annealed to room temperature with the speed of 5 DEG C/h.
CN201610021399.0A 2016-01-13 2016-01-13 Neodymium-doped fluorphosphate glass and preparation method thereof Active CN105601106B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109095755A (en) * 2018-08-16 2018-12-28 中国建筑材料科学研究总院有限公司 The processing method of glass preform
CN113024111A (en) * 2021-03-17 2021-06-25 中国科学院上海光学精密机械研究所 Nd for improving 900nm fluorescence intensity3+Doped quartz glass and preparation method thereof
CN113264677A (en) * 2018-10-31 2021-08-17 成都光明光电有限责任公司 Laser neodymium glass doped with fluorophosphate

Citations (3)

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Publication number Priority date Publication date Assignee Title
US4120814A (en) * 1977-02-28 1978-10-17 Hoya Corporation Fluorophosphate-base laser glasses
CN102211872A (en) * 2011-03-23 2011-10-12 中国科学院上海光学精密机械研究所 3 mu m luminous rare earth ion doped fluorophosphate laser glass and preparation method thereof
CN103011588A (en) * 2007-03-06 2013-04-03 Hoya株式会社 Optical glass, preform for press forming, optical element, and processes for producing these

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120814A (en) * 1977-02-28 1978-10-17 Hoya Corporation Fluorophosphate-base laser glasses
CN103011588A (en) * 2007-03-06 2013-04-03 Hoya株式会社 Optical glass, preform for press forming, optical element, and processes for producing these
CN102211872A (en) * 2011-03-23 2011-10-12 中国科学院上海光学精密机械研究所 3 mu m luminous rare earth ion doped fluorophosphate laser glass and preparation method thereof

Non-Patent Citations (1)

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Title
裔关宏等: "掺Nd3+含磷氟铝酸盐玻璃光谱特性", 《硅酸盐通报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109095755A (en) * 2018-08-16 2018-12-28 中国建筑材料科学研究总院有限公司 The processing method of glass preform
CN113264677A (en) * 2018-10-31 2021-08-17 成都光明光电有限责任公司 Laser neodymium glass doped with fluorophosphate
CN113024111A (en) * 2021-03-17 2021-06-25 中国科学院上海光学精密机械研究所 Nd for improving 900nm fluorescence intensity3+Doped quartz glass and preparation method thereof
CN113024111B (en) * 2021-03-17 2022-11-08 中国科学院上海光学精密机械研究所 Nd for improving 900nm fluorescence intensity 3+ Doped quartz glass and preparation method thereof

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