CN1927752A - Infrared transparent fluozirconate microcrystalline glass and preparation method thereof - Google Patents
Infrared transparent fluozirconate microcrystalline glass and preparation method thereof Download PDFInfo
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- CN1927752A CN1927752A CNA200610116576XA CN200610116576A CN1927752A CN 1927752 A CN1927752 A CN 1927752A CN A200610116576X A CNA200610116576X A CN A200610116576XA CN 200610116576 A CN200610116576 A CN 200610116576A CN 1927752 A CN1927752 A CN 1927752A
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- Prior art keywords
- glass
- fluozirconate
- fluorozirconate
- preparation
- devitrified
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000005386 fluorozirconate glass Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 230000006911 nucleation Effects 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 5
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 2
- 229910017768 LaF 3 Inorganic materials 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims 1
- 239000005383 fluoride glass Substances 0.000 abstract description 13
- 239000013081 microcrystal Substances 0.000 abstract description 7
- 238000003723 Smelting Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 3
- 229910002319 LaF3 Inorganic materials 0.000 abstract 2
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 abstract 2
- 229910007998 ZrF4 Inorganic materials 0.000 abstract 1
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- 239000006121 base glass Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 abstract 1
- 238000009738 saturating Methods 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000000146 host glass Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/325—Fluoride glasses
-
- 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
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
Abstract
The present invention is infrared transmitting fluorozirconate microcrystal glass and its preparation process, and features that LaF3 is added into ZrF4-BaF2-YF3-AlF3 fluoride glass components to form the fluorozirconate microcrystal glass in the molar composition of: ZrF4 50-55 mol%, BaF2 15-33 mol%, YF3 10-22 mol%, AlF3 3-7 mol%, and LaF3 2-8 mol%. The preparation process includes the first smelting process to prepare fluorozirconate glass and the subsequent precise heat treatment to microcrystallize the base glass into infrared transmitting fluorozirconate microcrystal glass. The preparation process is simple, and the prepared fluorozirconate microcrystal glass has excellent resistance to transparency loss and higher mechanical performance than fluoride glass. The fluorozirconate microcrystal glass is suitable for use as the optical window material in medium infrared band.
Description
Technical field
The present invention relates to the fluozirconate devitrified glass, particularly a kind of infrared fluozirconate devitrified glass with and preparation method thereof, be characterized in that this devitrified glass has very high transmitance in middle-infrared band, compare that its physical strength has bigger enhancing with fluoride glass.
Background technology
In the past few decades, people have carried out a large amount of research to the crystalline phase that how to form uniform sub-micron scale in silicon-based glass.Relative traditional glass, devitrified glass has excellent calorifics and mechanical property, as low thermal expansivity and high Young's modulus, especially when crystallite phase size in the devitrified glass during less than certain wave band, this wave band just there is the very high characteristic that sees through, has improved the calorifics and the mechanical property of glass widely.
The fluoride glass specific refractory power is little, and phonon energy is low, has good infrared transmission performance in 0.2～7 mu m waveband scope, makes fluoride glass become the popular candidate material that laser is used.Succeeding in developing of bulk fluoride glass makes these materials also receive publicity day by day as the application of infrared optical device.Yet the optical application that the low chemical stability of fluoride glass and mechanical property have hindered it.As everyone knows, fluoride glass is heat-treated micritization, make its even crystallization can improve the physical strength and the thermal property of glass, crystallization to fluoride glass has also carried out a large amount of research both at home and abroad, obtained some progress, but controlled the crystallization process of fluoride glass how, thereby it is good to obtain infrared transmission performance, the uniform fluoride microcrystal glass of crystalline phase in the glass, particularly the fluozirconate devitrified glass is never obtained big progress.At home, also less than report about the fluozirconate devitrified glass.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of infrared fluozirconate devitrified glass and preparation method thereof, and this devitrified glass not only has good anti-devitrification behavior and mechanical property, and has good transmitance in middle-infrared band.
Technical solution of the present invention is as follows:
A kind of infrared fluozirconate devitrified glass and preparation method thereof is characterized in that at ZrF
4-BaF
2-YF
3-AlF
3Add LaF in the fluoride glass component
3
The compositing range of described infrared fluozirconate devitrified glass is as follows:
Form mol%
ZrF
4 50～55
BaF
2 20～33
YF
3 8～20
AlF
3 5～7
LaF
3 2～6。
The concrete preparation method of the fluozirconate devitrified glass that the present invention is saturating infrared may further comprise the steps:
Founding of A, Fluorozirconate glass: form selected prescription and each raw material of weighing according to above-mentioned glass, after dusty raw materials mixed, putting into platinum crucible melts at 1000～1050 ℃ globars electric furnace, fusing is after clarified 15～20 minutes fully, glass metal is cast on the graphite jig of preheating, glass is moved into rapidly has been warming up to glass transformation temperature (T then
g) near retort furnace in anneal.Annealing process is: at glass transformation temperature (T
g) near insulation 3～4 hours, and then reduce to 200 ℃ with 3 ℃/hour speed, at last reduce to room temperature, fully cooling back taking-up glass sample with 5 ℃/hour speed.
The preparation method of B, fluozirconate devitrified glass:, the glass sample that makes is heated to above T by room temperature with 10 ℃/minute speed according to glass heat analysis (DTA) data
gTemperature nucleation after 4～5 hours more than 20 ℃ is heated to the first crystallization peak temperature point (T with 0.5 ℃/minute speed again
x) near crystallization 30～50 minutes, to take out behind 1 ℃/minute the speed cool to room temperature, obtain transparent fluozirconate devitrified glass again.
The invention has the advantages that:
The anti-devitrification behavior of saturating infrared fluozirconate devitrified glass and the physical and chemical performance of the present invention's preparation are good.
The saturating infrared fluozirconate devitrified glass satisfactory mechanical property of the present invention's preparation the experiment proved that the devitrified glass after the thermal treatment all has bigger enhancing than the fluoride glass physical strength.
The saturating infrared fluozirconate devitrified glass of the present invention's preparation has good transmitance in middle-infrared band.
Infrared fluozirconate devitrified glass preparation method of the present invention is simple, and production cost is also lower.
Description of drawings
Fig. 1 is the differential thermal curve of glass in embodiment 1 and 3.
Fig. 2 is the fluozirconate devitrified glass that the present invention obtained and the infrared transmittivity of host glass, and thickness of sample is 2mm.
Embodiment
Table 1 has provided the composition of raw materials of the glass of 5 specific embodiments of the present invention.
Only the glass formula composition is different with 2 for embodiment 1, and the melting technology of glass is identical.Detailed process from glass smelting to the thermal treatment micritization is:
(1) founding of Fluorozirconate glass: according to each raw material of glass formula weighing in the table 1, after dusty raw materials mixed, putting into platinum crucible melts in 1000～1050 ℃ globars electric furnace, fusing is after clarified 15～20 minutes fully, glass metal is cast on the graphite jig of preheating, glass is moved into rapidly in the retort furnace that has been warming up to 310 ℃ anneals then.Annealing process is: be incubated 3～4 hours at 310 ℃, and then reduce to 200 ℃ with 3 ℃/hour speed, reduce to room temperature with 5 ℃/hour speed at last, glass sample is taken out in the cooling back fully.
(2) preparation method of fluozirconate devitrified glass:, the glass sample that makes is heated to above T by room temperature with 10 ℃/minute speed according to glass heat analysis (DTA) data
gTemperature nucleation after 4～5 hours more than 20 ℃ is heated to the first crystallization peak temperature point (T with 0.5 ℃/minute speed again
x) near crystallization 30～50 minutes, last to take out behind 1 ℃/minute the speed cool to room temperature, obtain transparent fluozirconate devitrified glass.In the concrete implementation process, for embodiment 1, its nucleation temperature is 340 ℃, and crystallization temperature is 380 ℃; For embodiment 2, its nucleation temperature is 345 ℃, and crystallization temperature is 380 ℃.
Embodiment: 3,4 and 5:
Concrete preparation process is as follows:
The first step: the glass ingredient according to the embodiment described in the table 13,4 and 5 is prepared burden; The glass smelting process of founding the technological process of embodiment 3,4 and 5 fluoride glasses and embodiment 1 and 2 is basic identical, and the glass melting temperature of glass and ANNEALING OF GLASS temperature all slightly raise.
Second step: the preparation technology of embodiment 3,4 and 5 fluoride microcrystal glass and embodiment 1 and 2 basic identical just according to glass heat analysis (DTA) data, is heated to above T by room temperature with 10 ℃/minute speed with the glass sample that makes
gTemperature nucleation after 4～5 hours more than 20 ℃ is heated to the first crystallization peak temperature point (T with 0.5 ℃/minute speed again
x) near crystallization 30～50 minutes, last to take out behind 1 ℃/minute the speed cool to room temperature, obtain transparent fluozirconate devitrified glass.The nucleation of each embodiment and crystallization temperature are listed in the table 1 in the specific implementation process.
The fluozirconate devitrified glass that is obtained by above-mentioned preparation process is transparent and physical and chemical performance is good.
Among the present invention Fluorozirconate glass and devitrified glass thereof infrared transmittivity be illustrated in fig. 2 shown below, as can be seen from the figure, compare host glass, the infrared transmittivity of devitrified glass all descends to some extent among the embodiment, but still about 70%.Tested the Vickers' hardness (seeing Table 2) of glass before and after the thermal treatment simultaneously, contrast can find, after the thermal treatment among all embodiment the Vickers' hardness of glass in various degree enhancing is all arranged.
Table 1: the glass formula of concrete 5 embodiment
| Embodiment |
| 1 | Embodiment 2 | | Embodiment 4 | Embodiment 5 | |
| Glass ingredient (mol%) | 50ZrF 4-33BaF 2- 8YF 3- 7AlF 5-2LaF 3 | 53ZrF 4-30BaF 2- 9YF 3- 5AlF 5-3LaF 3 | 55ZrF 4-20BaF 2- 16YF 3- 5AlF 5-4LaF 3 | 54ZrF 4-23BaF 2- 13YF 3- 5AlF 5-5LaF 3 | 50ZrF 4-31BaF 2- 6YF 3- 7AlF 5-6LaF 3 |
| The transparency | Transparent | Transparent | Transparent | Transparent | Transparent |
| Transition temperature (℃) | 321 | 322 | 326 | 329 | 331 |
| Nucleation temperature (℃) | 340 | 345 | 350 | 353 | 355 |
| Crystallization temperature (℃) | 380 | 380 | 380 | 380 | 380 |
Table 2: the Vickers' hardness of glass before and after the thermal treatment among each embodiment
| Embodiment | ||
| 1 | Embodiment 2 | | Embodiment 4 | Embodiment 5 | ||
| Hv(Gpa) | Host glass | 2.21 | 2.33 | 2.28 | 2.36 | 2.18 |
| Devitrified glass | 2.65 | 2.86 | 2.72 | 3.21 | 2.98 |
Claims (2)
1, a kind of infrared fluozirconate devitrified glass is characterized in that its molar percentage consists of:
Form mol%
ZrF
4 50～55
BaF
2 20～33
YF
3 8～20
AlF
3 5～7
LaF
3 2～6。
2, the preparation method of the described infrared fluozirconate devitrified glass of claim 1 is characterized in that this method comprises the following steps:
1. founding of Fluorozirconate glass: according to the composition described in the claim 1, each raw material of weighing behind the selected formula rate, after dusty raw materials mixed, putting into platinum crucible melts at 1000～1050 ℃ globars electric furnace, the clarification of fusing back is 15～20 minutes fully, glass metal is cast on the graphite jig of preheating, glass is moved into rapidly has been warming up to glass transformation temperature (T then
g) retort furnace in anneal, annealing process is: at glass transformation temperature (T
g) be incubated 3～4 hours, reduce to 200 ℃ with 3 ℃/hour speed then, reduce to room temperature with 5 ℃/hour speed again, glass is taken out in the cooling back fully;
The preparation method of 2. transparent fluozirconate devitrified glass: according to the glass heat analytical data, the glass that makes is heated to above glass transformation temperature nucleation after 4～5 hours more than 20 ℃ by room temperature with 10 ℃/minute speed, is heated to the first crystallization peak temperature point (T with 0.5 ℃/minute speed again
x) crystallization 30～50 minutes, to take out behind 1 ℃/minute the speed cool to room temperature, obtain transparent fluozirconate devitrified glass again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610116576XA CN1927752A (en) | 2006-09-27 | 2006-09-27 | Infrared transparent fluozirconate microcrystalline glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610116576XA CN1927752A (en) | 2006-09-27 | 2006-09-27 | Infrared transparent fluozirconate microcrystalline glass and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1927752A true CN1927752A (en) | 2007-03-14 |
Family
ID=37857909
Family Applications (1)
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|---|---|---|---|
| CNA200610116576XA Pending CN1927752A (en) | 2006-09-27 | 2006-09-27 | Infrared transparent fluozirconate microcrystalline glass and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030476A (en) * | 2010-11-03 | 2011-04-27 | 中国科学院上海光学精密机械研究所 | Cobalt magnesium aluminum-doped silicon-based nano microcrystalline glass containing lanthanumoxide and preparation method thereof |
| RU2487840C1 (en) * | 2011-11-15 | 2013-07-20 | Общество С Ограниченной Ответственностью "Димонта" | FLUORIDE OPTICAL GLASS, CAPABLE OF LUMINESCENCE IN 1000-1700 nm RANGE, METHODS OF PRODUCING SAID GLASS AND FIBRE-OPTIC GUIDE |
| 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 |
| CN105366924A (en) * | 2014-09-01 | 2016-03-02 | 成都光明光电股份有限公司 | Glass annealing method and application thereof |
| CN107285627A (en) * | 2017-07-25 | 2017-10-24 | 华中科技大学 | A kind of fluoride glass and preparation method thereof |
| CN109704569A (en) * | 2019-03-14 | 2019-05-03 | 哈尔滨工程大学 | A kind of ZBYA fluoride glass and preparation method thereof |
| CN115650590A (en) * | 2022-09-26 | 2023-01-31 | 中国科学院上海光学精密机械研究所 | Containing YF 3 Crystalline phase fluoride glass ceramics and preparation method thereof |
-
2006
- 2006-09-27 CN CNA200610116576XA patent/CN1927752A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030476A (en) * | 2010-11-03 | 2011-04-27 | 中国科学院上海光学精密机械研究所 | Cobalt magnesium aluminum-doped silicon-based nano microcrystalline glass containing lanthanumoxide and preparation method thereof |
| RU2487840C1 (en) * | 2011-11-15 | 2013-07-20 | Общество С Ограниченной Ответственностью "Димонта" | FLUORIDE OPTICAL GLASS, CAPABLE OF LUMINESCENCE IN 1000-1700 nm RANGE, METHODS OF PRODUCING SAID GLASS AND FIBRE-OPTIC GUIDE |
| CN105366924A (en) * | 2014-09-01 | 2016-03-02 | 成都光明光电股份有限公司 | Glass annealing method and application thereof |
| CN105366924B (en) * | 2014-09-01 | 2018-09-18 | 成都光明光电股份有限公司 | Glass method for annealing and its application |
| 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 |
| CN107285627A (en) * | 2017-07-25 | 2017-10-24 | 华中科技大学 | A kind of fluoride glass and preparation method thereof |
| CN107285627B (en) * | 2017-07-25 | 2020-07-10 | 华中科技大学 | Fluoride glass and preparation method thereof |
| CN109704569A (en) * | 2019-03-14 | 2019-05-03 | 哈尔滨工程大学 | A kind of ZBYA fluoride glass and preparation method thereof |
| CN109704569B (en) * | 2019-03-14 | 2021-11-23 | 哈尔滨工程大学 | ZBYA fluoride glass and preparation method thereof |
| CN115650590A (en) * | 2022-09-26 | 2023-01-31 | 中国科学院上海光学精密机械研究所 | Containing YF 3 Crystalline phase fluoride glass ceramics and preparation method thereof |
| CN115650590B (en) * | 2022-09-26 | 2023-09-01 | 中国科学院上海光学精密机械研究所 | Containing YF 3 Crystal phase fluoride microcrystalline glass and preparation method thereof |
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