CN102260042B - Bismuth-doped phosphate optical glass and preparation method thereof - Google Patents
Bismuth-doped phosphate optical glass and preparation method thereof Download PDFInfo
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- CN102260042B CN102260042B CN201110131171.4A CN201110131171A CN102260042B CN 102260042 B CN102260042 B CN 102260042B CN 201110131171 A CN201110131171 A CN 201110131171A CN 102260042 B CN102260042 B CN 102260042B
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- glass
- bismuth
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- 239000005304 optical glass Substances 0.000 title claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 12
- 239000010452 phosphate Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 22
- 229910017119 AlPO Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000005086 pumping Methods 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 101100194003 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) rco-3 gene Proteins 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 229910000149 boron phosphate Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000003321 amplification Effects 0.000 description 7
- 238000003199 nucleic acid amplification method Methods 0.000 description 7
- 239000013307 optical fiber Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- -1 ytterbium rare earth ion Chemical class 0.000 description 2
- CWCCJSTUDNHIKB-UHFFFAOYSA-N $l^{2}-bismuthanylidenegermanium Chemical compound [Bi]=[Ge] CWCCJSTUDNHIKB-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 1
- LFTVQMXNFSJCFX-UHFFFAOYSA-N bismuth ytterbium Chemical compound [Yb].[Bi] LFTVQMXNFSJCFX-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000006017 silicate glass-ceramic Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Glass Compositions (AREA)
Abstract
The invention provides a method for preparing bismuth-doped phosphate-based optical glass by using a machine, which comprises the following steps of: preparing and uniformly mixing 44.9 to 75 molar percent of BPO4, 0 to 35 molar percent of AlPO4, 20 to 45 molar percent of RO and/or RCO3 and 0.1 to 5 molar percent of Bi2O3; raising the temperature of a mixture to be between 1,150 and 1,400 DEG C, and preserving heat for 30 to 180 minutes to make raw materials melted into liquid; and quickly pouring a melt, flattening, annealing at the temperature of between 500 and 600 DEG C for 0.5 to 6 hours, and naturally cooling to room temperature to obtain the bismuth-doped phosphate-based optical glass. Strong near infrared ultra-wideband fluorescence can be obtained by laser pumping, the melting temperature is obviously reduced compared with that of quartz glass, micro-crystallization is not needed, and the glass has high mechanical strength, and optical property of covering ultra wideband in the whole communication waveband, and is expected to be applied to the technical fields of ultra-wideband optical amplifiers, high-power lasers, tunable lasers and the like.
Description
Technical field
The present invention relates to opticglass, particularly a kind of phosphate optical glass of mixing bismuth and preparation method thereof.
Background technology
On March 4th, 1998, the quiet patent (special permission discloses flat 11-29334) that waits the people to apply for being entitled as " mixing secret silica glass, optical fiber and image intensifer manufacture method " of the liana of Mitsubishi Cable Ind Ltd.They utilize the zeolite of bismuth exchange as dispersion medium, and comprehensive sol-gel method and high-temperature melting method have prepared under the air and mixed the secret ion Bi of pentavalent
5+Silica glass, draw out corresponding optical fiber, realized the light amplification at 1.3 μ m places under the 800nm pumping.The photoluminescence peak of this glass is positioned near the 1130nm, and maximum fluorescence halfwidth is 250nm, and maximum fluorescence lifetime is 650 μ s, and stimulated emission cross section is approximately 1.0 * 10-20cm
2. on February 22 calendar year 2001, liana is quiet to wait the people to apply for being entitled as " optical fiber and image intensifer " (the open 2002-252397 of special permission) again, and its basic glass consists of: A1
2O
3-SiO
2-Bi
2O
3, under the 1750oC air, found, draw out corresponding optical fiber, realized the light amplification at 1.3 μ m places under the 0.8 μ m pumping.
December 13 calendar year 2001, on June 18th, 2002, on December 25th, 2002, this positive first-class of the bank of Nippon Sheet Glass Co Ltd has applied for being entitled as patent (the open 2003-183047 of special permission of " red glass and transparent glass-ceramics thereof ", " light amplification glass optical fiber ", " infrared lumious material and optical amplification medium " continuously, 2004-20994,2003-283028), its basic glass consists of A1
2O
3-SiO
2Corresponding product presents red or red-brown; Red glass its color after crystallization is handled does not have obvious change, but character such as its thermotolerance and physical strength obviously strengthen; Pumping wavelength pumping with being positioned at the 400-850nm zone can access the fluorescence that highest peak is positioned at the 1000-1600nm interval, and can realize the light amplification of wavelength between 1000-1400nm.
Calendar year 2001, Fujimoto and Nakatsuka be at Jpn. J. App. Phys., 40, (2001) L279 one literary composition reported under the 1760oC high temperature under air preparation pentavalent bismuth ion Bi
5+The A1 that mixes
2O
3-SiO
2Glass, a large amount of bubble exist make its transmitance at infrared region be reduced to ~ about 30%, this has limited this SiO to a great extent
2The practical application of base glass.The Qiu Jianrong of Zhejiang University etc. has applied for a series of being entitled as " Ytterbium-bismuth co-doped phosphate base opticglass and preparation method thereof " continuously, " nano bismuth cluster doped silicon dioxide base optical glass and preparation method thereof ", " bismuth ion doped crystal that is used for tunable laser and broad band amplifier ", " mix the preparation method of bismuth germanium base optical glass bismuth blended high silicon oxygen near-infrared super-broadband emission glass ", " bismuth-nickel co-doped transparent silicate glass-ceramics and preparation method thereof " (patent publication No. 200710044174.8,200510024483.X, 200510023597.2,200410054216.2,200410054217.7,200710047760.8) and about the patent of bismuth doped-glass as the light amplification material.
The mode that they utilize transition metal ions such as nickel or erbium/ytterbium rare earth ion to mix altogether in above-mentioned patent improves the infraluminescence intensity of bismuth, and by adopting germanate and phosphate system to improve the glass melting temperature of glass, improve the physical strength of glass by micritization.Yet the infraluminescence intensity of original bismuth doped-glass is compared with the rare earth ion as fiber amplifier, relatively a little less than, be unfavorable for using as the image intensifer material; Though can improve glass intensity and glass is carried out micritization, the crystallite that forms in the glass matrix causes reflection and the refraction of light in glass easily, causes light transmissioning efficiency to reduce, and the light amplification effect weakens.
Summary of the invention
Higher for the melt temperature that overcomes above-mentioned silica glass, and need micritization to improve the shortcoming of glass machinery intensity, the invention provides a kind of phosphate optical glass of mixing bismuth and preparation method thereof, realize by following technical proposal.
A kind of phosphate base opticglass of mixing bismuth, formed by the component of following molar percentage:
BPO
4 44.9~75%
AlPO
4 0~35%
RO 10~45%
Bi
2O
3 0.1~5%。
Another purpose of the present invention is to provide a kind of preparation method who mixes the phosphate base opticglass of bismuth, following each processing step of process:
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 44.9~75%
AlPO
4 0~35%
RO and/or RCO
310 ~ 45%
Bi
2O
3 0.1~5%；
(2) compound in the step (1) is warming up to 1100 ~ 1400oC, is incubated 30 ~ 180 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, after under 400 ~ 600oC, annealing 0.5 ~ 6 hour, naturally cool to room temperature, namely get the silicophosphate base optical glass of mixing bismuth.
Described RO is MgO, CaO, SrO, BaO, PbO, one or several among the ZnO.
Described RCO
3Be MgCO
3, CaCO
3, SrCO
3, BaCO
3, PbCO
3, ZnCO
3In one or several.
The present invention has following advantage: this glass is except having the optical property of the ultra broadband that can cover whole communication band, its melt temperature obviously reduces with respect to silica glass, melt liquid viscosity reduces in the glass smelting process, thereby the defective in the glass and flaw (as bubble etc.) are less with respect to silica glass in the melt molding process, the mechanical property of glass improves, and the infraluminescence intensity of bismuth in glass is stronger.This glass can be sent out near-infrared band fluorescence, has stronger luminous intensity, long fluorescence lifetime, and wide gain bandwidth is suitable as gain media and is applied to optical amplifier and/or laser apparatus.This glass melting temperature obviously reduces with respect to silica glass, thereby the viscosity of molten mass reduces, eliminating influence of air bubbles will easier realization, and glass has physical strength preferably simultaneously.The phosphate glass that above-mentioned bismuth mixes has the optical property of the ultra broadband that can cover 900 ~ 1700 nm wave bands under the laser excitation of 800 nm wavelength around, under 700 nm wavelength around laser excitations, can produce and cover 850 ~ 1450 nm wave bands, central peak is positioned at the ultra broadband near-infrared fluorescent of 1100 nm, be expected at ultra broadband optics amplifier, superpower laser, technical fields such as tunable laser are applied.
Embodiment
Be described further below in conjunction with the present invention of embodiment.
Embodiment 1
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 44.9%
AlPO
4 15%
CaCO
3 10%
Bi
2O
3 0.1%；
(2) compound in the step (1) is warming up to 1100oC, is incubated 60 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, annealing naturally cooled to room temperature after 3 hours under 550oC, namely got the silicophosphate base optical glass of mixing bismuth, was made up of the component of following molar percentage: BPO
4: 44.9%; AlPO
4: 15%; CaO:40%; Bi
2O
3: 0.1%.
Embodiment 2
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 60%
ZnCO
3 40%
MgO 5%
Bi
2O
3 1%；
(2) compound in the step (1) is warming up to 1200oC, is incubated 120 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, annealing naturally cooled to room temperature after 3 hours under 570oC, namely got the silicophosphate base optical glass of mixing bismuth, was made up of the component of following molar percentage: BPO
4: 60%; CaO:40%; MgO:5%; Bi
2O
3: 1%.
Embodiment 3
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 75%
AlPO
4 5%
BaCO
3 10%
PbO 10%
ZnO 5%
Bi
2O
3 5%；
(2) compound in the step (1) is warming up to 1400oC, is incubated 180 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, annealing naturally cooled to room temperature after 6 hours under 600oC, namely got the silicophosphate base optical glass of mixing bismuth, was made up of the component of following molar percentage: BPO
4: 75%; AlPO
4: 5%; BaO:10%; PbO:10%; Bi
2O
3: 5%.
Embodiment 4
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 50%
AlPO
4 35%
SrO 30%
Bi
2O
3 3%；
(2) compound in the step (1) is warming up to 1300oC, is incubated 30 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, annealing naturally cooled to room temperature after 0.5 hour under 400oC, namely got the silicophosphate base optical glass of mixing bismuth, was made up of the component of following molar percentage: BPO
4: 50%; AlPO
4: 35%; SrO:30%; Bi
2O
3: 3%.
Embodiment 5
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 70%
AlPO
4 25%
CaO 10%
BaO 10%
MgCO
3 10%
SrCO
3 10%
PbCO
3 5%
Bi
2O
3 3%；
(2) compound in the step (1) is warming up to 1400oC, is incubated 90 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, annealing naturally cooled to room temperature after 4 hours under 560oC, namely got the silicophosphate base optical glass of mixing bismuth, was made up of the component of following molar percentage: BPO
4: 70%; AlPO
4: 25%; CaO:10%; BaO:10%; MgO:10%; SrO:10%; PbO:5%; Bi
2O
3: 3%.
Claims (2)
1. phosphate base opticglass of mixing bismuth is characterized in that being made up of the component of following molar percentage:
BPO
4 44.9~75%
AlPO
4 0~35%
RO 20~45%
Bi
2O
3 0.1~5%
Wherein, RO is MgO, CaO, SrO, BaO, one or several among the PbO.
2. preparation method who mixes the phosphate base opticglass of bismuth is characterized in that through following each processing step:
(1) get the raw materials ready by following molar percentage, and mix:
BPO
4 44.9~75%
AlPO
4 0~35%
RO and/or RCO
320 ~ 45%
Bi
2O
3 0.1~5%；
Wherein, RO is MgO, CaO, SrO, BaO, one or several among the PbO; RCO
3Be MgCO
3, CaCO
3, SrCO
3, BaCO
3, PbCO
3In one or several;
(2) compound in the step (1) is warming up to 1150 ~ 1400oC, is incubated 30 ~ 180 minutes, make raw materials melt become liquid;
(3) melt in the step (2) is toppled over fast and flatten, after under 500 ~ 600oC, annealing 0.5 ~ 6 hour, naturally cool to room temperature, namely get the silicophosphate base optical glass of mixing bismuth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110131171.4A CN102260042B (en) | 2011-05-20 | 2011-05-20 | Bismuth-doped phosphate optical glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110131171.4A CN102260042B (en) | 2011-05-20 | 2011-05-20 | Bismuth-doped phosphate optical glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102260042A CN102260042A (en) | 2011-11-30 |
| CN102260042B true CN102260042B (en) | 2013-09-11 |
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918080A (en) * | 2004-02-18 | 2007-02-21 | 日本板硝子株式会社 | Glass composition that emits fluorescence in infrared wavelength region and method of amplifying signal light using the same |
| CN101117271A (en) * | 2007-07-25 | 2008-02-06 | 中国科学院上海光学精密机械研究所 | Ytterbium-bismuth co-doped phosphonate based optical glass and method for making same |
| CN101503276A (en) * | 2009-03-11 | 2009-08-12 | 昆明理工大学 | Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10311820A1 (en) * | 2003-03-13 | 2004-09-30 | Schott Glas | Semiconductor light source used in lighting comprises a semiconductor emitter, especially an LED, and a luminescent glass body |
-
2011
- 2011-05-20 CN CN201110131171.4A patent/CN102260042B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918080A (en) * | 2004-02-18 | 2007-02-21 | 日本板硝子株式会社 | Glass composition that emits fluorescence in infrared wavelength region and method of amplifying signal light using the same |
| CN101117271A (en) * | 2007-07-25 | 2008-02-06 | 中国科学院上海光学精密机械研究所 | Ytterbium-bismuth co-doped phosphonate based optical glass and method for making same |
| CN101503276A (en) * | 2009-03-11 | 2009-08-12 | 昆明理工大学 | Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof |
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| Publication number | Publication date |
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| CN102260042A (en) | 2011-11-30 |
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