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DE3500578A1 - Optical glass having refractive indices of from 1.73 to 1.80 and Abbe numbers >/= 49 - Google Patents

Optical glass having refractive indices of from 1.73 to 1.80 and Abbe numbers >/= 49

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Publication number
DE3500578A1
DE3500578A1 DE19853500578 DE3500578A DE3500578A1 DE 3500578 A1 DE3500578 A1 DE 3500578A1 DE 19853500578 DE19853500578 DE 19853500578 DE 3500578 A DE3500578 A DE 3500578A DE 3500578 A1 DE3500578 A1 DE 3500578A1
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DE
Germany
Prior art keywords
weight
sio2
refractive indices
optical glass
good
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.)
Granted
Application number
DE19853500578
Other languages
German (de)
Other versions
DE3500578C2 (en
Inventor
Volkmar 6500 Mainz Geiler
Danuta Dipl.-Ing. 6204 Taunusstein Grabowski
Ludwig Dipl.-Chem. 6501 Klein-Winternheim Roß
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Original Assignee
Schott Glaswerke AG
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Filing date
Publication date
Application filed by Schott Glaswerke AG filed Critical Schott Glaswerke AG
Priority to DE19853500578 priority Critical patent/DE3500578C2/en
Priority to JP337086A priority patent/JPS61219738A/en
Publication of DE3500578A1 publication Critical patent/DE3500578A1/en
Application granted granted Critical
Publication of DE3500578C2 publication Critical patent/DE3500578C2/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

A novel optical glass having refractive indices of from 1.73 to 1.80 and Abbe numbers >/= 49, which is distinguished by good devitrification stability, good transmission throughout the wavelength range from 370 to 1400 nm, good alkali resistance and good resistance to changing climatic conditions, comprises (% by weight): SiO2 0.5-5.0, B2O3 28.0-34.0, ZnO 0.5-4.0, La2O3 40.0-50.0, Y2O3 6.0-10.5, HfO2 0.0-2.0, Gd2O3 3.0-8.0, ZrO2 1.0-8.0, Ta2O 5 0.0-3.0, WO3 0.0-2.0, where SiO2 + HfO2 + ZrO2 = 0.5-14.5.

Description

Beschreibungdescription

Die Erfindung betrifft ein neues optisches Glas mit Brechwerten 1,73 bis 1,80 und Abbezahlen x 49.The invention relates to a new optical glass with a refractive index of 1.73 up to 1.80 and paying off x 49.

Der Stand der Technik ist in der DE-OS 31 02 690 ausführlich dargestellt. In einigen der dort erwähnten Patentanmeldungen wird der Versuch beschrieben, die extreme optische Lage in Systemen mit viel Yb203 - z.B. bis 40 Gew.-(J 78 025 383) oder bis 65 Gew.-% (J 81 78 447) oder bis 32 Gew.-% (DE-OS 31 30 715) zu erreichen. Dabei zeigen diese Gläser verminderte Transmission im Bereich 850 bis 1000 nm Wellenlänge und sind wegen des hohen Yb203-Preises sehr teuer. In der DE-OS 2237259 werden die gewünschten optischen Lagen nur mit bis zu 53 Gew.-% Cd0 und bis zu 30 Gew.-% Ta205 bei 20 bis 30 Gew.-% Anteilen an Mo-Oxiden erreicht.The prior art is shown in detail in DE-OS 31 02 690. In some of the patent applications mentioned there, the attempt is described which extreme optical position in systems with a lot of Yb203 - e.g. up to 40 wt .- (J 78 025 383) or up to 65% by weight (J 81 78 447) or up to 32% by weight (DE-OS 31 30 715). These glasses show reduced transmission in the range from 850 to 1000 nm wavelength and are very expensive because of the high Yb203 price. In DE-OS 2237259 the desired optical layers only with up to 53% by weight of Cd0 and up to 30% by weight of Ta205 reached at 20 to 30 wt .-% proportions of Mo oxides.

CdO-haltige Gläser entsprechen nicht mehr dem heutigen Umweltschutzbedürfnis und Ta205 führt aufgrund seines hohen Preises in größeren Anteilen zu sehr teuren Gläsern. Außerdem lassen sich in diesen Systemen bei Brechzahlen > 1,75 nur noch Abbezahlen < 50 erschmelzen.Glasses containing CdO no longer meet today's environmental protection requirements and Ta205 leads to very expensive ones in larger proportions due to its high price Glasses. In addition, in these systems, refractive indices> 1.75 can only be used Pay off <50 melt.

Die Gläser gemäß J 77 155 615 und US 41 11 707 benötigen über 17 Gew.-% Gd203, wobei die Stabilität der Gläser sehr gering ist. Die Gläser gemäß DE-OS 31 02 690 und DE-OS 31 30 066 sind gekennzeichnet durch einen hohen Gehalt an Nb205 - bis zu 11 Gew.-% (DE-OS 31 02 690) - und durch Fehlen von Gd203 (DE-OS 31 30 066).The glasses according to J 77 155 615 and US 41 11 707 require more than 17% by weight Gd203, whereby the stability of the glasses is very low. The glasses according to DE-OS 31 02 690 and DE-OS 31 30 066 are characterized by a high content of Nb205 - Up to 11 wt .-% (DE-OS 31 02 690) - and the lack of Gd203 (DE-OS 31 30 066).

Die Gläser gemäß DE-OS 33 07 497 sind gekennzeichnet durch Fehlen von Hf02, Ta205 und W03.The glasses according to DE-OS 33 07 497 are characterized by lack by Hf02, Ta205 and W03.

Ziel der Erfindung ist es, einen Zusammensetzungsbereich für ein optisches Glas mit den Brechwerten 1,73 bis 1,80 und einer Abbezahl >, 49 zu finden, wobei die Entglasungsstabilität des Glases ausreichend für die Anforderungen der optischen Glasindustrie sein soll. Dieses Ziel wird mit einem Glas gemäß den Patentansprüchen erreicht.The aim of the invention is to provide a composition range for an optical Glass with a refractive index of 1.73 to 1.80 and an Abbe number> .49 can be found, whereby the devitrification stability of the glass is sufficient for the requirements of the optical Glass industry is supposed to be. This aim is achieved with a glass according to the claims achieved.

Die erfindungsgemäßen Gläser erfüllen nicht nur die Forderung nach guter Entglasungsstabilität, sondern auch die nach guter Transmission, besonders im gesamten Bereich von 370 bis 1400 nm Wellenlänge, nach guter Alkaliresistenz, Unempfindlichkeit gegen Fleckenbildung und guter Klimawechselresistenz (entsprechende Prüfverfahren sind im Schott-Katalog "Optisches Glas", Nr. 311 d, 1980 angegeben).The glasses according to the invention not only meet the requirement for good devitrification stability, but also that of good transmission, especially in the entire range from 370 to 1400 nm wavelength, after good alkali resistance, Insensitivity to staining and good climate change resistance (corresponding Test methods are given in the Schott catalog "Optical Glass", No. 311d, 1980).

Die gute Kristallisationsstabilität wird durch bestimmte Anteile an SiO2, B203, ZrO2, Y203. Gd203 und durch ausgewogene Zusätze von HfO2 - bis zu 1,5 Gew.-%, Ta205 - bis zu 3 Gew.-%, WO3 - bis zu 1 Gew.-% erreicht. Die drei Oxide HfO2, Ta2O5 und W03 wirken in den wohlausgewogenen geringen Mengen besonders kristallisationsstabilisierend.The good crystallization stability is due to certain proportions of SiO2, B203, ZrO2, Y203. Gd203 and through balanced additions of HfO2 - up to 1.5 % By weight, Ta205 - up to 3% by weight, WO3 - up to 1% by weight achieved. The three oxides HfO2, Ta2O5 and W03 have a particularly stabilizing effect on crystallization in the well-balanced small amounts.

Tabelle 1 enthält 11 Zusammensetzungsbeispiele gemäß der vorliegenden Erfindung.Table 1 contains 11 composition examples according to the present invention Invention.

Die erfindungsgemäßen Gläser werden folgendermaßen hergestellt: Die Rohstoffe (Oxide, Carbonate, ev. Fluoride und Nitrate) werden abgewogen. Ein Läutermittel, wie As203 in Anteilen von 0,1 bis 0,5 Gew.-%, wird zugegeben und gut gemischt. Das Glasgemenge wird bei ca. 1280 - 1320 OC im Platin- oder Keramiktiegel eingeschmolzen, danach geläutert und mittels eines Rührers gut homogenisiert. Bei einer Gußtemperatur von 1080 -1180 OC wird das Glas zu den gewünschten Abmessungen verarbeitet.The glasses according to the invention are produced as follows: The Raw materials (oxides, carbonates, possibly fluorides and nitrates) are weighed. A purifying agent like As203 in proportions of 0.1-0.5% by weight, add and mix well. That Glass batch is melted down in a platinum or ceramic crucible at approx. 1280 - 1320 OC, then refined and well homogenized using a stirrer. At a casting temperature from 1080 -1180 OC the glass is processed to the desired dimensions.

Schmelzbeispiel für 100 kg berechnetes Glas Oxid Gew.-% Rohstoff Einwaage (kg) SiO2 0,80 Quarzmehl 0,80 B203 30,40 H3B03 53,90 ZnO 2,00 ZnO 2,01 La2O3 43,00 La2O3 43,01 Y203 9,20 y203 9,29 ZrO2 5,50 ZrO2 5,51 Gd203 5,30 Gd2O3 5,31 Ta205 3,00 Ta205 3,00 WO3 0,70 W03 0,70 123,53 As203 0,10 As2O3 0,10 Läutermittel 123,63 Gemenge Die Eigenschaften dieses Glases sind in Tabelle 1, Beispiel 6 angegeben.Melting example for 100 kg calculated glass oxide wt .-% raw material weight (kg) SiO2 0.80 Quartz powder 0.80 B203 30.40 H3B03 53.90 ZnO 2.00 ZnO 2.01 La2O3 43.00 La2O3 43.01 Y203 9.20 y203 9.29 ZrO2 5.50 ZrO2 5.51 Gd203 5.30 Gd2O3 5.31 Ta205 3.00 Ta205 3.00 WO3 0.70 W03 0.70 123.53 As203 0.10 As2O3 0.10 refining agent 123.63 Mixture The properties of this glass are given in Table 1, Example 6.

Tabelle 1 1 2 3 4 5 6 7 8 9 10 11 SiO2 2,50 2,50 2,50 2,50 1,80 0,80 4,50 1,20 1,70 2,00 3,50 B2O3 33,00 30,40 32,00 32,00 28,80 30,40 33,20 28,80 30,00 28,70 32,00 ZnO 2,40 2,00 2,40 2,40 1,50 2,00 3,60 1,50 3,60 0,90 2,60 La2O3 42,00 41,00 41,00 41,00 42,00 43,00 43,00 43,10 45,00 41,00 49,00 Y2O3 8,20 9,20 8,20 8,20 10,10 9,20 6,00 10,10 8,00 10,10 6,00 ZrO2 4,50 6,50 4,50 4,50 7,50 5,50 1,00 7,50 6,00 7,50 2,00 Gd2O3 5,00 6,00 5,00 5,00 6,90 5,30 3,00 7,00 4,00 7,70 3,00 HfO2 -- -- -- -- -- -- 1,50 1,50 1,50 As2O3 0,20 0,20 0,20 0,20 0,20 0,10 0,20 0,10 0,20 0,20 0,10 Ta2O5 0,70 0,70 0,70 0,70 0,70 3,00 -- 0,70 -- 0,80 WO3 0,70 TiO2 2,0 Cs2O 1,50 1,50 1,50 1,50 0,50 -- -- -- -- 1,10 0,40 PbO -- -- 2,0 Nb2O5 F- -- 0,85 nd 1,7475 1,7637 1,7505 1,7607 1,7816 1,7826 1,7306 1,7957 1,7752 1,7802 1,7442 d 51,77 50,48 50,34 49,00 49,50 49,20 54,00 49,30 50,13 49,60 53,50Table 1 1 2 3 4 5 6 7 8 9 10 11 SiO2 2.50 2.50 2.50 2.50 1.80 0.80 4.50 1.20 1.70 2.00 3.50 B2O3 33.00 30.40 32.00 32.00 28.80 30.40 33.20 28.80 30.00 28.70 32.00 ZnO 2.40 2.00 2.40 2.40 1.50 2.00 3.60 1.50 3.60 0.90 2.60 La2O3 42.00 41.00 41.00 41.00 42.00 43.00 43.00 43.10 45.00 41.00 49.00 Y2O3 8.20 9.20 8.20 8.20 10.10 9.20 6.00 10.10 8.00 10.10 6.00 ZrO2 4.50 6.50 4.50 4.50 7.50 5.50 1.00 7.50 6.00 7.50 2.00 Gd2O3 5.00 6.00 5.00 5.00 6.90 5.30 3.00 7.00 4.00 7.70 3.00 HfO2 - - - - - - 1.50 1.50 1.50 As2O3 0.20 0.20 0.20 0.20 0.20 0.10 0.20 0.10 0.20 0.20 0.10 Ta2O5 0.70 0.70 0.70 0.70 0.70 3.00 - 0.70 - 0.80 WO3 0.70 TiO2 2.0 Cs2O 1.50 1.50 1.50 1.50 0.50 - - - - 1.10 0.40 PbO - - 2.0 Nb2O5 F- - 0.85 nd 1.7475 1.7637 1.7505 1.7607 1.7816 1.7826 1.7306 1.7957 1.7752 1.7802 1.7442 d 51.77 50.48 50.34 49.00 49.50 49.20 54.00 49.30 50.13 49.60 53.50

Claims (1)

Optisches Glas mit Brechwerten von 1,73 bis 1,80 und Abbezahlen >, 49 Patentansprüche: 1. Optisches Glas mit Brechwerten 1,73 bis 1,80 und Abbezahlen # 49, gekennzeichnet durch folgende Zusammensetzung (in Gew.-%): SiO2 0,5 - 5,0 B203 28,0 - 34,0 ZnO 0,5 - 4,0 La203 40,0 - 50,0 Y203 6,0 - 10,5 HfO2 0,0 - 2,0 Gd2O3 3,0 - 8,0 ZrO2 1,0 - 8,0 1a205 0,0 - 3,0 W03 0,0 - 2,0, wobei SiO2 + HfO2 + Zr02 = 0,5 - 14,£ 2. Glas nach Anspruch 1, gekennzeichnet durch folgende Zusammensetzung (in Gew.-%): SiO2 0,5 - 2,5 B203 28,0 - 30,0 ZnO 0,5 - 2,0 La203 40,0 - 45,0 Y203 6,0 - 10,5 HfO2 0,5 - 1,5 Gd203 5,0 - 8,0 ZrO2 4,0 - 8,0 Ta205 0,5 - 3,0 WO3 0,2 - 1,0, wobei SiO2 + Zr02 + Hf02 = 0,5 - 10,5.Optical glass with refractive indices from 1.73 to 1.80 and Abbezahlen>, 49 Claims: 1. Optical glass with refractive indices 1.73 to 1.80 and Abbezahl # 49, characterized by the following composition (in% by weight): SiO2 0.5 - 5.0 B203 28.0 - 34.0 ZnO 0.5 - 4.0 La203 40.0 - 50.0 Y203 6.0 - 10.5 HfO2 0.0 - 2.0 Gd2O3 3.0 - 8.0 ZrO2 1.0 - 8.0 1a205 0.0 - 3.0 W03 0.0 - 2.0, where SiO2 + HfO2 + Zr02 = 0.5 - £ 14 2. Glass according to claim 1, characterized by following composition (in% by weight): SiO2 0.5 - 2.5 B203 28.0 - 30.0 ZnO 0.5 - 2.0 La203 40.0 - 45.0 Y203 6.0 - 10.5 HfO2 0.5 - 1.5 Gd203 5.0 - 8.0 ZrO2 4.0 - 8.0 Ta205 0.5 - 3.0 WO3 0.2 - 1.0, where SiO2 + Zr02 + Hf02 = 0.5 - 10.5. 3. Glas nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es (in Gew.-%) enthält: Cs20 0,0 - 2,0 EM20 0,0 - 2,0 wobei M20 = Li2O, Na20, K20, Cs20.3. Glass according to claim 1 or 2, characterized in that it (in % By weight) contains: Cs20 0.0 - 2.0 EM20 0.0 - 2.0 where M20 = Li2O, Na20, K20, Cs20. 4. Glas nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es (in Gew.-%) enthält: PbO 0,0 - 2,0.4. Glass according to one of claims 1 to 3, characterized in that that it contains (in% by weight): PbO 0.0 - 2.0. 5. Glas nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es (in Gew.-%) enthält: TiO2 0,0 - 2,0.5. Glass according to one of claims 1 to 4, characterized in that that it contains (in% by weight): TiO2 0.0 - 2.0. 6. Glas nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es (in Gew.-%) enthält: Nb205 0,0 - 1,0.6. Glass according to one of claims 1 to 5, characterized in that that it contains (in% by weight): Nb205 0.0 - 1.0. 7. Glas nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß 0,0 - 1,0 Gew.-% Sauerstoffionen durch Fluorionen ersetzt sind.7. Glass according to one of claims 1 to 6, characterized in that that 0.0-1.0% by weight of oxygen ions are replaced by fluorine ions.
DE19853500578 1985-01-10 1985-01-10 Optical glass with refractive indices from 1.73 to 1.80 and Abbe numbers ≥ 49 Expired DE3500578C2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19853500578 DE3500578C2 (en) 1985-01-10 1985-01-10 Optical glass with refractive indices from 1.73 to 1.80 and Abbe numbers ≥ 49
JP337086A JPS61219738A (en) 1985-01-10 1986-01-10 Optical glass having refractive index of 1.73-1.80 and abbe's number of more than 49

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19853500578 DE3500578C2 (en) 1985-01-10 1985-01-10 Optical glass with refractive indices from 1.73 to 1.80 and Abbe numbers ≥ 49

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DE3500578A1 true DE3500578A1 (en) 1986-07-10
DE3500578C2 DE3500578C2 (en) 1987-02-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062712A1 (en) * 2001-02-05 2002-08-15 Koninklijke Philips Electronics N.V. Multicomponent glass, glass fiber, twister and taper
US7297647B2 (en) * 2004-02-26 2007-11-20 Schott Ag Lead- and arsenic-free optical lanthanum flint glasses

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DE10122263C2 (en) * 2001-05-08 2003-04-03 Schott Glas Optical glasses and their use
JP2009242210A (en) * 2008-03-31 2009-10-22 Ohara Inc Optical glass, optical element and optical device
JP5249697B2 (en) * 2008-09-26 2013-07-31 アルフレッド ユニバーシティ Optical glass
JP6096409B2 (en) * 2010-10-29 2017-03-15 株式会社オハラ Optical glass, preform and optical element
JP6049591B2 (en) * 2013-07-31 2016-12-21 株式会社オハラ Optical glass, preform material and optical element
JP6188553B2 (en) * 2013-07-31 2017-08-30 株式会社オハラ Optical glass, preform material and optical element
WO2015083616A1 (en) * 2013-12-03 2015-06-11 旭硝子株式会社 Optical glass, preform for press-molding, and optical element
JP6472657B2 (en) * 2014-12-26 2019-02-20 Hoya株式会社 Glass, glass material for press molding, optical element blank, and optical element
JP2017171578A (en) * 2017-06-23 2017-09-28 株式会社オハラ Optical glass and optical element

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3307497A1 (en) * 1983-03-03 1984-09-06 Schott Glaswerke, 6500 Mainz OPTICAL GLASS WITH BREAKING VALUES> = 1.70, PAYBACK <= 48, WITH GOOD DE-GLASS STABILITY AND GOOD CHEMICAL RESISTANCE

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS606297B2 (en) * 1980-05-30 1985-02-16 株式会社小原光学硝子製造所 optical glass

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3307497A1 (en) * 1983-03-03 1984-09-06 Schott Glaswerke, 6500 Mainz OPTICAL GLASS WITH BREAKING VALUES> = 1.70, PAYBACK <= 48, WITH GOOD DE-GLASS STABILITY AND GOOD CHEMICAL RESISTANCE

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062712A1 (en) * 2001-02-05 2002-08-15 Koninklijke Philips Electronics N.V. Multicomponent glass, glass fiber, twister and taper
US6690869B2 (en) 2001-02-05 2004-02-10 Koninklijke Philips Electronics N.V. Multicomponent glass, glass fiber, twister and taper
US7297647B2 (en) * 2004-02-26 2007-11-20 Schott Ag Lead- and arsenic-free optical lanthanum flint glasses

Also Published As

Publication number Publication date
JPS61219738A (en) 1986-09-30
DE3500578C2 (en) 1987-02-12
JPH0472779B2 (en) 1992-11-19

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