CN103539358B - The method of the controlled precipitation of a kind of super-broadband fiber amplifier transparent glass-ceramics crystalline phase - Google Patents
The method of the controlled precipitation of a kind of super-broadband fiber amplifier transparent glass-ceramics crystalline phase Download PDFInfo
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- CN103539358B CN103539358B CN201310446419.5A CN201310446419A CN103539358B CN 103539358 B CN103539358 B CN 103539358B CN 201310446419 A CN201310446419 A CN 201310446419A CN 103539358 B CN103539358 B CN 103539358B
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- glass
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- crystalline phase
- fiber amplifier
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 23
- 239000000835 fiber Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000001556 precipitation Methods 0.000 title claims description 11
- 239000006132 parent glass Substances 0.000 claims abstract description 19
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000007669 thermal treatment Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 abstract description 33
- 230000005855 radiation Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000146 host glass Substances 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 239000000156 glass melt Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The controlled separation method of fiber amplifier transparent glass-ceramics crystalline phase disclosed by the invention, the component of its parent glass comprises fixing component and variable component, wherein fixes component and is: SiO
241.9 parts, Al
2o
311.7 parts, ZnO? 34 parts, K
2o? 10.7 parts, transition metal ion oxide compound 0.01 ~ 1.5 part, set of variables is divided into: 0≤Li
2o≤10, by regulated variable component Li
2the content of O, separates out β-Zn in parent glass
2siO
4, Zn
1.7siO
4, Li
1.14zn
1.43siO
4and Li
2znSiO
4one or more in four kinds of crystallites, does the devitrified glass that present method prepares all have 1000 ~ 1600? nm ultra broadband fluorescence radiation performance, does is emission peak halfwidth 200 ~ 400? nm, can be applicable to super-broadband fiber amplifier.
Description
Technical field
The present invention relates to the method for the controlled precipitation of a kind of transparent glass-ceramics crystalline phase, the method for the especially controlled precipitation of super-broadband fiber amplifier transparent glass-ceramics crystalline phase.
Technical background
Devitrified glass refers to the class matrix material being distributed with nanocrystal in continuous print glassy phase.Normally, first preparation designs the host glass of component to its preparation method, then the host glass thermal treatment original position at a certain temperature prepared is separated out nanocrystal, namely obtains devitrified glass.The physico-chemical property that devitrified glass has glass is simultaneously stablized, and physical strength is high, is easy to the feature of processing, has again the feature of the low phonon energy of crystal, can reduce the radiationless transition probability of doping light emitting ionic, improve its quantum yield and luminous efficiency.Therefore, have a good application prospect in fields such as solid statelaser, optical communication and optical informations.
In super-broadband fiber amplifier Application Areas, the research of existing many doped transition metal ions devitrified glasses.Pinchney etc. are at SiO
2-Al
2o
3-ZnO-K
2in O glass, obtain β-Zn by thermal treatment
2siO
4devitrified glass, achieves near-infrared super-broadband emission.Samson etc. are by Ni
2+optical fiber made by the spinel crystallites glass of doping, and the application of such material in broadband optical fiber amplifier and laser apparatus is advanced major step.Ma Hongping etc. also report Cr in succession
4+li doped
2znSiO
4, Li
1.14zn
1.43siO
4and Zn
1.7siO
4the near-infrared super-broadband emission feature of devitrified glass.But, can obtain by analyzing, in the preparation of current super-broadband fiber amplifier transparent glass-ceramics same glass ingredient host glass in major part can only separate out a kind of corresponding crystalline phase, and if want in host glass, separate out different crystallites, need to go to explore different substrates glass ingredient.If Ma Hongping etc. is respectively at 40SiO
2-5Al
2o
3-10B
2o
3-35ZnO-10K
2o, 41.9SiO
2-11.7Al
2o
3-34.0ZnO-10.7K
2o, 48.2SiO
2-16.0Al
2o
3-12.7ZnO-5.8Li
2o-14.6K
2o and 45.5SiO
2-14Al
2o
3-23.5ZnO-4.0Li
2o-12.9K
2o host glass kind has separated out β-Zn
2siO
4, Zn
1.7siO
4, Li
2znSiO
4and Li
1.14zn
1.43siO
4crystallite.Though above devitrified glass all achieves near-infrared luminous more than 200nm of broadband at 1000-1600nm near infrared region.But can find, even separate out the crystallite of close type, the component of its host glass is completely different, do not realize the crystallite of separating out two or more in same host glass simultaneously yet.
Although Zhou Shifeng etc. propose the research of the devitrified glass containing two or more 1 ~ 1000nm crystallite in the glass at doped transition metal ions in disclosed ultra-wideband near-infrared luminous transparent glass-ceramic patent of invention, achieve the object widening doped transition metal ions devitrified glass broad-band illumination scope, but in their research, do not relate to the controlled precipitation of crystallite crystalline phase.
Summary of the invention
The present invention is directed to crystalline phase in existing transparent glass-ceramics preparation process and separate out uncontrollable problem, propose the method for the controlled precipitation of a kind of super-broadband fiber amplifier transparent glass-ceramics crystalline phase, with the controlled precipitation of polycrystalline phase in optimized integration glass.
The method of the controlled precipitation of fiber amplifier transparent glass-ceramics crystalline phase, is characterized in that the component of parent glass comprises fixing component and variable component, and wherein fixing component is:
SiO
241.9 parts
Al
2o
311.7 parts
ZnO34 part
K
2o10.7 part
Transition metal ion oxide compound 0.01 ~ 1.5 part
Described transition metal ion is: Cr
4+, Ni
2+, Co
2+, Fe
3+or V
5+,
Set of variables is divided into: 0≤Li
2o≤10,
By regulated variable component Li
2the content of O, separates out β-Zn in parent glass
2siO
4, Zn
1.7siO
4, Li
1.14zn
1.43siO
4and Li
2znSiO
4one or more in four kinds of crystallites, during preparation, mix the component of parent glass, in 1350 ~ 1500 DEG C of fusings, be incubated 10 ~ 30 minutes, pour in the mould of preheating, at 500 DEG C, be incubated 1 hour, Temperature fall to room temperature, then 650 ~ 850 DEG C of thermal treatments 1 ~ 4 hour.
Transparent glass-ceramics prepared by the present invention all has the ultra broadband fluorescence property of 1000 ~ 1600nm.
Transparent glass-ceramics emission peak halfwidth prepared by the present invention is 200 ~ 400nm.
The present invention passes through at SiO
2-Al
2o
3-ZnO-Li
2o-K
2only Li is adjusted in O glass system
2the content of O, the controlled precipitation of different crystalline phase is achieved first in same host glass kind, optimize the preparation technology of different crystalline phase devitrified glass, also lay a good foundation for same host glass kind realizes the precipitation of one or more crystalline phases simultaneously, widened transient metal doped devitrified glass near-infrared super-broadband emission scope further.
Accompanying drawing explanation
Fig. 1 embodiment 1,2 and 3 obtains the XRD figure spectrum of transparent glass-ceramics;
Fig. 2 embodiment 1,2 and 3 obtains the fluorescence spectrum collection of illustrative plates of transparent glass-ceramics.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
Take the SiO of 41.9g respectively
2, 11.7g Al
2o
3, 34g the K of ZnO, 10.7g
2the Cr of O, 0.01g
2o
3, after said components is mixed, at 1350 DEG C after fusing, be incubated 10 minutes, poured into by glass melt in the mould of preheating, being transferred to temperature is be incubated 1 hour in the retort furnace of 500 DEG C, then close retort furnace, allow its Temperature fall to room temperature, obtain parent glass.
Parent glass, 650 DEG C of thermal treatments 4 hours, is then down to room temperature, obtains separating out β-Zn
2siO
4nanocrystalline devitrified glass.
The XRD figure spectrum of this transparent glass-ceramics is shown in Fig. 1, and Fig. 2 is shown in by fluorescence spectrum collection of illustrative plates.Can be obtained by Fig. 1, in this transparent glass-ceramics, crystallite crystalline phase is β-Zn
2siO
4; Can be obtained by Fig. 2, this devitrified glass is launched peak position and is positioned at 1335nm, halfwidth 240nm.
Embodiment 2:
Take the SiO of 41.9g respectively
2, 11.7g Al
2o
3, 34g the Li of ZnO, 1.5g
2the K of O, 10.7g
2the NiO of O, 1.5g, after said components being mixed, at 1500 DEG C after fusing, be incubated 30 minutes, poured into by glass melt in the mould of preheating, being transferred to temperature is be incubated 1 hour in the retort furnace of 500 DEG C, then close retort furnace, allow its Temperature fall to room temperature, obtain parent glass.
Parent glass, 850 DEG C of thermal treatments 1 hour, is then down to room temperature, obtains separating out β-Zn
2siO
4and Zn
1.7siO
4nanocrystalline devitrified glass.
The XRD figure spectrum of this transparent glass-ceramics is shown in Fig. 1, and Fig. 2 is shown in by fluorescence spectrum collection of illustrative plates.Can be obtained by Fig. 1, in this transparent glass-ceramics, crystallite crystalline phase is β-Zn
2siO
4, Zn
1.7siO
4; Can be obtained by Fig. 2, peak position launched by this devitrified glass, and to lay respectively at 1335nm(halfwidth be 240nm) and 1306nm(halfwidth be 235nm), obtain the broadband infrared luminescence more than 300nm altogether by the combination of two emission peaks.
Embodiment 3:
Take the SiO of 41.9g respectively
2, 11.7g Al
2o
3, 34g the Li of ZnO, 2.5g
2the K of O, 10.7g
2the CoO of O, 0.5g, after said components being mixed, at 1450 DEG C after fusing, be incubated 15 minutes, poured into by glass melt in the mould of preheating, being transferred to temperature is be incubated 1 hour in the retort furnace of 500 DEG C, then close retort furnace, allow its Temperature fall to room temperature, obtain parent glass.
Parent glass, 700 DEG C of thermal treatments 2 hours, is then down to room temperature, obtains separating out Zn
1.7siO
4nanocrystalline devitrified glass.
The XRD figure spectrum of this transparent glass-ceramics is shown in Fig. 1, and Fig. 2 is shown in by fluorescence spectrum collection of illustrative plates.Can be obtained by Fig. 1, in this transparent glass-ceramics, crystallite crystalline phase is Zn
1.7siO
4; Can be obtained by Fig. 2, this devitrified glass is launched peak position and is positioned at 1306nm, halfwidth 235nm.
Embodiment 4:
Take the SiO of 41.9g respectively
2, 11.7g Al
2o
3, 34g the Li of ZnO, 3.5g
2the K of O, 10.7g
2the Fe of O, 1.0g
2o
3, after said components is mixed, at 1400 DEG C after fusing, be incubated 20 minutes, poured into by glass melt in the mould of preheating, being transferred to temperature is be incubated 1 hour in the retort furnace of 500 DEG C, then close retort furnace, allow its Temperature fall to room temperature, obtain parent glass.
Parent glass, 700 DEG C of thermal treatments 3.5 hours, is then down to room temperature, obtains separating out β-Zn
2siO
4, Zn
1.7siO
4and Li
1.14zn
1.43siO
4nanocrystalline devitrified glass.
XRD test result can obtain, and in this transparent glass-ceramics, crystallite crystalline phase is β-Zn
2siO
4, Zn
1.7siO
4, Li
1.14zn
1.43siO
4; Fluorescence spectrum test can obtain, peak position launched by this devitrified glass, and to lay respectively at 1335nm(halfwidth be 240nm), 1306nm(halfwidth is 235nm) and 1265nm(halfwidth be 225nm), the combination of three emission peaks obtains altogether more than 350nm broadband infrared luminescence.
Embodiment 5:
Take the SiO of 41.9g respectively
2, 11.7g Al
2o
3, 34g the Li of ZnO, 10g
2the K of O, 10.7g
2the V of O, 0.5g
2o
5, after said components is mixed, at 1450 DEG C after fusing, be incubated 15 minutes, poured into by glass melt in the mould of preheating, being transferred to temperature is be incubated 1 hour in the retort furnace of 500 DEG C, then close retort furnace, allow its Temperature fall to room temperature, obtain parent glass.
Parent glass, 700 DEG C of thermal treatments 2 hours, is then down to room temperature, obtains separating out Li
2znSiO
4nanocrystalline devitrified glass.
XRD test result can obtain, and in this transparent glass-ceramics, crystallite crystalline phase is Li
2znSiO
4; Fluorescence spectrum test result can obtain, and this devitrified glass is launched peak position and is positioned at 1210nm, halfwidth 250nm.
The method steps that embodiment 6-16 prepares devitrified glass is identical with embodiment 1, the oxide-doped amount of the consumption of each component, transition metal ion, glass smelting system and parent glass heat treating regime, and the particular case such as emission peak positions and halfwidth that XRD tests the crystallite phase of the devitrified glass obtained, fluorescence spectrometry obtains refers to table 1.
Table 1
Claims (1)
1. a method for the controlled precipitation of fiber amplifier transparent glass-ceramics crystalline phase, is characterized in that the component of parent glass comprises fixing component and variable component, and wherein fixing component is by mass:
SiO
241.9 parts
Al
2o
311.7 parts
ZnO34 part
K
2o10.7 part
Transition metal ion oxide compound is by mass: 0.01 ~ 1.5 part
Described transition metal ion is: Cr
4+, Ni
2+, Co
2+, Fe
3+or V
5+,
Variable component is by mass: 0≤Li
2o≤10,
By regulated variable component Li
2the content of O, separates out Li in parent glass
1.14zn
1.43siO
4or Li
2znSiO
4or β-Zn
2siO
4, Zn
1.7siO
4, Li
1.14zn
1.43siO
4and Li
2znSiO
4two or more in four kinds of crystallites, during preparation, mixes the component of parent glass, in 1350 ~ 1500 DEG C of fusings, be incubated 10 ~ 30 minutes, pour in the mould of preheating, at 500 DEG C, be incubated 1 hour, Temperature fall to room temperature, then 650 ~ 850 DEG C of thermal treatments 1 ~ 4 hour.
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|---|---|---|---|
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|---|---|---|---|
| CN201310446419.5A CN103539358B (en) | 2013-09-26 | 2013-09-26 | The method of the controlled precipitation of a kind of super-broadband fiber amplifier transparent glass-ceramics crystalline phase |
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| Publication Number | Publication Date |
|---|---|
| CN103539358A CN103539358A (en) | 2014-01-29 |
| CN103539358B true CN103539358B (en) | 2016-03-02 |
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| CN116282926B (en) * | 2022-11-28 | 2024-08-13 | 武汉理工大学 | High-strength transparent zinc lithium silicate glass ceramic capable of being strengthened and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184157C (en) * | 1999-10-18 | 2005-01-12 | 康宁股份有限公司 | Transparent glass-ceramics based on alpha-and beta-willemite |
| CN101353228A (en) * | 2008-09-05 | 2009-01-28 | 浙江大学 | Ultra-wideband near-infrared luminous transparent glass-ceramic |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001028944A1 (en) * | 1999-10-18 | 2001-04-26 | Corning Incorporated | Transparent lithium zinc magnesium orthosilicate glass-ceramics |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184157C (en) * | 1999-10-18 | 2005-01-12 | 康宁股份有限公司 | Transparent glass-ceramics based on alpha-and beta-willemite |
| CN101353228A (en) * | 2008-09-05 | 2009-01-28 | 浙江大学 | Ultra-wideband near-infrared luminous transparent glass-ceramic |
Non-Patent Citations (2)
| Title |
|---|
| Spectroscopy and crystal-field analysis of Cr4+-doped transparent silicate glass-ceramics;Hongping Ma et.al;《Journal of Non-Crystalline Solids》;20101216;第357卷;第2294-2297页 * |
| 超宽带光放大用新型发光材料;周时凤等;《硅酸盐学报》;20060930;第34卷(第9期);第1130-1136页 * |
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