DE957339C - Practically fluorine-free optical glasses - Google Patents
Practically fluorine-free optical glassesInfo
- Publication number
- DE957339C DE957339C DEL9099A DEL0009099A DE957339C DE 957339 C DE957339 C DE 957339C DE L9099 A DEL9099 A DE L9099A DE L0009099 A DEL0009099 A DE L0009099A DE 957339 C DE957339 C DE 957339C
- Authority
- DE
- Germany
- Prior art keywords
- boric acid
- alkaline earth
- lanthanum oxide
- earth cations
- alkali
- 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
Links
- 239000005304 optical glass Substances 0.000 title claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 22
- 150000001768 cations Chemical class 0.000 claims description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 238000002845 discoloration Methods 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 238000011160 research Methods 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- -1 lithium Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
- C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing 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
- 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
-
- 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
- C03C3/253—Silica-free oxide glass compositions containing germanium
Landscapes
- 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
(WiGBl. S. 175)(WiGBl. P. 175)
AUSGEGEBEN AM 31. JANUAR 1957ISSUED JANUARY 31, 1957
KLASSE 32 b GRUPPE INTERNAT. KLASSE C 03 C CLASS 32 b GROUP INTERNAT. CLASS C 03 C
L popp IVc/ 32 bL popp IVc / 32 b
sind als Erfinder genannt wordenhave been named as inventors
Praktisch fluorfreie optische GläserPractically fluorine-free optical glasses
Das Hauptpatent bat angefangen am 27. Februar 19SlThe main patent started on February 27, 19Sl
Patentanmeldung bekanntgemacht am 29. November 1951Patent application published November 29, 1951
Patenterteilung bekanntgemacht am 10. Januar 19'57Patent granted on January 10, 19'57
Gegenstand der Erfindung sind praktisch fluorfreie optische Gläser aus Alkali und/oder Erdalkalikationen, Borsäure und Lanthanoxyd nach Patent 949 686. Die im Hauptpatent angegebenen Reihen von optischen Gläsern besitzen neben vorzüglichen optischen Werten (Breöhungszahl und Dispersion) gute chemische und mechanische Eigenschaften.The invention relates to practically fluorine-free optical glasses made from alkali and / or alkaline earth cations, Boric acid and lanthanum oxide according to patent 949 686. The series given in the main patent of optical glasses have excellent optical values (brooching number and dispersion) good chemical and mechanical properties.
Die angegebenen Zusammensetzungen der Schmelzen bzw. Gläser des* Hauptpatents können nach vorliegender Erfindung dahingehend erweitert werden, daß ein Verhältnis Kation zur Borsäure bzw. Lanthanoxyd zur Borsäure bis zu noch höheren Werten angewendet wird. Dadurch ist man in der Lage, optische Gläser mit noch günstigeren optischen Werten zu erschmelzen, ohne ihre mechanischen und chemischen Eigenschaften der genannten Gläser zu verschlechtern.The specified compositions of the melts or glasses of the * main patent can be found in present invention to the effect that a ratio of cation to boric acid or Lanthanum oxide is used to boric acid up to even higher values. This puts you in the Able to melt optical glasses with even more favorable optical values without losing their mechanical properties and to worsen chemical properties of said glasses.
Erfindungsgemäß zeichnen sich die Gläser der vorliegenden Erfindung dadurch aus, daß für das Verhältnis Alkali und/oder Erdalkalikationen zur Borsäure und für das Verhältnis Lanthanoxyd zur Borsäure eine obere Grenze, gegeben durch die allgemeine GleichungAccording to the invention, the glasses of the present invention are characterized in that for the Ratio of alkali and / or alkaline earth cations to boric acid and for the ratio of lanthanum oxide to Boric acid has an upper limit given by the general equation
y = α χ + b, y = α χ + b,
gilt, wobei χ zwischen o,i und ι liegt und das Molverhältnis Alkali und/oder Erdalkalikationen zur Borsäure (beispielsweise Li/B.,O3, Ca/B2O3,applies, where χ is between o, i and ι and the molar ratio of alkali and / or alkaline earth cations to boric acid (for example Li / B., O 3 , Ca / B 2 O 3 ,
Li + Ca/B2O3, Ca + Sr/B2O3), y das Molvefhältnis Lanthanoxyd zur Borsäure (La2O3AB2O3) und α und b zwei positive Zahlenwerte bedeuten, deren Summe bei Verwendung von Alkalikationen 0,4 und bei Verwendung von Erdalkalikationen 0,5 ist. Bei einem vorgegebenen x, also einem vorgegebenen Molverhältnis Lithium zur Borsäure, ist der aus der Gleichung sich ergebende 3;-Wert als oberer Grenzwert gegeben. Umgekehrt kann zu einem vorgegebenen 3>-Wert ein eindeutiger Λτ-Wert gewählt werden.Li + Ca / B 2 O 3 , Ca + Sr / B 2 O 3 ), y is the molar ratio of lanthanum oxide to boric acid (La 2 O 3 AB 2 O 3 ) and α and b are two positive numerical values, the sum of which when using alkali cations 0.4 and when using alkaline earth cations is 0.5. At a given x, that is to say a given molar ratio of lithium to boric acid, the 3; value resulting from the equation is given as the upper limit value. Conversely, a unique Λτ value can be selected for a given 3> value.
Die Gleichung besitzt nur dann volle Geltung, wenn χ zwischen 0,1 und 1 liegt, da über diese Grenzen hinaus die Gläser nicht mehr interessant sind. Es sei hier ein kleines Gebiet innerhalb der angegebenen Grenzen ausdrücklich ausgenommen, und zwar zeigt die Erfahrung, daß im Gebiet, das roh beschrieben zwischen χ kleiner als 0,21 und y kleiner als 0,12 liegt, ohne besondere Stabilisatoren keine Gläser erhalten werden. Für y größer als 0,12 bei gleichbleibenden jtr-Werten werden jedoch ausgezeichnete Gläser erschmolzen.The equation is only fully valid if χ is between 0.1 and 1, since beyond these limits the glasses are no longer of interest. A small area within the specified limits is expressly excluded here, and experience shows that in the area that is roughly described between χ less than 0.21 and y less than 0.12, no glasses can be obtained without special stabilizers. For y greater than 0.12 with constant jtr values, however, excellent glasses are melted.
Die Kationen, also das Lithium, können in Form von Lithiumborat, Lithiumlanthanat, Lithiumcarbonat oder ganz oder zum Teil, wie im Hauptpatent schon angegeben, als Lithiumfluorid oder aus Mischungen der genannten Verbindungen eingesetzt werden. Dabei sind die Maßnahmen beim Schmelzen zu treffen, die im Hauptpatent angegeben wurden, also· bei Verwendung von reaktionsfähigen Schmelzen, beispielsweise von Carbonaten oder Fluoriden, muß die Schmelztemperatur so hoch und die Schmelzdauer so lang gewählt sein, daß praktisch die gesamte Kohlensäure bzw. das Fluor als Bortrifluorid entweichen kann.The cations, i.e. lithium, can be in the form of lithium borate, lithium lanthanate, lithium carbonate or in whole or in part, as already stated in the main patent, as lithium fluoride or from mixtures of the compounds mentioned are used. The measures are at To meet melts, which were specified in the main patent, so · when using reactive Melts, for example of carbonates or fluorides, the melting temperature must be so high and the melting time be chosen so long that practically all of the carbonic acid or the fluorine can escape as boron trifluoride.
Für die Erdalkalikationen — es kommen im wesentlichen nur Calcium, Strontium oder Barium in Frage — nimmt die eingangs genannte Gleichung zweckmäßig folgende Formen an:For the alkaline earth cations - essentially only calcium, strontium or barium are used in question - the equation mentioned at the beginning expediently takes the following forms:
für Calcium y = 0,05 χ + 0,4for calcium y = 0.05 χ + 0.4
für Strontium y = 0,1 χ + 0,35for strontium y = 0.1 χ + 0.35
für Barium ^ = 0,15 χ + 0,3,for barium ^ = 0.15 χ + 0.3,
wobei wieder χ das Verhältnis der jeweiligen Kationen zu B2O3 und y wieder das Verhältnis Lanthanoxyd zur Borsäure bedeutet. Auch hier gelten die gleichen Angaben wie für das Lithium. Es können die Erdalkalikationen in Form von Boraten, Lanthanaten, Carbonaten oder Fluoriden eingesetzt werden, wobei für die letzten beiden wieder die oben angegebenen Schmelzbedingungen zu beachten sind. Die Grenze der Gleichungen, die sinnvoll für diese Gläser angegeben werden können, liegt für χ wieder, wie gefordert, zwischen 0,1 bis i.where χ again denotes the ratio of the respective cations to B 2 O 3 and y again denotes the ratio of lanthanum oxide to boric acid. Here, too, the same information applies as for lithium. The alkaline earth cations in the form of borates, lanthanates, carbonates or fluorides can be used, the melting conditions given above again having to be observed for the last two. The limit of the equations that can be meaningfully given for these glasses is again, as required, between 0.1 and i for χ.
Wird ein Teil des Lanthanoxyds durch andere Oxyde ersetzt, wie Zirkonoxyd, Yttriumoxyd, Indiumoxyd, so ist es zweckmäßig, die Molprozente dieser Verbindungen dem Lanthanoxyd zuzuzählen, wobei die gleichen Grenzen Geltung haben mögen. Es ist selbstverständlich, daß diesen Glasschmelzen bzw. Gläsern Substanzen für die Stabilisierung zur Verhinderung der Entglasung, zur Erhöhung der chemischen Beständigkeit oder Entfärbung, zugegeben werden können, wobei die Gesamtmenge der Zusätze 5 Gewichtsprozent im fertigen Glas nicht überschreiten soll.If part of the lanthanum oxide is replaced by other oxides, such as zirconium oxide, yttrium oxide, Indium oxide, it is advisable to add the mole percent of these compounds to the lanthanum oxide, whereby the same limits may apply. It goes without saying that this glass melts or glazing substances for stabilization, to prevent devitrification, to increase chemical resistance or discoloration, can be added, with the total amount the additives should not exceed 5 percent by weight in the finished glass.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEL9099A DE957339C (en) | 1951-02-26 | 1951-05-26 | Practically fluorine-free optical glasses |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1066068X | 1951-02-26 | ||
| DEL9099A DE957339C (en) | 1951-02-26 | 1951-05-26 | Practically fluorine-free optical glasses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE957339C true DE957339C (en) | 1957-01-31 |
Family
ID=25984992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEL9099A Expired DE957339C (en) | 1951-02-26 | 1951-05-26 | Practically fluorine-free optical glasses |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE957339C (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US21175A (en) * | 1858-08-17 | Washing-machine | ||
| US2434147A (en) * | 1945-08-04 | 1948-01-06 | Eastman Kodak Co | Optical glass |
| US2434148A (en) * | 1935-09-03 | 1948-01-06 | Eastman Kodak Co | Optical glass |
| US2434146A (en) * | 1935-09-03 | 1948-01-06 | Eastman Kodak Co | Optical glass |
| US2466392A (en) * | 1945-08-04 | 1949-04-05 | Eastman Kodak Co | Optical glass |
| US2466394A (en) * | 1945-06-29 | 1949-04-05 | Eastman Kodak Co | Preparation of esters of acids of phosphorus |
-
1951
- 1951-05-26 DE DEL9099A patent/DE957339C/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US21175A (en) * | 1858-08-17 | Washing-machine | ||
| US2434148A (en) * | 1935-09-03 | 1948-01-06 | Eastman Kodak Co | Optical glass |
| US2434146A (en) * | 1935-09-03 | 1948-01-06 | Eastman Kodak Co | Optical glass |
| US2466394A (en) * | 1945-06-29 | 1949-04-05 | Eastman Kodak Co | Preparation of esters of acids of phosphorus |
| US2434147A (en) * | 1945-08-04 | 1948-01-06 | Eastman Kodak Co | Optical glass |
| US2466392A (en) * | 1945-08-04 | 1949-04-05 | Eastman Kodak Co | Optical glass |
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