CN101503276B - Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof - Google Patents
Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof Download PDFInfo
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- CN101503276B CN101503276B CN2009100941841A CN200910094184A CN101503276B CN 101503276 B CN101503276 B CN 101503276B CN 2009100941841 A CN2009100941841 A CN 2009100941841A CN 200910094184 A CN200910094184 A CN 200910094184A CN 101503276 B CN101503276 B CN 101503276B
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- glass
- aluminum
- bismuth
- based optical
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000005304 optical glass Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- -1 strontium-aluminum-boron Chemical compound 0.000 title claims description 10
- 239000011521 glass Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 2
- 239000000377 silicon dioxide Substances 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910004116 SrO 2 Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 3
- 230000004907 flux Effects 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000004891 communication Methods 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 abstract 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005086 pumping Methods 0.000 description 7
- 230000003321 amplification Effects 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 239000013307 optical fiber Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- BEJRNLMOMBGWFU-UHFFFAOYSA-N bismuth boron Chemical compound [B].[Bi] BEJRNLMOMBGWFU-UHFFFAOYSA-N 0.000 description 3
- 229910001451 bismuth ion Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 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
- 238000005516 engineering process Methods 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
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Glass Compositions (AREA)
Abstract
The invention provides bismuth doped Si-Al-B based optical glass and a preparation method thereof. The optical glass is characterized by comprising the following glass matrixes based on molar percentage: 44 to 55 percent of strontium oxide, 20 to 29 percent of aluminum oxide, 20 to 29 percent of diboron trioxide, 0.1 to 5 percent of dibismuth trioxide, and 0.5 to 1 percent of silicon dioxide or lithium carbonate which is added into the glass matrixes as a fusion aid. The fusion temperature of the glass is obviously reduced compared with quartz glass; and the glass has optical performance covering an ultra-wide band of a communication waveband between 1,000 and 1,600nm , and is expected to be applied in the technical fields of an ultra-wide band optical amplifier, a high power laser, a tunable laser and the like.
Description
Technical field
The present invention relates to opticglass, particularly a kind of strontium-aluminum-boron based optical glass of mixing bismuth, this glass can be sent out near infrared communication band fluorescence, have long fluorescence lifetime, and wide gain bandwidth is suitable as gain media and is applied to optical amplifier and/or laser apparatus.
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 pentavalent bismuth ion Bi
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
2On 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: Al
2O
3-SiO
2-Bi
2O
3, under 1750 ℃ of 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 Al
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 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., and 40, preparation pentavalent bismuth ion Bi under air reported under 1760 ℃ of high temperature in (2001) L279 one literary composition
5+Adulterated Al
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.
Summary of the invention
The objective of the invention is for the higher shortcoming of the melt temperature that overcomes above-mentioned silica glass, a kind of strontium-aluminum-boron based optical glass of mixing bismuth and preparation method thereof is provided, 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 has an optical property of the ultra broadband that can cover 1000nm ~ 1600nm scope communication band, be expected at ultra broadband optics amplifier, superpower laser, technical fields such as tunable laser are applied.
The invention provides bismuth doped strontium-aluminum-boron based glass, by forming of following molar percentage:
SrO
2 44~55mol％
Al
2O
3 20~29mol％
B
2O
3 20~29mol％
SiO
2(K
2CO
3) 0.5~1mol％
Bi
2O
3 0.1~5mol％
Bismuth doped strontium-aluminum-boron based glass provided by the invention makes by following process steps:
(1), get the raw materials ready by following prescription after, mix then.
SrO
2 44~55mol％
Al
2O
3 20~29％
B
2O
3 20~29mol％
SiO
2(K
2CO
3) 0.5~1mol％
Bi
2O
3 0.1~5mol％
(2), above-mentioned compound is warming up to 1350 ~ 1500 ℃, be incubated 30 minutes ~ 120 minutes, make raw materials melt become liquid, feed reducing gas simultaneously: 97% nitrogen adds 3% hydrogen or ammonia, or the powdered carbon of packing in stove is as reducing atmosphere; Then above-mentioned melt is poured over fast on the stainless steel plate and flattens, transfer in the annealing furnace with another block plate, 520 ℃ down annealing naturally cool to room temperature with stove after 2 hours, taking-up promptly gets this bismuth doped strontium-aluminum-boron based glass.
The present invention compares with the silica glass method that bismuth ion is mixed in preparation, has following outstanding advantage:
This glass is except having the optical property of the ultra broadband that can cover 1000nm ~ 1600nm scope 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 in the melt molding process (as bubble etc.) less with respect to silica glass.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment, but protection scope of the present invention is not limited in these examples.
Embodiment 1
(1), forms by mole per-cent: 55SrO
2-20Al
2O
3-23.9B
2O
3-1SiO
2-0.1Bi
2O
3(add back summation should equal 100), take by weighing raw material 20g altogether, and with the above-mentioned raw materials ground and mixed evenly after, insert in the corundum crucible;
(2), be placed in the high temperature box furnace in the alumina crucible with above-mentioned charging, in High Temperature Furnaces Heating Apparatus, put into carbon dust simultaneously, 1250 ℃ of constant temperature 3 hours, make raw materials melt become liquid, so that thoroughly eliminate bubble, then melt is poured over fast on the stainless steel plate and and flattens with another block plate, transferring in the annealing furnace descends annealing after 2 hours in 520 ℃, naturally cool to room temperature with stove, take out and promptly get the adulterated strontium aluminium of bismuth boron glass with infrared excess broad-band illumination performance, this glass can produce fluorescence under the laser pumping of 800nm, fluorescence centre is positioned near the 1300nm, and the fluorescence halfwidth surpasses 200nm.
Embodiment 2
(1), forms by mole per-cent: 44SrO
2-25.5Al
2O
3-29B
2O
3-0.5K
2CO
3-1Bi
2O
3(add back summation should equal 100), take by weighing raw material 20g altogether, and with the above-mentioned raw materials ground and mixed evenly after, insert in the corundum crucible;
(2), be placed in the high temperature box furnace in the alumina crucible with above-mentioned charging, add under 3% hydrogen atmosphere in 97 nitrogen %, 1300 ℃ of constant temperature 2 hours, make raw materials melt become liquid, so that thoroughly eliminate bubble, then melt is poured over fast on the stainless steel plate and and flattens with another block plate, transferring in the annealing furnace descends annealing after 2 hours in 520 ℃, naturally cool to room temperature with stove, take out and promptly get this glass of the adulterated strontium aluminium of bismuth boron glass meeting generation fluorescence under the laser pumping of 800nm with infrared excess broad-band illumination performance, fluorescence centre is positioned near the 1300nm, and the fluorescence halfwidth surpasses 200nm.
Embodiment 3
(1), forms by mole per-cent: 50SrO
2-22Al
2O
3-22B
2O
3-1SiO
2-5Bi
2O
3, take by weighing altogether 20g of raw material, and with the above-mentioned raw materials ground and mixed evenly after, insert in the corundum crucible;
(2), be placed in the high temperature box furnace in the alumina crucible with above-mentioned charging, under ammonia atmosphere, 1500 ℃ of constant temperature 0.5 hour, make raw materials melt become liquid, so that thoroughly eliminate bubble, then melt is poured over fast on the stainless steel plate and and flattens with another block plate, transferring in the annealing furnace descends annealing after 2 hours in 520 ℃, naturally cool to room temperature with stove, take out and promptly get the adulterated strontium aluminium of bismuth boron glass with infrared excess broad-band illumination performance, this glass can produce fluorescence under the laser pumping of 800nm, fluorescence centre is positioned near the 1300nm, and the fluorescence halfwidth surpasses 200nm.
Claims (2)
1. bismuth doped strontium-aluminum-boron based optical glass is characterized in that the molar percentage of this glass is composed as follows:
SrO
2 44～55mol％
Al
2O
3 20～29mol％
B
2O
3 20～29mol％
SiO
2Or K
2CO
30.5～1mol%
Bi
2O
3 0.1～5mol％
2. the preparation method of bismuth doped strontium-aluminum-boron based optical glass according to claim 1 is characterized in that making by following process steps:
(1), forms and content according to glass, consist of by mole per-cent: strontium dioxide 44%～55%, aluminium sesquioxide 20%～29%, boron trioxide 20%-29%, bismuthous oxide bismuth trioxide 0.1～5%, the silicon-dioxide or the salt of wormwood that add 0.5%-1% in the glass matrix are made each raw material of flux proportioning weighing, mix then;
(2) in High Temperature Furnaces Heating Apparatus in 1250 ℃～1500 ℃ constant temperature 0.5～3 hour, make raw materials melt become liquid, feed reducing gas simultaneously: 97% nitrogen adds 3% hydrogen or all packs carbon dust into as reducing atmosphere with ammonia or in stove; Be cast on the metal plate and after glass metal is come out of the stove and flatten with metal sheet;
(3), the glass that obtains is transferred in the annealing furnace 520 ℃ of anneal 2 hours, naturally cool to room temperature, obtain the adulterated strontium-aluminum-boron based optical glass of bismuth with stove.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100941841A CN101503276B (en) | 2009-03-11 | 2009-03-11 | Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100941841A CN101503276B (en) | 2009-03-11 | 2009-03-11 | Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101503276A CN101503276A (en) | 2009-08-12 |
| CN101503276B true CN101503276B (en) | 2011-03-30 |
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ID=40975667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100941841A Expired - Fee Related CN101503276B (en) | 2009-03-11 | 2009-03-11 | Bismuth doped strontium-aluminum-boron based optical glass and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260042B (en) * | 2011-05-20 | 2013-09-11 | 昆明理工大学 | Bismuth-doped phosphate optical glass and preparation method thereof |
| CN110752283A (en) * | 2019-10-12 | 2020-02-04 | 华南理工大学 | Broadband near-infrared LED device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038834C (en) * | 1993-11-26 | 1998-06-24 | 株式会社小原 | Optical glass |
-
2009
- 2009-03-11 CN CN2009100941841A patent/CN101503276B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038834C (en) * | 1993-11-26 | 1998-06-24 | 株式会社小原 | Optical glass |
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| Publication number | Publication date |
|---|---|
| CN101503276A (en) | 2009-08-12 |
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Granted publication date: 20110330 Termination date: 20140311 |