DE3138138C2 - Th0 2 - and Cd0-free optical glass with refractive indices 1.73 - 1.88 and Abbe numbers of 35 - 52 - Google Patents

Th0 2 - and Cd0-free optical glass with refractive indices 1.73 - 1.88 and Abbe numbers of 35 - 52

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Publication number
DE3138138C2
DE3138138C2 DE19813138138 DE3138138A DE3138138C2 DE 3138138 C2 DE3138138 C2 DE 3138138C2 DE 19813138138 DE19813138138 DE 19813138138 DE 3138138 A DE3138138 A DE 3138138A DE 3138138 C2 DE3138138 C2 DE 3138138C2
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DE
Germany
Prior art keywords
weight
refractive indices
optical glass
abbe numbers
free optical
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
Application number
DE19813138138
Other languages
German (de)
Other versions
DE3138138A1 (en
Inventor
Volkmar 6500 Mainz-Finthen Geiler
Karl Dr. 6204 Taunusstein Mennemann
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 6500 Mainz
Schott Glaswerke AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schott Glaswerke 6500 Mainz, Schott Glaswerke AG filed Critical Schott Glaswerke 6500 Mainz
Priority to DE19813138138 priority Critical patent/DE3138138C2/en
Priority to FR8216032A priority patent/FR2513621A1/en
Priority to GB08227105A priority patent/GB2106497B/en
Priority to JP16516282A priority patent/JPS5869741A/en
Publication of DE3138138A1 publication Critical patent/DE3138138A1/en
Application granted granted Critical
Publication of DE3138138C2 publication Critical patent/DE3138138C2/en
Expired legal-status Critical Current

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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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium

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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

Das neue optische Glas mit Brechwerten von 1,73-1,88 und Abbezahlen von 35-52 liegt im System B ↓2O ↓3 - La ↓2O ↓3 - Y ↓2O ↓3 - WO ↓3 - ZrO ↓2 und hat einen erheblichen Fluoridgehalt. Dank dieser Zusammensetzung ist es außerordentlich entglasungsstabil, und dank des Fehlens von CdO und ThO ↓2 ist es auch umweltfreundlich.The new optical glass with refractive indices of 1.73-1.88 and Abbe numbers of 35-52 is in the system B ↓ 2O ↓ 3 - La ↓ 2O ↓ 3 - Y ↓ 2O ↓ 3 - WO ↓ 3 - ZrO ↓ 2 and has a significant amount of fluoride. Thanks to this composition, it is extremely stable to devitrification, and thanks to the absence of CdO and ThO ↓ 2, it is also environmentally friendly.

Description

B2O3 B 2 O 3 19-37 Gew.-%19-37% by weight La2O3 La 2 O 3 39-49 Gew.-%39-49% by weight Y2O3 Y 2 O 3 5-10Gew.-%5-10% by weight La2O3 + Y2O3 La 2 O 3 + Y 2 O 3 44-55Gew.-%44-55% by weight WO3 WHERE 3 1-20 Gew.-%1-20% by weight ZrO2 ZrO 2 3- 9Gew.-o/o3- 9 weight o / o

wobei 1 —4% der Menge an O2~-Ionen durch F~- Ionen ersetzt sind.1 - 4% of the amount of O 2 - ions being replaced by F - ions.

2. Glas nach Anspruch 1, dadurch gekennzeichnet, daß es zusätzlich enthält:2. Glass according to claim 1, characterized in that it additionally contains:

ZnOZnO

O -14Gew.-9O -14 Weight -9

3. Glas nach Anspruch 1 und 2, dadurch gekennzeichnet, daß es zusätzlich enthält:3. Glass according to claim 1 and 2, characterized in that it additionally contains:

Nb2O5 Nb 2 O 5

0-9Gew.-%0-9% by weight

4. Glas nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß es zusätzlich enthält:4. Glass according to claim 1 to 3, characterized in that it additionally contains:

TiO2 TiO 2

0-8Gew.-%0-8% by weight

5. Glas nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß es zusätzlich enthält:5. Glass according to claim 1 to 4, characterized in that it additionally contains:

PbOPbO

6. Glas nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es zusätzlich enthält:6. Glass according to claim 1 to 5, characterized in that it additionally contains:

Ta2O5 Ta 2 O 5

Die vorliegende Erfindung betrifft optische Gläser mit Brechwerten von 1.73-1.88 und Abbezahlen von 35-52, die frei sind von den giftigen Oxiden des CdO und ThO2, mit ausgezeichneter Entgiasungsstabilität erschmolzen werden können, und die weiterhin relativ geringe Gemengekosten verursachen, da auf teures Ta2Oj verzichtet werden kann im Vergleich zu bekannten optischen Gläsern ähnlicher Lage. Ein wesentliches Merkmal dieser Gläser ist die gleichzeitige Anwesenheit von WO3 und Fluorid-Ionen, die die beschriebene hohe Entgiasungsstabilität bedingen, und der Verzicht auf Erdalkali- und Alkalioxide, die einen gegenläufigen Effekt ausüben; Erdalkali- und Alkalioxide bilden bekanntlich ionische Fluoride mit hoher Kristallisationstendenz. The present invention relates to optical glasses with refractive indices of 1.73-1.88 and Abbe numbers of 35-52, which are free from the toxic oxides of CdO and ThO 2 , can be melted with excellent degassing stability, and which furthermore cause relatively low batch costs because expensive Ta 2 Oj can be dispensed with in comparison to known optical glasses of a similar position. An essential feature of these glasses is the simultaneous presence of WO 3 and fluoride ions, which cause the high degassing stability described, and the absence of alkaline earth and alkali metal oxides, which have an opposing effect; Alkaline earth and alkali oxides are known to form ionic fluorides with a high tendency to crystallize.

Die Möglichkeit, u.a. Fluorid-Ionen ins Glas einzubringen, wurde beschrieben in der DE-OS 27 56 160. Gläser entsprechend dieser DE-OS haben jedoch den Nachteil, daß sie gleichzeitig SiO2 enthalten, was leicht zur Glastrübung führt; außerdem sind lediglich Brechwerte bis 1.80 zu erreichen, und sie sind zudem recht teuer, da sie Anteile von > 17 Gew.-% Gd2O3 enthalten. Schließlich weisen sie nicht die für eine Produktion zu fordernde Entgiasungsstabilität auf, da der Anteil der Seltenerd-Oxide La2O3 + Gd2O3 + Y2O3 >58Gew.-% beträgtThe possibility of introducing fluoride ions into the glass, among other things, has been described in DE-OS 27 56 160. However, glasses according to this DE-OS have the disadvantage that they also contain SiO 2 , which easily leads to glass clouding; in addition, only refractive indices of up to 1.80 can be achieved, and they are also quite expensive, since they contain proportions of> 17% by weight of Gd 2 O 3. Finally, they do not have the degassing stability required for production, since the proportion of rare earth oxides La 2 O 3 + Gd 2 O 3 + Y 2 O 3 is > 58% by weight

In der DE-AS 26 33 946 werden fluoridhaltige Gläser auf der Basis B2O3 - La2O3 - Y2O3 beschrieben; diese Gläser enthalten jedoch notwendigerweise teuresDE-AS 26 33 946 describes fluoride-containing glasses based on B 2 O 3 - La 2 O 3 - Y 2 O 3 ; however, these glasses necessarily contain expensive ones

to Ta2Os, um eine genügende Entgiasungsstabilität zu erreichen, da offenbar der im Zusammenwirken mit Fluorid ausgezeichnete stabilisierende Effekt des WO3 nicht erkannt wurde.
Das gleiche gilt für die sehr weit gefaßte DE-AS 26 52 747; diese Gläser können zwar WO3 wahlweise enthalten, jedoch ist eine teilweise Substitution von Sauerstoff durch Fluorid-Ionen nicht vorgesehen.to Ta 2 Os, in order to achieve sufficient degassing stability, since apparently the stabilizing effect of WO 3, which is excellent in interaction with fluoride, was not recognized.
The same applies to the very broad DE-AS 26 52 747; Although these glasses can optionally contain WO 3 , partial substitution of oxygen by fluoride ions is not envisaged.

Gläser entsprechend der DE-OS 27 54 255 überschneiden zwar teilweise das Lagegebiet im nd-vd-Dia- gramm der vorliegenden Anmeldung, jedoch fehlt diesen Gläsern als kristallisationshemmende Komponente ein WO3- und Fluorionenzusatz.Glasses according to DE-OS 27 54 255, although overlap in part, the location area in nd vd-diagnostic program of the present application, however, these glasses is missing as the crystallization retarding component is a WO 3 - ions and fluorine ions addition.

Die Gläser gemäß der Erfindung enthalten 19-37 Gew.-% B2O3 als Hauptglasbildner und 1 20 Gew.-°/o WO3 als Hilfsglasbildner, wobei 1 -4% der O2--lonen des Glases durch 2 F~-Ionen ersetzt sind. Als weitere substantielle Komponenten dienen La2O3 mit 39-49Gew.-% und Y2O3 mit 5-10Gew.-% zur Brechwerterhöhung, um die angestrebten optischen Werte zu erzielen. Der Gesamtanteil der Seltenerdoxide beträgt 44 - 55 Gew.-%. Zur Brechwerterhöhung wird auch ZrO2 in Anteilen von 3 —9 Gew.-% zugesetzt. 1 -4% der Sauerstoffionen werden durch Fluorid-Ionen ersetzt. Ein geringerer Anteil als 1% zeigt nicht die wünschenswerte deutliche Verminderung der Kristallisationstendenz, wirkt sich hingegen negativ auf das Fließverhalten während des Gusses aus (Viskosität wird zu stark vermindert).
Das für die Eigenschaften der erfindungsgemäßen Gläser entscheidende Merkmal scheint das gemeinsame Vorhandensein von WO3 und F zu sein.The glasses according to the invention contain 19-37% by weight of B 2 O 3 as the main glass former and 1 20 % by weight of WO 3 as an auxiliary glass former, with 1-4% of the O 2 ions in the glass by 2 F ~ -Ions are replaced. La 2 O 3 with 39-49% by weight and Y 2 O 3 with 5-10% by weight serve as further substantial components to increase the refractive index in order to achieve the desired optical values. The total proportion of rare earth oxides is 44-55% by weight. To increase the refractive index, ZrO 2 is also added in proportions of 3-9% by weight. 1 -4% of the oxygen ions are replaced by fluoride ions. A proportion less than 1% does not show the desirable significant reduction in the tendency to crystallize, but has a negative effect on the flow behavior during casting (viscosity is reduced too much).
The characteristic that is decisive for the properties of the glasses according to the invention appears to be the common presence of WO 3 and F.

0 —4Gew.-% Weitere mögliche Komponenten sind ZnO (0—140-4% by weight Further possible components are ZnO (0-14

Gew.-o/o), Nb2O5 (0-9 Gew.-°/o), TiO2 (0-8 Gew.-o/o), PbO (0-12 Gew.-%) und Ta2O5 (0-4 Gew.-°/o), wobei auf Ta2O5 wegen des hohen Preises ganz verzichtet werden sollte. Von diesen genannten Komponenten ist bekannt, daß sie Fluoride kovalenten Charakters oder komplexe Fluoride bilden, daß sich also deren Zusatz nicht negativ auf die Entgiasungsstabilität auswirkt. Sie dienen dazu, höhere Brechwerte zu erreichen bzw. gewünschte Abbewerte einzustellen.% By weight, Nb 2 O 5 (0-9% by weight), TiO 2 (0-8% by weight), PbO (0-12% by weight) and Ta 2 O 5 (0-4% by weight), whereby Ta 2 O 5 should be completely dispensed with because of its high price. It is known of these components mentioned that they form fluorides of a covalent character or complex fluorides, so that their addition does not have a negative effect on the degassing stability. They serve to achieve higher refractive indices or to set the desired devaluations.

Die Fluorionen bewirken neben ihrem kristallisationshemmenden Effekt eine leichtere Aufschmelzbarkeit des Gemenges. Als bevorzugte fluoreinbringende Komponenten werden LaF3 bzw. YF3 benutzt.In addition to their crystallization-inhibiting effect, the fluorine ions make the mixture easier to melt. LaF 3 and YF 3 are used as preferred fluorine-introducing components.

Gläser gemäß der Erfindung werden folgendermaßen erschmolzen. Die Oxide (Carbonate, Nitrate bzw. Fluoride) werden entsprechend ihren Anteilen abgewogen, ein kleiner Anteil Läutermittel, z. B. As2O3, wird zugesetzt, und anschließend wird gut gemischt. Dieses Gemenge wird im Pt-Tiegel bei ca. 1200-13000C eingeschmolzen, geläutert homogenisiert und gerührt bis zur Gußtemperatur von 1030-1070°C. Anschließend wird in eine Eisenform gegossen.Glasses according to the invention are melted as follows. The oxides (carbonates, nitrates or fluorides) are weighed according to their proportions. B. As 2 O 3 is added, followed by mixing well. This batch is melted in Pt crucibles at about 1200-1300 0 C, homogenized, purged and stirred until the casting temperature of 1030 to 1070 ° C. Then it is poured into an iron mold.

In der nachstehenden Tabelle sind einige beispielhafte Zusammensetzungen gemäß der Erfindung zusammengefaßt. Some exemplary compositions according to the invention are summarized in the table below.

0-12Gew.-%0-12% by weight

TabelleTabel

Beispiele
1Examples
1 22 33 44th 55 66th B2O3 B 2 O 3 31353135 21,0521.05 36,5036.50 20302030 27,1027.10 29,4529.45 La2O3
Y2O3 La 2 O 3
Y 2 O 3 45,65
8,8045.65
8.80 41,10
5,2541.10
5.25 39,25
5,2039.25
5.20 41,50
5,1041.50
5.10 4835
6,654835
6.65 44,95
6,7544.95
6.75 WO3
ZrO2 WHERE 3
ZrO 2 1,15
7,201.15
7.20 8,10
5,358.10
5.35 2,60
4,052.60
4.05 18,55
5,3018.55
5.30 3,80
8,453.80
8.45 1,65
6,451.65
6.45 ZnO
Nb2O5
TiO2
PbO
Ta2O5 ZnO
Nb 2 O 5
TiO 2
PbO
Ta 2 O 5 2,60
3,252.60
3.25 7,45
11,707.45
11.70 12,4012.40 2,80
6,452.80
6.45 1,60
1,10
2,951.60
1.10
2.95 0,85
3,00
6,900.85
3.00
6.90 nd
vdnd
vd 1,7880
47,401.7880
47.40 1,8700
36,001.8700
36.00 1,7360
51,001.7360
51.00 1,8610
36,201.8610
36.20 1,8110
44,801.8110
44.80 1,8281
38,901.8281
38.90 F-%F-% 1,51.5 2,32.3 3,53.5 3,23.2 2,02.0 1,91.9

F-% Δ Anzahl der O2--Ionen in %, die durch 2 F" ersetzt worden sind.F-% Δ number of O 2 ions in% that have been replaced by 2 F ".

(Gew.-(Weight

Beispiel 7Example 7 B2O3 B 2 O 3 31353135 La2OjLa 2 Oj 47,0547.05 Y2O3 Y 2 O 3 8,808.80 WO3 WHERE 3 5,205.20 ZrO2 ZrO 2 7,607.60 F-F- 1,801.80 ndnd 1.78 401.78 40 VdVd 48,3048.30

Claims (1)

Patentansprüche:Patent claims: 1. ThO2- und CdO-freies optisches Glas im Glassystem 1. ThO 2 - and CdO-free optical glass in the glass system B2O3 - La2O3 - YaO3 - ZrO2 - FB 2 O 3 - La 2 O 3 - YaO 3 - ZrO 2 - F mit Brechwerten 1.73-1.8S und Abbezahlen von 35-52,gekennzeichne t durch folgende Zusammensetzung: with refractive index 1.73-1.8S and Abbe numbers from 35-52, characterized by the following composition:
DE19813138138 1981-09-25 1981-09-25 Th0 2 - and Cd0-free optical glass with refractive indices 1.73 - 1.88 and Abbe numbers of 35 - 52 Expired DE3138138C2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE19813138138 DE3138138C2 (en) 1981-09-25 1981-09-25 Th0 2 - and Cd0-free optical glass with refractive indices 1.73 - 1.88 and Abbe numbers of 35 - 52
FR8216032A FR2513621A1 (en) 1981-09-25 1982-09-23 OPTICAL GLASS FREE OF THO2 AND CDO, HAVING REFRACTIVE INDEX FROM 1.73 TO 1.88 AND ABBE INDEX FROM 35 TO 52
GB08227105A GB2106497B (en) 1981-09-25 1982-09-23 Tho2-and cdo-free, optical glass with refractive indices 1.73-1.88 and abbe numbers 35-52
JP16516282A JPS5869741A (en) 1981-09-25 1982-09-24 Tho2-free cdo-free optical glass having 1.73-1.88 reflective constant and 35-52 abbe's number

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813138138 DE3138138C2 (en) 1981-09-25 1981-09-25 Th0 2 - and Cd0-free optical glass with refractive indices 1.73 - 1.88 and Abbe numbers of 35 - 52

Publications (2)

Publication Number Publication Date
DE3138138A1 DE3138138A1 (en) 1983-04-14
DE3138138C2 true DE3138138C2 (en) 1983-10-27

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DE19813138138 Expired DE3138138C2 (en) 1981-09-25 1981-09-25 Th0 2 - and Cd0-free optical glass with refractive indices 1.73 - 1.88 and Abbe numbers of 35 - 52

Country Status (4)

Country Link
JP (1) JPS5869741A (en)
DE (1) DE3138138C2 (en)
FR (1) FR2513621A1 (en)
GB (1) GB2106497B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3307497C2 (en) 1983-03-03 1985-09-12 Schott Glaswerke, 6500 Mainz Optical glass in the system Si0? 2? - B? 2? 0? 3? - La 2 0 3 - Zr0? 2? - alkali oxide - alkaline earth oxide - Zn0 - F with refractive index? 1.70, Payoff? 48, with good devitrification stability and good chemical resistance

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JP4017832B2 (en) * 2001-03-27 2007-12-05 Ｈｏｙａ株式会社 Optical glass and optical components
TWI594966B (en) * 2010-10-08 2017-08-11 Ohara Kk Optical glass, preform and optical element
JP6096409B2 (en) * 2010-10-29 2017-03-15 株式会社オハラ Optical glass, preform and optical element
JP5731358B2 (en) * 2011-09-01 2015-06-10 株式会社オハラ Optical glass, preform and optical element
JP5800766B2 (en) * 2011-10-28 2015-10-28 株式会社オハラ Optical glass, preform and optical element
JP5875572B2 (en) * 2013-04-05 2016-03-02 株式会社オハラ Optical glass, preform material and optical element
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JP5979723B2 (en) * 2013-07-31 2016-08-31 株式会社オハラ Optical glass and optical element
JP6462244B2 (en) * 2014-01-07 2019-01-30 日本電気硝子株式会社 Optical glass
JP6462245B2 (en) * 2014-01-07 2019-01-30 日本電気硝子株式会社 Optical glass
CN109734304B (en) * 2019-03-28 2021-12-07 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1529337A (en) * 1966-12-12 1968-06-14 Jenaer Glas Schott Gen Veb Borate optical glasses
JPS5215510A (en) * 1975-07-28 1977-02-05 Nippon Chemical Ind Optical glass
JPS5285210A (en) * 1976-01-09 1977-07-15 Fuji Photo Film Co Ltd Optical glass
US4120732A (en) * 1977-12-12 1978-10-17 Kabushiki Kaisha Ohara Kogaku Garasu Seizosho Optical glass
JPS55121925A (en) * 1979-03-14 1980-09-19 Ohara Inc Optical glass
JPS565345A (en) * 1979-06-28 1981-01-20 Nippon Kogaku Kk <Nikon> Optical glass

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3307497C2 (en) 1983-03-03 1985-09-12 Schott Glaswerke, 6500 Mainz Optical glass in the system Si0? 2? - B? 2? 0? 3? - La 2 0 3 - Zr0? 2? - alkali oxide - alkaline earth oxide - Zn0 - F with refractive index? 1.70, Payoff? 48, with good devitrification stability and good chemical resistance

Also Published As

Publication number Publication date
FR2513621B1 (en) 1985-05-17
JPS6332735B2 (en) 1988-07-01
GB2106497A (en) 1983-04-13
FR2513621A1 (en) 1983-04-01
GB2106497B (en) 1985-04-03
DE3138138A1 (en) 1983-04-14
JPS5869741A (en) 1983-04-26

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Owner name: SCHOTT GLAS, 55122 MAINZ, DE