DE3123057A1 - OPTICAL FLUOROPHOSPHATE GLASSES IN AREA N (DOWN ARROW) E (DOWN ARROW) = 1.43-1.48 AND V (DOWN ARROW) E (DOWN ARROW) = 92-82 - Google Patents

OPTICAL FLUOROPHOSPHATE GLASSES IN AREA N (DOWN ARROW) E (DOWN ARROW) = 1.43-1.48 AND V (DOWN ARROW) E (DOWN ARROW) = 92-82

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Publication number
DE3123057A1
DE3123057A1 DE19813123057 DE3123057A DE3123057A1 DE 3123057 A1 DE3123057 A1 DE 3123057A1 DE 19813123057 DE19813123057 DE 19813123057 DE 3123057 A DE3123057 A DE 3123057A DE 3123057 A1 DE3123057 A1 DE 3123057A1
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Germany
Prior art keywords
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optical
glasses
fluoride
fluorophosphate glasses
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
DE19813123057
Other languages
German (de)
Other versions
DE3123057C2 (en
Inventor
Herbert Dipl.-Chem. Dr. DDR 6902 Jena-Neulobeda Bürger
Doris Dipl.-Chem. Dr. Ehrt
Klaus Dipl.-Chem. DDR 6900 Jena Gerth
Erich Dipl.-Chem. Dr. DDR 6902 Jena-Neulobeda Heidenreich
Thomas Dipl.-Chem. DDR 5320 Apolda Kittel
Werner Prof. Dipl.-Chem. Dr. Vogel
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.)
Jenoptik AG
Original Assignee
Jenaer Glaswerk GmbH
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 Jenaer Glaswerk GmbH filed Critical Jenaer Glaswerk GmbH
Publication of DE3123057A1 publication Critical patent/DE3123057A1/en
Application granted granted Critical
Publication of DE3123057C2 publication Critical patent/DE3123057C2/de
Granted 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
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus

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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)

Description

Optische KLuorophosphatgläser im Bereich von η = 1,43-1548 und ν = 92-82Optical fluorophosphate glasses in the range of η = 1.43-1 5 48 and ν = 92-82

Die Erfindung "betrifft optische Fluor ο phosphatglas er im Bereich von η = 1,43-1,43 und ν = 92-82 mit großer positiver anomaler Teildispersion und geringer Dispersion« Diese Gläser sind in der Lage, im wissenschaftlichen Gerätebau das sekundäre Spektrum optischer Systeme zu korrigieren· Sie sind dabei sowohl in mikro- als auch in makrooptischen Apochromaten einsetzbar.The invention "relates to optical fluorine ο phosphate glass in the field of η = 1.43-1.43 and ν = 92-82 with large positive anomalous Partial dispersion and low dispersion “These glasses are capable of being used in scientific device construction Correct the secondary spectrum of optical systems · You are doing both micro- and macro-optical Apochromats can be used.

Bisher werden in der Praxis beim Bau von besonders leistungsstarken Apochromaten meistens CaFp-Sinkristalle mit den optischen Parametern ne = 1,435, ve = 94,8, P-^1 = 0,477 und ΔΡ χ,, = 0,047 eingesetzt. Sie haben gegenüber Gläsern die bekannten ITachteile, daß ihre Herstellung bedeutend teurer und z« Z. nur in kleineren Abmessungen möglich'ist und sie sich schlechter be- und verarbeiten lassen, da sie bevorzugte Spaltrichtungen besitzen. Außerdem beeinträchtigen auftretende Kristallwachstumsfehler ihre optische Qualität. In dem genannten Dispersionsbereich sind sowjetische Patentgläser bekannt (DDR-Anmeldung: IVP 104 071). Diese Gläser beruhen auf der Basis von Bariummonofluorophosphat, BaPO3]?, als glasbildende Komponente. Ohne BaPO^I1 ist in dem genannten Patent keine Glasbildung möglich. Angaben zur Größe der anomalen ieildispersion (δΡ -ρ,-bzw. δ ν -Werte) werden in demSo far, CaFp sinking crystals with the optical parameters n e = 1.435, v e = 94.8, P- ^ 1 = 0.477 and ΔΡ χ ,, = 0.047 have been used in practice in the construction of particularly powerful apochromats. Compared to glasses, they have the well-known disadvantages that their production is significantly more expensive and currently only possible in smaller dimensions, and they are more difficult to work and process because they have preferred splitting directions. In addition, any crystal growth defects that occur impair their optical quality. Soviet patent glasses are known in the aforementioned dispersion range (GDR application: IVP 104 071). These glasses are based on barium monofluorophosphate, BaPO 3 ] ?, as a glass-forming component. Without BaPO ^ I 1 , no glass formation is possible in the patent mentioned. Information on the size of the anomalous oil dispersion (δΡ -ρ, and δ ν -values) is given in the

um « β · around «β

Patent nicht gemacht. Fluorophosphatgläser in dem genannten Dispersionsbereich auf der Basis von BaPO0I1 "besitzen eine geringe Viskosität und eine relativ große Eristallisationsneigung« Das ist für die Herstellung, Verarbeitung und Qualität der optischen Gläser nicht günstig·Patent not made. Fluorophosphate glasses in the above-mentioned dispersion range based on BaPO 0 I 1 "have a low viscosity and a relatively high tendency to crystallize. This is not favorable for the production, processing and quality of the optical glasses.

Das Ziel der Erfindung besteht in der Entwicklung von optischen Gläsern mit geringer Dispersion und hoher positiver anormaler Teildispersion, die in der Lage sind, sowohl in Mikro- als auch in Makrooptiken das sekundäre Spektrum korrigieren su können. Die Gläser sollen ein verfahrenstechnisch günstiges Verhalten aufweisen.The aim of the invention is to develop optical glasses with low dispersion and high positive anomalies Partial dispersion capable of both micro and Correct the secondary spectrum in macro optics. The glasses should behave favorably in terms of process technology exhibit.

Die gestellte Aufgabe wird erfindungsgemäß dadurch gelöst, daß Gläser aus 5,0-10,0 Mo 1% Metaphosphat und 95,0-90,0 II0I& Fluoriden erschmolzen werden. Dabei werden hauptsächlich als Metaphosphat Sr(POo) ρ und als Fluoride Kalzium·? Aluminiuin- und Magnesiumfluorid in folgenden Konzentrationen eingesetzt:The object set is achieved according to the invention in that glasses made from 5.0-10.0 Mo 1% metaphosphate and 95.0-90.0% IIOI & fluorides are melted. Mainly as metaphosphate Sr (POo) ρ and as fluoride calcium ·? Aluminum and magnesium fluoride used in the following concentrations:

Sr(PO3)2, La(PO3)3 5,0-10,0Sr (PO 3 ) 2 , La (PO 3 ) 3 5.0-10.0

MgF2, LiF 0-30,0 Mol/SMgF 2 , LiF 0-30.0 mol / S

CaF2, SrF2 36,0-57,0 Mol/5CaF 2 , SrF 2 36.0-57.0 moles / 5

AlF3, LaF3, SbF3 24,0-38,0 Mol%AlF 3 , LaF 3 , SbF 3 24.0-38.0 mol%

Gemäß der Erfindung kann Kalziumfluorid auch durch 0-51,0 Mo 1% Strontiumfluorid substituiert werden» Dadurch wird die Brechzahl erhöht, ohne daß sich die anderen optischen Parameter wesentlich verändern.According to the invention, calcium fluoride can also be added by 0-51.0 Mo 1% Strontium fluoride can be substituted »This increases the refractive index without affecting the other optical parameters change significantly.

Außerdem können erfindungsgemäß zur Erhöhung der Viskosität 0-2,5 Mo1% Strontiummetaphosphat durch Lanthanmetaphosphat ersetzt werden. Weiterhin ist es gemäß der Erfindung möglich, in dem oben genannten Konzentrationsbereich .Aluminiumfluorid" bis zu 10,0 Ho1% durch Lanthanfluorid oder Antimonfluorid und Magnesiumfluorid bis zu 26,0 Mol% durch Lithiumfluorid zu ersetzen. In addition, according to the invention, to increase the viscosity, 0-2.5 mol% of strontium metaphosphate can be replaced by lanthanum metaphosphate. Furthermore, it is possible according to the invention to replace aluminum fluoride up to 10.0 Ho 1% with lanthanum fluoride or antimony fluoride and magnesium fluoride up to 26.0 mol% with lithium fluoride in the above-mentioned concentration range.

Ausführungsbeispiele zu den erfindungsgeniäßen Zusammensetzungen σ l.nd in den nachfolgenden Tabellen angegeben. Zur Ileratollung der Gläser werden die Gerne ngekomponent en Jr(P03)2, Ia(PO3)3, LiP, MgP2, GaP2, Ali1.,, LaP3, SbP3 gut gemischt und portionsweise in einem Tiegel, vorzugsweise aus Platin, in einem Elektroofen bei ca. 13OQ K eingeschmolzen, Zur Läuterung wird die Temperatur kurzzeitig um 50-100 K erhöht und anschließend bis zu Temperaturen von 1100-1000 K homogenisiert. Bei 1000-950 K wird die Glasschmelze in vorgewärmte Pormen, bevorzugt aus Kohlenstoff, gegossen und im Kühlofen mit 1-2 K/min auf Raumtemperatur gekühlt. Die Schmelzen zeigen nur geringe Verdampfungserscheinungen, lassen sich bis zu niedrigen Temperaturen homogenisieren und besitzen eine sehr geringe Kristallisationsneigung. J j in weiterer Vorteil der erfindungsgemäßen Gläser besteht darin, daß sie eine für Pluorophosphatgläser selir hohe Gießviskosität aufweisen. Das wirkt sich außerordentlich günstig auf die Homogenität der Gläser aus.Embodiments of the compositions σ l.nd according to the invention are given in the tables below. To oleo the glasses, the common components Jr (P0 3 ) 2 , Ia (PO 3 ) 3 , LiP, MgP 2 , GaP 2 , Ali 1 , LaP 3 , SbP 3 are mixed well and in portions in a crucible, preferably Made of platinum, melted in an electric furnace at around 130K. For refining, the temperature is briefly increased by 50-100K and then homogenized up to temperatures of 1100-1000K. At 1000-950 K, the molten glass is poured into preheated pores, preferably made of carbon, and cooled to room temperature in a cooling furnace at 1-2 K / min. The melts show only minor evaporation phenomena, can be homogenized down to low temperatures and have a very low tendency to crystallize. Another advantage of the glasses according to the invention is that they have a casting viscosity which is high for fluorophosphate glasses. This has an extremely beneficial effect on the homogeneity of the glasses.

Die Erfindung wird an den folgenden Ausführungsbeispielen demonstriert. Sie ist jedoch nicht nur auf die angeführten Beispiele beschränkt. Es werden einige Zusammensetzungen der Gemenge erfindungsgemäßer Gläser in Molprozent mit ermittelten optischen Daten aufgeführt. Aus den gemessenen Brechzahlen wurden die Abbe-Zahl ν = e , die relative TeildispersionThe invention is demonstrated using the following working examples. However, it is not restricted to the examples given. Some compositions of the mixtures of glasses according to the invention are listed in mol percent with determined optical data. The Abbe number ν = e , the relative partial dispersion, were derived from the measured refractive indices

V~ nC
P ,p, = ng " 11F* und die anomale Teildispers ion V ~ n C
P, p, = n g " 11 F * and the anomalous partial dispersion

der GleichungÄP_™, = P^, - 0,57035 + 0,00143 χ νο berechnet. gz gü öthe equationÄP_ ™, = P ^, - 0.57035 + 0.00143 χ ν ο calculated. gz gü ö

Mol% /ITr. 1Mol% / ITr. 1

CaP.CaP.

gP·gP

gPgP

5,05.0 5,05.0 10,010.0 10,010.0 10,010.0 -- 10,010.0 10,010.0 20,020.0 30,030.0 57,057.0 51,051.0 48,048.0 42,042.0 36,036.0 38,038.0 34,034.0 32,032.0 28,028.0 24,024.0 1,445491.44549 1,436331.43633 1,466451.46645 1,464711.46471 1,461431.46143 90,990.9 92,492.4 86,186.1 85,585.5 85,085.0 0,47500.4750 0,47180.4718 0,47230.4723 0,47720.4772 0,47300.4730 0,0400.040 0,0390.039 0,0300.030 0,0340.034 0,0300.030

Mol# / Nr,Mole # / no,

1010

3 La(PO3) 3 La (PO 3 )

GaP2 SrP2 GaP 2 SrP 2

5,05.0 5,05.0 10,010.0 10,010.0 5,05.0 2,52.5 -- -- -- -- 1,01.0 2,52.5 10,010.0 10,010.0 10,010.0 10,010.0 5,05.0 5,05.0 25,525.5 -- 16,016.0 -- 34,034.0 27,027.0 25,525.5 51,051.0 32,032.0 48,048.0 17,017.0 27,027.0 34,034.0 34,0 ·34.0 · 32,032.0 32,032.0 38,038.0 36,036.0 1,445021.44502 1,451661.45166 1,467711.46771 1,469081.46908 1,448411.44841 1,454321.45432 90,790.7 90,790.7 87,787.7 87,087.0 91,391.3 90,190.1 0,47610.4761 0,47250.4725 0,47460.4746 0,47420.4742 0,48250.4825 0,48170.4817 0,0400.040 0,0360.036 0,0340.034 0,0330.033 0,0470.047 0,0450.045

Hol,; / iir.Hol ,; / iir. 1212th 1313th -- 1,469301.46930 1414th 1,486851.48685 1515th 1616 5,05.0 1717th ::rCro,)9 :: rCro,) 9 5,05.0 10,010.0 85,985.9 10,010.0 82,782.7 5,05.0 10,010.0 1,473241.47324 10,010.0 I.'.1"?1 I. '. 1 "? 1 10,010.0 10,010.0 0,47530.4753 10,010.0 0,47530.4753 10,010.0 10,010.0 85,385.3 10,010.0 CaP0 CaP 0 51,051.0 48,048.0 0,0320.032 48,048.0 0,0280.028 51,051.0 48,048.0 0,47470.4747 48,048.0 Al?o Al? O 29,029.0 31,031.0 22,022.0 33,033.0 27,027.0 0,0310.031 22,022.0 LaI? o LaI? O 5,05.0 1,01.0 1919th 10,010.0 2020th -- -- -- -- -- 1,01.0 2222nd 10,010.0 no n o 1,4-18091.4-1809 1,430591.43059 1,476S71.476S7 V0 V 0 90,590.5 92,792.7 84,584.5 T-J..T-J .. 0,0/10150.0 / 1015 0,47870.4787 0,47860.4786 0,0450.045 0,0460.046 0,0340.034 Lo l·;; / Hr.Lo l · ;; / Mr. 1818th 2121st 2323

5,05.0 5,05.0 5,05.0 10,010.0 10,010.0 10,010.0 8,08.0 6,06.0 3,53.5 7,07.0 10,510.5 14,014.0 2,02.0 4,04.0 6,56.5 13,013.0 19,519.5 26,026.0 51 ,051, 0 51,051.0 51,051.0 42,042.0 36,036.0 20,020.0 -- -- -- -- -- 10,010.0 34,034.0 34,034.0 34,034.0 28,028.0 24,024.0 20,020.0 1,442311.44231 1,440771,44077 1,439481.43948 1,464891.46489 1,462211.46221 1,461571.46157 91,091.0 91,991.9 92,392.3 85,985.9 85,285.2 85,585.5 0,47010.4701 0,47360.4736 0,46900.4690 0,47030.4703 0,47770.4777 0,46880.4688 0,0440.044 0,0400.040 0,0360.036 0,0270.027 0,0340.034 0,0250.025

Claims (2)

Patentansprüche:Patent claims: Optische Pluorophosphatgläser mit geringer Dispersion und großer positiver anomaler Teildispersion zur Korrektur des sekundären Spektrums optischer Systeme, dadurch gekennzeichnet, daß sie vor allem aus Strontiumnietaphospha.t, Kalziumfluorid, Magnesiumfluorid und Aluminiumfluorid erschmolzen werden und in folgender Konsentration vorliegen: Sr(POJ2, La(POj3 5,0-10,0 MolfiOptical fluorophosphate glasses with low dispersion and large positive anomalous partial dispersion for the correction of the secondary spectrum of optical systems, characterized in that they are mainly melted from strontiumnietaphospha.t, calcium fluoride, magnesium fluoride and aluminum fluoride and are present in the following concentration: Sr (POJ 2 , La ( POj 3 5.0-10.0 Molfi MgP2, LiP 0-30,0 HoIJSMgP 2 , LiP 0-30.0 HoIJS CaP2, SrP2 36,0-57,0 Hol; JCaP 2 , SrP 2 36.0-57.0 Hol; J AIP.,, LaP3, SbP3 24,0-38,0 MoIiSAIP. ,, LaP 3 , SbP 3 24.0-38.0 MoIiS 2. Optische Pluorophosphatgläser nach Anspruch 1, dadurch gekennzeichnet, daß2. Optical fluorophosphate glasses according to claim 1, characterized marked that La(POJ3 0-2,5 Mol>5La (POJ 3 0-2.5 moles> 5 LiP 0-26,0 MoIJSLiP 0-26.0 MoIJS SrP2 0-51,0 MoIJg : SrP 2 0-51.0 MoIJg : LaP3 0-10,0 Mol% vorhanden sind.LaP 3 0-10.0 mole percent are present.
DE19813123057 1980-08-04 1981-06-11 OPTICAL FLUOROPHOSPHATE GLASSES IN AREA N (DOWN ARROW) E (DOWN ARROW) = 1.43-1.48 AND V (DOWN ARROW) E (DOWN ARROW) = 92-82 Granted DE3123057A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DD22309580A DD156054A3 (en) 1980-08-04 1980-08-04 OPTICAL FLUOROPHOSPHATE GLASSES IN THE FIELD OF N LOW E = 1.43-1.48 AND V LOW E = 92-82

Publications (2)

Publication Number Publication Date
DE3123057A1 true DE3123057A1 (en) 1982-04-08
DE3123057C2 DE3123057C2 (en) 1988-01-07

Family

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DE19813123057 Granted DE3123057A1 (en) 1980-08-04 1981-06-11 OPTICAL FLUOROPHOSPHATE GLASSES IN AREA N (DOWN ARROW) E (DOWN ARROW) = 1.43-1.48 AND V (DOWN ARROW) E (DOWN ARROW) = 92-82

Country Status (4)

Country Link
DD (1) DD156054A3 (en)
DE (1) DE3123057A1 (en)
FR (1) FR2487813A1 (en)
GB (1) GB2083454B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9015090D0 (en) * 1990-07-09 1990-08-29 British Telecomm Method for the preparation of halide glass articles
JP2001510771A (en) * 1997-07-24 2001-08-07 コーニング インコーポレイテッド Transparent lanthanum fluoride glass ceramic
JP4570576B2 (en) * 2005-03-30 2010-10-27 Ｈｏｙａ株式会社 Optical glass, press-molding preform and manufacturing method thereof, and optical element and manufacturing method thereof
JP4498315B2 (en) * 2005-07-28 2010-07-07 Ｈｏｙａ株式会社 Optical glass, optical element and manufacturing method thereof
JP5004202B2 (en) 2005-09-14 2012-08-22 Ｈｏｙａ株式会社 Optical glass, precision press-molding preform and optical element
CN113336439B (en) * 2021-07-02 2022-07-01 湖北新华光信息材料有限公司 High-dispersion-coefficient optical glass, preparation method thereof and optical element

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD104071A1 (en) * 1973-04-23 1974-02-20

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1146032A (en) * 1955-01-29 1957-11-05 Jenaer Glaswerk Schott & Gen Fluoride-based, glucinium-free and phosphate-containing glass
FR2227236A1 (en) * 1973-04-27 1974-11-22 Tallin Stekolny Tarbeklaas High-dispersion optical glass - based on barium fluorophosphate and fluorides of aluminium, magnesium, calcium and strontium
DD153969A3 (en) * 1980-04-14 1982-02-17 Herbert Buerger OPTICAL FLUORIDE GLASSES

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD104071A1 (en) * 1973-04-23 1974-02-20

Also Published As

Publication number Publication date
GB2083454B (en) 1984-02-08
GB2083454A (en) 1982-03-24
DD156054A3 (en) 1982-07-28
FR2487813A1 (en) 1982-02-05
DE3123057C2 (en) 1988-01-07
FR2487813B1 (en) 1985-04-12

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