CN105601106B - Neodymium-doped fluorphosphate glass and preparation method thereof - Google Patents

Neodymium-doped fluorphosphate glass and preparation method thereof Download PDF

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CN105601106B
CN105601106B CN201610021399.0A CN201610021399A CN105601106B CN 105601106 B CN105601106 B CN 105601106B CN 201610021399 A CN201610021399 A CN 201610021399A CN 105601106 B CN105601106 B CN 105601106B
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glass
neodymium
doped
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fluophosphate
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CN105601106A (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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    • 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

A kind of neodymium-doped fluophosphate laser glass and preparation method thereof, the glass are mainly made up of the phosphate of low content and the divalence of high content and trivalent metal fluorides, and the Mole percent composition of the cation of the glass is：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 be 82.49~82.59%.Compared with existing neodymium-doped fluophosphate laser glass, neodymium-doped fluorphosphate glass of the present invention have it is excellent into glass properties, high fluorescence, life-span be low, nonlinear factor and the characteristics of alkali-free, amplify suitable for solid-state laser.

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, the neodymium-doped fluorine phosphorus Silicate glass have it is excellent into glass properties, high fluorescence, life-span be low, nonlinear factor and the characteristics of alkali-free, swash suitable for solid-state Light amplification.
Background technology
Neodymium doped phosphate glass is current device superlaser fusion system big in the world uniquely widely used working substance Matter, main function are that enough energy storage and gain are provided for laser aid laser amplifier.Wherein Nd3+The ion fluorescence life-span is important One of gain performance parameter, and nonlinear refractive index n2Also it is one of important output performance parameter.Compared to neodymium-doped phosphoric acid Salt glass, neodymium-doped fluorphosphate glass have that refractive index and nonlinear refractive index are low and the characteristics of fluorescence lifetime is high, wherein, low folding The rate of penetrating is advantageous to suppress amplified spontaneous emission effect (ASE) inside neodymium glass；Low nonlinearity refractive index and high fluorescence lifetime are favourable In raising device output performance by a relatively large margin.United States Patent (USP) 4,120,814 and 4,225,459 reports the low n of series2Neodymium-doped fluorine Phosphorus glass, it is characterized in that n2=0.6-0.7, the alkali metal fluoride containing 2-15wt% is to reduce nonlinear refractive index.Alkali gold The presence of category fluoride can reduce the transition temperature and thermal stability of glass, not only cause glass easy under high power state Destroy, and it is difficult glass is faced very big preparation when prepared by the equal large scale of bloom.
The content of the invention
It is it is an object of the invention to provide a kind of neodymium-doped fluophosphate laser glass and preparation method thereof, the characteristics of the glass With low nonlinearity coefficient, high fluorescence lifetime, large scale preparation is easily carried out, is had excellent into glass properties and good analysis Brilliant stability.Meet the requirement of high energy laser system energy storage and amplification.
The technical solution of the present invention is as follows：
A kind of neodymium-doped fluophosphate laser glass, its feature are the glass mainly by the phosphate and high content of low content Divalence and trivalent metal fluorides composition, the cation of the glass Mole percent composition is：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+：0.5~1.6, F-/(F-+O2-) mol ratio be 82.49~82.59%.
The preparation method of described neodymium-doped fluophosphate laser glass, its feature are that this method comprises the following steps：
1) first with Al (PO3)3、Sr(H2PO4)2、Ba(PO3)2、MgF2、CaF2、SrF2、 BaF2、AlF3、YF3And NdF3Make To introduce the raw material of the ion, molar percentage and the choosing of the described cation of neodymium-doped fluophosphate laser glass composition are selected Surely the raw material of ion is introduced, glass powder is weighed, stirs to form glass batch；
2) described batch is added into progress clinker in platinum crucible to found, melting temperature is 1050 DEG C, is melted Glass metal is poured into the large scale platinum crucible of sealing, and metal level leads to nitrogen protection, after glass metal is clarified 60 minutes, is cooled to 730 DEG C are stirred 6 hours, and mixing speed is 80 revs/min；680 DEG C are at the uniform velocity cooled to afterwards is incubated 30 minutes, while leaf oar rotating speed 20 revs/min are down to, then material leakage is molded on 350 DEG C of cast iron die is preheated to；
3) glass poured into a mould is put into and had warmed up into 450 DEG C of Muffle furnace, 8 hours are incubated, with 1 DEG C/h of speed Degree is annealed to 300 DEG C, is then annealed to room temperature with 5 DEG C/h of speed.
Experiment shows, is the characteristics of glass system of the present invention, while high fluorescence lifetime and low nonlinearity is maintained, glass Glass has well into glass properties, outstanding crystallization stability energy and the higher transition temperature than neodymium doped phosphate glass. Sample cast thickness is when be 6cm, found and forming process in without crystallization appearance.
Beneficial effects of the present invention are：
Nd3+Fluorescence lifetime of the ion in body series is 336-530 μ s, nonlinear refractive index n2For 0.58-0.6 × 1013esu.Glass transformation temperature is 457-459 DEG C, and crystallization property is outstanding, and viscograph shows that it has good viscosity characteristicses.
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
Embodiment
The present invention is further elaborated with reference to embodiments.
The cation mole percentage composition of 5 embodiment glass of neodymium-doped fluophosphate laser glass of the present invention and F-/(F-+ O2-) mol ratio is as shown in table 1.The Nd of corresponding glass is given in table3+Ion concentration, fluorescence lifetime, n2And transition temperature.
The cation mole percentage composition of the neodymium-doped fluorphosphate glass embodiment of table 1 and property
Component (mol%) 1# 2# 3# 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
Tg/ DEG C of transition temperature 457 457 458 459 459
Embodiment 1：
The first step, 1# glass formulas are chosen according to table 1, and following molfraction is used according to cation mole percentage composition Raw material weighs 8kg powders：1Al(PO3)3,1Ba(PO3)2, 3.05Sr(H2PO4)2, 27.6AlF3,7.8MgF2, 19.1CaF2, 16.05SrF2, 8.5BaF2, 3.5YF3, 0.2NdF3, batch is stirred.
Second step, batch is added into progress clinker in platinum crucible and founded, melting temperature is 1050 DEG C.The glass melted Glass liquid is poured into the large scale platinum crucible of sealing, and metal level leads to nitrogen protection.After glass metal is clarified 60 minutes, it is cooled to 730 DEG C are stirred 6 hours, and mixing speed is 80 revs/min；680 DEG C are at the uniform velocity cooled to afterwards is incubated 30 minutes, while leaf oar rotating speed 20 revs/min are down to, then material leakage is molded on 350 DEG C of cast iron die is preheated to；
3rd step, the glass poured into a mould is put into and had warmed up into 450 DEG C of Muffle furnace, 8 hours are incubated, with 1 DEG C/h Speed be annealed to 300 DEG C, room temperature is then annealed to 5 DEG C/h of speed.
Embodiment 2：
The first step, 3# glass formulas are chosen according to table 1, and following molfraction is used according to cation mole percentage composition Raw material weighs 8kg powders：1Al(PO3)3,1Ba(PO3)2, 3.05Sr(H2PO4)2, 27.5AlF3,7.8MgF2, 19.0CaF2, 15.95SrF2, 8.5BaF2, 3.5YF3, 0.8NdF3, batch is stirred.
Second step, batch is added into progress clinker in platinum crucible and founded, melting temperature is 1050 DEG C.Melt Glass metal is poured into the large scale platinum crucible of sealing, and metal level leads to nitrogen protection.After glass metal is clarified 60 minutes, it is cooled to 730 DEG C are stirred 6 hours, and mixing speed is 80 revs/min；680 DEG C are at the uniform velocity cooled to afterwards is incubated 30 minutes, while leaf oar rotating speed 20 revs/min are down to, then material leakage is molded on 350 DEG C of cast iron die is preheated to；
3rd step, the glass poured into a mould is put into and had warmed up into 450 DEG C of Muffle furnace, be incubated 8 hours, with 1 DEG C/it is small When speed be annealed to 300 DEG C, room temperature is then annealed to 5 DEG C/h of speed.
Embodiment 3：
The first step, 5# glass formulas are chosen according to table 1, and following molfraction is used according to cation mole percentage composition Raw material weighs 8kg powders：1Al(PO3)3,1Ba(PO3)2,3Sr(H2PO4)2, 27.2AlF3,7.7MgF2, 18.8CaF2, 15.8SrF2, 8.4BaF2, 3.4YF3, 1.6NdF3, batch is stirred.
Second step, batch is added into progress clinker in platinum crucible and founded, melting temperature is 1050 DEG C.Melt Glass metal is poured into the large scale platinum crucible of sealing, and metal level leads to nitrogen protection.After glass metal is clarified 60 minutes, it is cooled to 730 DEG C are stirred 6 hours, and mixing speed is 80 revs/min；680 DEG C are at the uniform velocity cooled to afterwards is incubated 30 minutes, while leaf oar rotating speed 20 revs/min are down to, then material leakage is molded on 350 DEG C of cast iron die is preheated to；
3rd step, the glass poured into a mould is put into and had warmed up into 450 DEG C of Muffle furnace, be incubated 8 hours, with 1 DEG C/it is small When speed be annealed to 300 DEG C, room temperature is then annealed to 5 DEG C/h of speed.
After tested, the Nd of glass3+Ion concentration, fluorescence lifetime, n2And transition temperature is as shown in table 1.Experiment shows, this hair Bright neodymium-doped fluorphosphate glass have it is excellent into glass properties, high fluorescence, life-span be low, nonlinear factor and the characteristics of alkali-free, fit Amplify for solid-state laser.

Claims (2)

1. a kind of neodymium-doped fluophosphate laser glass, it is characterised in that the glass is mainly by a small amount of phosphate and divalence and trivalent gold Belong to fluoride composition, the molar percentage composition of the cation of the glass is：
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+：0.5~1.6, F-/(F-+O2-) mol ratio be 82.49~82.59%.
2. the preparation method of the neodymium-doped fluophosphate laser glass described in claim 1, it is characterised in that this method includes following Step：
1) first with Al (PO3)3、Sr(H2PO4)2、Ba(PO3)2、MgF2、CaF2、SrF2、BaF2、AlF3、YF3And NdF3As drawing Enter the raw material of the ion, select moles the hundred of the cation that neodymium-doped fluophosphate laser glass composition is described in claim 1 Divide the raw material for comparing and selecting and introduce ion, weigh glass powder, stir to form glass batch；
2) described batch is added into progress clinker in platinum crucible to found, melting temperature is 1050 DEG C, the glass melted Liquid is poured into the large scale platinum crucible of sealing, and metal level leads to nitrogen protection, after glass metal is clarified 60 minutes, is cooled to 730 DEG C stirring 6 hours, mixing speed be 80 revs/min；680 DEG C are at the uniform velocity cooled to afterwards and is incubated 30 minutes, while leaf oar rotating speed is down to 20 revs/min, then material leakage is molded on 350 DEG C of cast iron die is preheated to；
3) glass poured into a mould is put into and had warmed up into 450 DEG C of Muffle furnace, be incubated 8 hours, moved back with 1 DEG C/h of speed Then fire is annealed to room temperature to 300 DEG C with 5 DEG C/h of speed.
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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
CN109206008B (en) * 2018-10-31 2021-07-27 成都光明光电有限责任公司 Laser neodymium glass doped with fluorophosphate
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

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
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
掺Nd3+含磷氟铝酸盐玻璃光谱特性;裔关宏等;《硅酸盐通报》;19920430(第2期);第44-47页 *

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