CN1298652C - Fluorozirconate glass containing tellurium dioxide - Google Patents
Fluorozirconate glass containing tellurium dioxide Download PDFInfo
- Publication number
- CN1298652C CN1298652C CNB2005100241757A CN200510024175A CN1298652C CN 1298652 C CN1298652 C CN 1298652C CN B2005100241757 A CNB2005100241757 A CN B2005100241757A CN 200510024175 A CN200510024175 A CN 200510024175A CN 1298652 C CN1298652 C CN 1298652C
- Authority
- CN
- China
- Prior art keywords
- glass
- fluorozirconate
- teo
- fluoride
- tellurium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000005386 fluorozirconate glass Substances 0.000 title claims abstract description 16
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 32
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 3
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 3
- 229910017768 LaF 3 Inorganic materials 0.000 claims description 3
- 239000005383 fluoride glass Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- 229910002319 LaF3 Inorganic materials 0.000 abstract 1
- 229910003069 TeO2 Inorganic materials 0.000 abstract 1
- 229910007998 ZrF4 Inorganic materials 0.000 abstract 1
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000007496 glass forming Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 abstract 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000005371 ZBLAN Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 1
- 108010023321 Factor VII Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000000146 host glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- -1 optical waveguides Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FEPMHVLSLDOMQC-UHFFFAOYSA-N virginiamycin-S1 Natural products CC1OC(=O)C(C=2C=CC=CC=2)NC(=O)C2CC(=O)CCN2C(=O)C(CC=2C=CC=CC=2)N(C)C(=O)C2CCCN2C(=O)C(CC)NC(=O)C1NC(=O)C1=NC=CC=C1O FEPMHVLSLDOMQC-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
-
- 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
- C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
-
- 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
-
- 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
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
TeO-containing2The fluorozirconate glass comprises the following main compounds in percentage by mole: TeO2：2～12，ZrF4：45～60，BaF2：25～35，LaF3+AlF3+YF3: 5 to 11. The glass has high transmittance in the near ultraviolet to middle infrared wave band. He-ShiCompared with the prior fluoride glass, the fluoride glass has better chemical stability and glass forming performance, and is suitable for manufacturing large-size infrared materials.
Description
Technical field
The present invention relates to Fluorozirconate glass, particularly a kind of Fluorozirconate glass that contains tellurium dioxide.Be characterized in to middle-infrared band very high seeing through being arranged, and have high anti-devitrification ability, can be made into large-sized optical material near ultraviolet.
Background technology
Fluoride glass has optical application prospect widely, as is used to prepare material of infrared window, ultra-low-loss fiber, optical waveguides, fiber amplifier etc.The research of the large size fluoride glass that chemical stability is good is the focus of fluoride glass research always.With ZrF
1For the fluoride glass of the main moiety of glass is called Fluorozirconate glass.Compare with other fluoride glass, the not only formation ability of Fluorozirconate glass is good, and optical property is also very good, is the main fluoride glass matrix of preparation fluoride fiber.Although developed many new systems, all easy devitrification of nearly all system.Poulain reported two kinds of typical Fluorozirconate glass ZBLA and ZBLAN (referring to J.Non-Cryst.Solids, 1983,56:1-14).With ZBLA (56ZrF
434BaF
26LaF
34AlF
3) have good infrared property for the Fluorozirconate glass of representative.But because the one-tenth glass properties of its difference, the thickness that also should not form is greater than the large-size glass report of 15mm at present.Although after introducing NaF on the basis of this composition, ZBLAN forms and has good devitrification resistance energy, and obtained thickness greater than the glass material of 30mm (referring to Mater.Sci.Forum, 1991,67﹠amp; 68:13-16), but because the adding of NaF, the chemical stability of glass reduces, and is not suitable for use in the infrared window in the atmosphere.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the problem of existing Fluorozirconate glass, a kind of Fluorozirconate glass that contains tellurium dioxide is provided, it is under the prerequisite of not damaging its chemical stability, substantially keep pure fluoride glass infrared property, improve the one-tenth glass properties of fluozirconate, and can obtain the large size infrared glass.
Technical solution of the present invention is as follows:
A kind of TeO that contains
2Fluorozirconate glass, it is characterized in that in the Fluorozirconate glass component, adding TeO
2, the compositing range of its glass is as follows:
Form mol%
TeO
2： 2～12
ZrF
4： 45～60，
BaF
2： 25～35，
LaF
3+AlF
3+YF
3： 5～11。
The preparation process of this glass is: ZrF
4With NH
4ZrF
5Form introduce, other fluorochemicals are high-purity fluoride raw material.This glass prepares in two steps, at first makes the grog of oxide-free in platinum crucible, is adding TeO more then
2The glass grog 830 ℃ found after, add TeO
2Stir the back, is poured in the preheating template.Glass is annealed at transition temperature, then furnace cooling.
Be usually used in weighing index Δ T (the Δ T=T that component becomes the glass properties quality
x-T
g) and S, S=(Tx-Tg) (Tp-Tx)/Tg, wherein T
gBe the transition temperature of glass, T
xFor the crystallization of glass begins temperature, T
pBe the crystallization peak temperature.Δ T and the big more glass that helps into more of S value are fit to the preparation large-size glass.
Adopt the above-mentioned glass that fluozirconate is formed and the preparation method prepares that contains tellurium dioxide, after tested, the S value of resulting glass significantly improves than former pure fluorochemical, has kept the good visible infrared property of former fluoride glass simultaneously substantially.The cutoff wavelength of gained glass is greater than 6um, and the glass phonon energy is low, becomes glass properties good, is fit to preparation infrared laser optical fiber and is used as fiber amplifier host glass and other optical materials.
Description of drawings
Fig. 1 is respectively the embodiment of the invention 6 (TZF1) and pure fluorochemical is formed 57ZrF
434BaF
24.5LaF
34.5AlF
3(ZF1) differential thermal of prepared glass (DTA) curve.
Fig. 2 is the transmittance curve figure of the embodiment of the invention 6.
Embodiment:
Following table is enumerated the molar percentage of six specific embodiments of the present invention and is formed, and has also provided corresponding measured and calculate the characteristic temperature of glass of gained and the size of anti-crystallization ability stable factor S simultaneously.Wherein, the characteristic temperature value of glass obtains by differential thermal analysis, and the temperature rise rate in the test process is 10 ℃/min.
| TeO 2 | ZrF 4 | BaF 2 | MF 3 | |||
| LaF 3 | AlF 3 | YF 3 | ||||
| 1 | 2 | 60 | 28 | 4 | 6 | 0 |
| 2 | 12 | 45 | 35 | 0 | 4 | 4 |
| 3 | 8 | 52 | 31 | 5 | 4 | 0 |
| 4 | 6 | 55 | 34 | 2 | 0 | 3 |
| 5 | 4 | 60 | 25 | 5 | 3 | 3 |
| 6 | 6 | 54 | 32 | 4 | 4 | 0 |
| Tg(℃) | T x(℃) | T p(℃) | T m(℃) | | |
| 1 | 295 | 380 | 414 | 539 | 9.1 |
| 2 | 300 | 400 | 438 | 516 | 12.6 |
| 3 | 296 | 389 | 422 | 526 | 10.4 |
| 4 | 296 | 380 | 412 | 531 | 9 |
| 5 | 296 | 383 | 412 | 537 | 8.5 |
| 6 | 298 | 397 | 433 | 520 | 12 |
Fig. 1 is respectively the embodiment of the invention 6 (TZF1) and pure fluorochemical is formed 57ZrF
434BaF
24.5LaF
34.5AlF
3(ZF1) differential thermal of prepared glass (DTA) curve.Wherein the TZF1 curve the Δ T of corresponding glass be 80 ℃, S is 6.78; And curve ZF1 the Δ T of corresponding glass be 100 ℃, S is 12.Bigger Δ T (Δ T=T
x-T
g) (S=(Tx-Tg) (Tp-Tx)/Tg) value shows that TZF1 has the better glass properties that becomes than ZF1, is fit to preparation large size infra-red material with S.
Fig. 2 is the transmittance curve of the glass sample (thickness of sample is 6mm) of the embodiment of the invention 6 at 0.3～7.0um.As seen from the figure, the Fluorozirconate glass that contains tellurium dioxide of the present invention has good near ultraviolet to being popular in performance at home and abroad.
Claims (1)
1, a kind of TeO that contains
2Fluorozirconate glass, it is characterized in that in the Fluorozirconate glass component, adding TeO
2, the compositing range of its glass is as follows:
Form mol%
TeO
2： 2～12
ZrF
4： 45～60，
BaF
2： 25～35，
LaF
3+AlF
3+YF
3： 5～11。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100241757A CN1298652C (en) | 2005-03-02 | 2005-03-02 | Fluorozirconate glass containing tellurium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100241757A CN1298652C (en) | 2005-03-02 | 2005-03-02 | Fluorozirconate glass containing tellurium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1673141A CN1673141A (en) | 2005-09-28 |
| CN1298652C true CN1298652C (en) | 2007-02-07 |
Family
ID=35045953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100241757A Expired - Fee Related CN1298652C (en) | 2005-03-02 | 2005-03-02 | Fluorozirconate glass containing tellurium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298652C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030275A (en) * | 2013-01-17 | 2013-04-10 | 中国科学院上海光学精密机械研究所 | Erbium ion doped intermediate infrared luminous fluorine tellurate glass |
| CN103241949A (en) * | 2013-05-21 | 2013-08-14 | 中国科学院上海光学精密机械研究所 | Lead oxide containing fluoroziconate glass and preparation method thereof |
| CN110156322A (en) * | 2019-06-12 | 2019-08-23 | 中国科学院上海光学精密机械研究所 | A kind of saturating infrared Fluorozirconate glass and preparation method thereof containing gallium oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105002A (en) * | 1993-08-12 | 1995-07-12 | 武汉大学 | Preparing fluozirconate glass by homogeneous coprecipitation method |
| JPH08313945A (en) * | 1995-05-18 | 1996-11-29 | Nippon Telegr & Teleph Corp <Ntt> | Optical amplifier |
| US6352949B1 (en) * | 1999-06-15 | 2002-03-05 | Peter Willems | Fluoro glass ceramic showing photostimulable properties |
-
2005
- 2005-03-02 CN CNB2005100241757A patent/CN1298652C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105002A (en) * | 1993-08-12 | 1995-07-12 | 武汉大学 | Preparing fluozirconate glass by homogeneous coprecipitation method |
| JPH08313945A (en) * | 1995-05-18 | 1996-11-29 | Nippon Telegr & Teleph Corp <Ntt> | Optical amplifier |
| US6352949B1 (en) * | 1999-06-15 | 2002-03-05 | Peter Willems | Fluoro glass ceramic showing photostimulable properties |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1673141A (en) | 2005-09-28 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SUZHOU HENGCANG INFRARED OPTICAL MATERIALS R & D Free format text: FORMER OWNER: SHANGHAI OPTICS AND PRECISION MECHANICS INSTITUTE, CHINESE ACADEMY OF SCIENCES Effective date: 20080711 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080711 Address after: No. 98, Yueyang Road, Chengxiang Town, Taicang, Jiangsu Patentee after: Suzhou Hengcang Infrared Optical Material Research and Development Center Co., Ltd. Address before: Shanghai 800-211 post office box Patentee before: Shanghai Optical Precision Machinery Inst., Chinese Academy of Sciences |
|
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI OPTICAL PRECISION MACHINERY INST., CHINES Free format text: FORMER OWNER: SUZHOU HENGCANG INFRARED OPTICAL MATERIAL RESEARCH AND DEVELOPMENT CENTER CO., LTD. Effective date: 20110916 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 215400 SUZHOU, JIANGSU PROVINCE TO: 201800 JIADING, SHANGHAI |
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| TR01 | Transfer of patent right |
Effective date of registration: 20110916 Address after: 201800 Shanghai 800-211 post office box Patentee after: Shanghai Optical Precision Machinery Inst., Chinese Academy of Sciences Address before: 215400 No. 98, Yueyang Road, Chengxiang Town, Jiangsu, Taicang Patentee before: Suzhou Hengcang Infrared Optical Material Research and Development Center Co., Ltd. |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20120302 |