CN103723919A - Oxyfluoride glass with low hydroxyl content and preparation method of oxyfluoride glass - Google Patents
Oxyfluoride glass with low hydroxyl content and preparation method of oxyfluoride glass Download PDFInfo
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- CN103723919A CN103723919A CN201310695081.7A CN201310695081A CN103723919A CN 103723919 A CN103723919 A CN 103723919A CN 201310695081 A CN201310695081 A CN 201310695081A CN 103723919 A CN103723919 A CN 103723919A
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- glass
- hydroxyl
- hydroxy radical
- radical content
- oxyfluoride
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Abstract
The invention relates to oxyfluoride glass with a low hydroxyl content and a preparation method of the oxyfluoride glass. The oxyfluoride glass is characterized in that heavy metal TeO2 is added into a fluoaluminic acid salt glass system to obviously reduce the hydroxyl content of the fluoaluminic acid salt glass system. The glass particularly comprises the following ingredients by mole fraction: 25-35% of AlF3, 10-15% of YF3, 12-20% of CaF2, 7-10% of SrF2, 7-10% of BaF2, 7-10% of MgF2 and 0-25% of TeO2, wherein the mole fraction sum of the ingredients is 100%. The glass is prepared with a fusion method through a capped platinum crucible and a silicon carbide rod electric furnace. According to the glass, the heavy metal TeO2 is introduced into the fluoaluminic acid salt glass, so that the transparency of the glass gets better; the heat stability is improved; the crystallization resistance of the glass is enhanced; the transmittance rate of a middle infrared region reaches 90%; a hydroxyl absorption peak at 2.9 micrometers becomes very weak; and a hydroxyl absorption coefficient is reduced to 1/15 % of the original absorption coefficient.
Description
Technical field
The present invention relates to fluorine oxygen glass of fluorine oxygen glass, particularly a kind of low hydroxy radical content and preparation method thereof.
Technical background
The advantages such as with traditional multi-component oxide glassy phase ratio, fluoride glass has in ultraviolet and middle-infrared band transparency range wide, and the lower and Abel's number of specific refractory power is large.In addition, fluoride glass also has lower phonon energy and stronger ionic linkage performance.The doping content of rare earth ion in fluoride glass can be very high, and the light emitting region of rare earth ion in fluoride glass is from extend to as seen mid infrared region always.Due to these unique performances of fluoride glass, with traditional multi-component oxide glassy phase ratio, it has the unrivaled advantage of traditional material in some field.
In recent years, 2～3 μ m laserable materials are subject to great attention both domestic and external.3 mu m waveband lasers are positioned in 2 transmission windows (1～3 μ m, 3～5 μ m) of atmosphere, and have covered a lot of important molecular spectrums.Therefore, in fields such as remote sensing, range finding, environment measuring, biotechnology and medical treatment, have a wide range of applications.For the more middle infrared lumious material of current research, fluorochemical has more importantly status, and the transmitance that low phonon energy and middle-infrared band are high is that other oxide glasses are unsurpassable.The research of fluoride glass only concentrates in the glass system of fluozirconate and fluoaluminate.Especially the ZBLAN glass that mixes rare earth ion in Fluorozirconate glass has obtained deep research, and has obtained actual application in middle infrared optical fiber laserable material.2010, Tokita reported at Er
3+in the ZBLAN optical fiber of doping, obtained tunable range at 2770-2880nm, output rating is at the laser of 8-11W.2011, Canadian scholar Dominic Faucher was at Er
3+the laser that the peak power output that has obtained 2.825 mu m wavebands in the single-mode fiber of doping is 20.6W, slope efficiency is 35.4%.But Fluorozirconate glass exists following shortcoming: the transition temperature of glass is lower, water tolerance and physical strength are lower.These drawbacks limit fluoride fiber ZBLAN in the further application of mid-infrared laser material fermentation, as the stable output of the further raising of power and power.Fluoroaluminate glass until phase early 1980s be just taken seriously gradually and demonstrate application prospect.AlF
3base fluoride glass is with AlF
3-MF
2(M is alkaline-earth metal) is representative, and its some performance characteristics have report very early.Fluoroaluminate glass compares with ZBLAN that to have glass transformation temperature high, the advantage of chemical stability and good mechanical property, and its chemical stability compares ZrF
4high 3 orders of magnitude of base glass, are hopeful to replace Fluorozirconate glass for infrared lumious material.But the AlF studying at present
3-MF
2at 2.9 μ m places, there is larger hydroxyl absorption peak in system.This impurity has multiple sources, and as the remaining oxygen in raw material, the moisture absorption of certain component, prepares environmental pollution in environmental process etc.Its absorbing wavelength is near 3 μ m, and this will affect it in the application aspect middle infrared lumious material.
Summary of the invention
Fluorine oxygen glass providing a kind of low hydroxy radical content and preparation method thereof is provided the technical problem to be solved in the present invention, and this glass has good stability, preferably infrared transmission performance and lower hydroxyl coefficient.
The technical solution that the present invention has is as follows:
A fluorine oxygen glass for low hydroxy radical content, the molar percentage of this glass is composed as follows:
The preparation method of the fluorine oxygen glass of above-mentioned low hydroxy radical content, comprises the following steps:
1. selected described glass forms and molar percentage, calculates the weight that corresponding each glass forms, and accurately takes each raw material, mixes formation compound;
2. described compound is put into platinum crucible and melted in the globars electric furnace of 900～950 ℃, in melting process, without passing into gas as protective atmosphere, clarification 10～15 minutes after fusing completely, is cast in glass metal in the mould of preheating;
3. glass is moved into rapidly and has been warming up to lower than glass transformation temperature (T
g) in the retort furnace of 10 ℃, be incubated 3～4 hours, then be down to room temperature with the speed of 10 ℃/h, completely cooling rear taking-up glass sample.
Technique effect of the present invention is as follows:
The present invention is at the upper introducing heavy metal oxide TeO in Fluoroaluminate glass basis
2.Whole transmitance is substantially constant remains on more than 90% in middle-infrared band for the fluorine oxygen glass of preparation, and near the hydroxy radical content 2.9 μ m obviously reduces, and its thermal property and glass forming ability are also significantly improved.
Disclosed by the invention is a kind of preparation method of fluorine oxygen glass of low hydroxy radical content.By the adjusting of component, in original Fluoroaluminate glass component, introduce a small amount of oxide compound TeO
2.TeO
2the fluorine oxygen glass of making that adds retained the advantage of original Fluoroaluminate glass, and its hydroxy radical content significantly reduced, the introducing of oxide compound is also improved the thermostability of glass.This will make it in middle-infrared band, have important application.
Given this, the preparation method of the fluorine oxygen glass of the low hydroxy radical content of the present invention is feasible and has actual application value.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention 1#, 2#, 3#, 4#, the infrared curve comparison figure that sees through in the glass that 5# and 6# obtain.
Fig. 2 is embodiment of the present invention 1#, 2#, 3#, 4#, the mid infrared region maximum transmission of the glass that 5# and 6# obtain and at the hydroxyl uptake factor at 2.9 μ m places with oxide concentration change curve.
Fig. 3 is the differential thermal curve comparison diagram of embodiment of the present invention 1# and glass that 4# obtains.
Fig. 4 is the invention process case 7#, 8#, the XRD curve comparison figure of the glass that 9# and 10# obtain.
Embodiment
In the present invention, the glass ingredient of 10 concrete case study on implementation of the fluorine oxygen glass of low hydroxy radical content is as shown in table 1:
Table 1: the glass formula of concrete 10 cases
Composition is as shown in 1# in table 1, and concrete preparation process is as follows:
The molar percentage forming according to 1# glass in table 1, calculates the corresponding weight that each forms, and takes each raw material and mixes; Compound is put into platinum crucible and in the globars electric furnace of 900 ℃～950 ℃, melt, clarification 15 minutes after fusing completely, is cast in glass metal in the mould of preheating; Glass is moved into rapidly in the retort furnace of the specific annealing temperature that heated up, is incubated 4 hours, then is down to room temperature with the speed of 10 ℃/h, completely cooling rear taking-up glass sample.
Test result to this glass is as follows:
Get a little sample after annealing, with agate mortar, wear into fine powdered, carry out differential thermal analysis test.
Sheet glass polishing that sample after annealing is processed into 10 * 20 * 1.0mm, test its infrared spectrum that sees through.The infrared of the fluorine oxygen glass embodiment 1# of the low hydroxy radical content of the present invention sees through spectrum as shown in Figure 1, and as shown in Figure 2, differential thermal analysis DSC curve as shown in Figure 3 for maximum transmission and 3 μ m uptake factors.Experiment shows, glass transparent degree is general, without crystallization, and middle infrared light transmission wide ranges, maximum transmission is greatly 94%, and at 2.9 μ m places, there is stronger hydroxyl absorption peak in it, and hydroxyl coefficient is larger.
Composition is as shown in 2# in table 1, and concrete preparation process is as embodiment 1
#
Test result to this glass is as follows:
Sheet glass polishing that sample after annealing is processed into 10 * 20 * 1.0mm, test its infrared spectrum that sees through.The infrared of the fluorine oxygen glass embodiment 2# of the low hydroxy radical content of the present invention sees through spectrum as shown in Figure 1, and maximum transmission and 3 μ m uptake factors are as shown in Figure 2.Experiment shows, glass transparent degree is good, and without crystallization, middle infrared light transmission scope reduces slightly, and maximum transmission is greatly 93%, and it exists faint hydroxyl absorption peak at 2.9 μ m places, and hydroxyl coefficient is less.
Composition is as shown in 3# in table 1, and concrete preparation process is as embodiment 1
#
Test result to this glass is as follows:
Sheet glass polishing that sample after annealing is processed into 10 * 20 * 1.0mm, test its infrared spectrum that sees through.The infrared of the fluorine oxygen glass embodiment 3# of the low hydroxy radical content of the present invention sees through spectrum as shown in Figure 1, and maximum transmission and 3 μ m uptake factors are as shown in Figure 2.Experiment shows, glass transparent degree is good, and without crystallization, middle infrared light transmission scope reduces slightly, and maximum transmission is greatly 92%, and it exists faint hydroxyl absorption peak at 2.9 μ m places, and hydroxyl coefficient is less.
Composition is as shown in 4# in table 1, and concrete preparation process is as embodiment 1
#
Test result to this glass is as follows:
Get a little sample after annealing, with agate mortar, wear into fine powdered, carry out differential thermal analysis test.
Sheet glass polishing that sample after annealing is processed into 10 * 20 * 1.0mm, test its infrared spectrum that sees through.The infrared of the fluorine oxygen glass embodiment 4# of the low hydroxy radical content of the present invention sees through spectrum as shown in Figure 1, and as shown in Figure 2, differential thermal analysis DSC curve as shown in Figure 3 for maximum transmission and 3 μ m uptake factors.Experiment shows, glass transparent degree is good, and without crystallization, middle infrared light transmission scope reduces slightly, and maximum transmission is greatly 91%, and it exists faint hydroxyl absorption peak at 2.9 μ m places, and hydroxyl coefficient is less.
Composition is as shown in 5# in table 1, and concrete preparation process is as embodiment 1
#
Test result to this glass is as follows:
Sheet glass polishing that sample after annealing is processed into 10 * 20 * 1.0mm, test its infrared spectrum that sees through.The infrared of the fluorine oxygen glass embodiment 5# of the low hydroxy radical content of the present invention sees through spectrum as shown in Figure 1, and maximum transmission and 3 μ m uptake factors are as shown in Figure 2.Experiment shows, glass transparent degree is good, and without crystallization, middle infrared light transmission scope reduces slightly, and maximum transmission is greatly in 90% left and right, and it exists faint hydroxyl absorption peak at 2.9 μ m places, and hydroxyl coefficient is less.
Composition is as shown in 6# in table 1, and concrete preparation process is as embodiment 1
#:
Test result to this glass is as follows:
Sheet glass polishing that sample after annealing is processed into 10 * 20 * 1.0mm, test its infrared spectrum that sees through.The fluorine oxygen glass embodiment 6# of the low hydroxy radical content of the present invention infrared sees through composes as shown in Figure 1 maximum transmission and 3 μ m uptake factors as shown in Figure 2.Experiment shows, glass transparent degree is good, and without crystallization, middle infrared light transmission scope further reduces, large 80% left and right of maximum transmission, and at 2.9 μ m places, there is faint hydroxyl absorption peak in it, and hydroxyl coefficient is less.
Embodiment 7#:
Composition is as shown in 7# in table 1, and concrete preparation process is as follows:
The molar percentage forming according to 7# glass in table 1, calculates the corresponding weight that each forms, and takes each raw material and mixes; Compound is put into platinum crucible and in the globars electric furnace of 900 ℃～950 ℃, melt, clarification 15 minutes after fusing completely, is cast in glass metal in the mould of preheating; Glass is moved into rapidly in the retort furnace of the specific annealing temperature that heated up, is incubated 2 hours, then is down to room temperature with the speed of 10 ℃/h, completely cooling rear taking-up glass sample.
Test result to this glass is as follows:
Get a little sample after annealing, with agate mortar, wear into fine powdered, carry out XRD analysis.As shown in Figure 3, experiment shows the XRD spectrum of the fluorine oxygen glass embodiment 7# of the low hydroxy radical content of the present invention, and glass transparent degree is general, has a small amount of crystallite phase.
Embodiment 8#:
Composition is as shown in 8# in table 1, and concrete preparation process is as 7#:
Test result to this glass is as follows:
Get a little sample after annealing, with agate mortar, wear into fine powdered, carry out XRD analysis.As shown in Figure 3, experiment shows the XRD spectrum of the fluorine oxygen glass embodiment 8# of the low hydroxy radical content of the present invention, and glass transparent degree is very weak, has more crystallite phase.
Embodiment 9#:
Composition is as shown in 9# in table 1, and concrete preparation process is as 7#:
Test result to this glass is as follows:
Get a little sample after annealing, with agate mortar, wear into fine powdered, carry out XRD analysis.As shown in Figure 3, experiment shows the XRD spectrum of the fluorine oxygen glass embodiment 9# of the low hydroxy radical content of the present invention, and glass transparent degree is good, does not have crystalline phase.
Composition is as shown in 10# in table 1, and concrete preparation process is as 7#:
Test result to this glass is as follows:
Get a little sample after annealing, with agate mortar, wear into fine powdered, carry out XRD analysis.As shown in Figure 3, experiment shows the XRD spectrum of the fluorine oxygen glass embodiment 10# of the low hydroxy radical content of the present invention, and glass transparent degree is good, does not have crystalline phase.
Claims (2)
1. a fluorine oxygen glass for low hydroxy radical content, is characterized in that, this glass is comprised of following component molar percentage:
2. the preparation method of the fluorine oxygen glass of low hydroxy radical content claimed in claim 1, comprises the following steps:
1. selected described glass forms and molar percentage, calculates the weight that corresponding each glass forms, and accurately takes each raw material, mixes formation compound;
2. described compound is put into platinum crucible and melted in the globars electric furnace of 900～950 ℃, in melting process, without passing into gas as protective atmosphere, clarification 10～15 minutes after fusing completely, is cast in glass metal in the mould of preheating;
3. glass is moved into rapidly in the retort furnace being warming up to lower than 10 ℃ of glass transformation temperatures, is incubated 3～4 hours, then is down to room temperature with the speed of 10 ℃/h, completely cooling rear taking-up glass.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217953A (en) * | 2015-09-17 | 2016-01-06 | 中国科学院上海光学精密机械研究所 | White-light emitting diode rare earth doped luminescent glass and preparation method thereof |
| CN105384352A (en) * | 2015-11-09 | 2016-03-09 | 苏州优康通信设备有限公司 | Fluorophosphate cladding glass optical fiber and preparation method thereof |
| WO2017124612A1 (en) * | 2016-01-21 | 2017-07-27 | 上海昕禾光电科技有限公司 | Low-dispersion oxyfluoride glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522979A (en) * | 2003-09-05 | 2004-08-25 | 中国科学院上海光学精密机械研究所 | Infrared permeating oxide fluoride glass |
| 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 fluorophosphates laser glass and preparation method thereof |
-
2013
- 2013-12-17 CN CN201310695081.7A patent/CN103723919A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522979A (en) * | 2003-09-05 | 2004-08-25 | 中国科学院上海光学精密机械研究所 | Infrared permeating oxide fluoride glass |
| 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 fluorophosphates laser glass and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217953A (en) * | 2015-09-17 | 2016-01-06 | 中国科学院上海光学精密机械研究所 | White-light emitting diode rare earth doped luminescent glass and preparation method thereof |
| CN105217953B (en) * | 2015-09-17 | 2018-03-20 | 中国科学院上海光学精密机械研究所 | White-light emitting diode rare earth doped luminescent glass and preparation method thereof |
| CN105384352A (en) * | 2015-11-09 | 2016-03-09 | 苏州优康通信设备有限公司 | Fluorophosphate cladding glass optical fiber and preparation method thereof |
| CN105384352B (en) * | 2015-11-09 | 2018-07-06 | 苏州优康通信设备有限公司 | A kind of fluorophosphate Caldding glass optical fiber and preparation method thereof |
| WO2017124612A1 (en) * | 2016-01-21 | 2017-07-27 | 上海昕禾光电科技有限公司 | Low-dispersion oxyfluoride glass |
| US20190077697A1 (en) * | 2016-01-21 | 2019-03-14 | Shanghai Xinhe Photoelectric Technology Co., Ltd. | Low-dispersion oxyfluoride glass |
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Application publication date: 20140416 |