WO2012143452A1 - Verre optique à indice de réfraction élevé - Google Patents

Verre optique à indice de réfraction élevé Download PDF

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Publication number
WO2012143452A1
WO2012143452A1 PCT/EP2012/057176 EP2012057176W WO2012143452A1 WO 2012143452 A1 WO2012143452 A1 WO 2012143452A1 EP 2012057176 W EP2012057176 W EP 2012057176W WO 2012143452 A1 WO2012143452 A1 WO 2012143452A1
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WIPO (PCT)
Prior art keywords
glass
mol
content
glasses
glass according
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Ceased
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PCT/EP2012/057176
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German (de)
English (en)
Inventor
Bianca Schreder
Simone Ritter
Ute Wölfel
Stefanie Hansen
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Schott AG
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Schott AG
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Publication date
Application filed by Schott AG filed Critical Schott AG
Priority to CN201280019510.2A priority Critical patent/CN103502165B/zh
Priority to KR1020137030854A priority patent/KR20140025481A/ko
Priority to JP2014505629A priority patent/JP6113714B2/ja
Publication of WO2012143452A1 publication Critical patent/WO2012143452A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear 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
    • 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
    • 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

Definitions

  • the present invention relates to an optical high-index bismuth oxide glass, as well as the production and use of such a glass.
  • preforms or preforms close to the final shape close to or close to the final geometry are directly adjacent to the glass melt such as As gobs or balls can be obtained.
  • End geometrical near preforms are suitable for the wieden / blackmail.
  • Such preforms can also advantageously be converted into optical elements such as lenses, aspheres, etc. by so-called (precision) blank pressing (Engl, "precise pressing” or “precise molding”).
  • the smaller glass melt volumes can be flexibly accommodated by short set-up times. Due to the comparatively lower number of cycles or quantities and the generally small geo- However, the added value of the process can not derive from the material value alone.
  • the products must leave the press in a condition that requires no elaborate tracking, cooling and / or cold post-processing. Due to the high geometrical accuracies required, precision tools with high-quality and therefore expensive mold materials must be used for such a pressing process. In the profitability of the manufactured products and / or materials, the service lives of such forms go down massively.
  • the glasses should also have an absorption edge or UV edge position or an absorption edge ⁇ 5 (ie the wavelength at which the pure transmission is 5%) measured on a glass sample of 10 mm thickness of less than or equal to 440 nm and also over
  • the precise pressing process can be processed and be suitable for the application areas of imaging, projection, telecommunications, optical communications, mobile drive and laser technology. They should also be easy to melt and process, and have a sufficient crystallization stability, which makes a production in continuously guided aggregates possible. Desirable is a "short" glass as possible in a viscosity range of 10 7.6 to 10 13 dPas.
  • a high refractive index optical glass comprising the following composition (in mole%, on an oxide basis): - Bi 2 0 3 at least 40
  • the glasses according to the invention have a refractive index n d of at least 1.9, preferably at least 2.0, most preferably at least 2.08 and / or preferably less than 2.2, more preferably less than 2.15.
  • the glasses have an Abbe number of 10 ⁇ Vd ⁇ 21, preferably at least 15 and / or at most 18.
  • the glasses according to the invention have a transformation temperature T g ⁇ 480 ° C, preferably T g ⁇ 450 ° C, more preferably T g ⁇ 420 ° C and most preferably T g ⁇ 400 ° C.
  • a so-called "low-Tg glass” is understood as meaning a glass having a low transformation temperature T g , ie preferably a T g of at most 480 ° C.
  • a so-called “short” glass is generally understood to mean a glass which has a very steep viscosity curve in the viscosity range from 10 2 to 10 13 dPas, ie whose viscosity changes greatly in this viscosity range even with a relatively small change in temperature .
  • the term "short” for a viscosity range of preferably 10 7.6 to 10 13 dPas apply.
  • the temperature interval ⁇ , in which the viscosity of this glass of 10 7.6 to 10 13 dPas falls at most 80 K, preferably at most 70 K, particularly preferably at most 60 K.
  • the "internal quality" of a glass is understood to mean that the glass contains as small a proportion as possible of bubbles and / or streaks and / or similar defects, or preferably is free of them
  • Direction Preferably in two mutually perpendicular directions no streaks detectable by the shadow method
  • the light source and the eye of the observer are held and the shadowing streaks determined by moving and tilting the glass sample (MIL-G-174A and similar standards), or the glass sample is irradiated with light and the streaks contained in the glass sample are projected onto a projection screen ( ISO 101 10-4).
  • the glass preferably has the blister class B1, more preferably B0 according to ISO 101 10-3.
  • X-free or “free of a component X” in the following means that the glass does not substantially contain this component X, ie that such a component is present at most as an impurity in the glass, however the glass composition is not added as a single component.
  • X stands for any component, such as F or Li 2 O.
  • Figure 1 shows a pure transmission curve of a glass according to Example 1, wherein the solid line, the pure transmission (Engl, "internal transmission") of a variant of the glass with a Cr content of 6 ppm and the broken line represents the pure transmission of a variant of the glass with a Cr content of less than 2 ppm.
  • Figure 2 shows the viscosity curve of a glass according to the invention according to example glass 2.
  • the vertical lines show the temperature interval ⁇ , in which the viscosity of this glass of 10 7.6 to 10 13 dPas decreases.
  • ⁇ is between 440 and 386 ° C, ie 54 K.
  • the base glass system of the glass according to the invention is a highly bismuth oxide-containing glass.
  • the glass according to the invention has a Bi 2 O 3 content of at least 40 mol%, preferably at least 45 mol%, particularly preferably more than 48 mol%.
  • the Bi 2 O 3 - Content is preferably at most 70 mol%, more preferably at most 60 mol%, particularly preferably at most 55 mol%.
  • Bi 2 0 3 contributes to the desired viscosity-temperature behavior ("short" glass) in the viscosity range from 10 7.6 to 10 13 dPas and also reduces the T g and increases the density of the glass
  • the maximum proportion of 70 mol% should not be exceeded since the intrinsic coloration of the Bi 2 O 3 would then have a negative effect on the transmission of the glass and the UV edge ⁇ 5 would be too far into the longer wavy region, ie
  • the minimum proportion of 40 mol% should likewise not be exceeded in order to ensure the low T g in combination with a high refractive index in the glass.
  • Bi 2 0 3 glass according to the invention contains as further glass formers Si0 2 , B 2 0 3 and / or Al 2 0 3 in a sum of 20 to 59 mol%, preferably at most 55 mol% and most preferably at most 50 mol %.
  • the glass according to the invention preferably contains at least 8 mol%, more preferably at least 10 mol% and / or at most 25 mol%, more preferably at most 20 mol% Si0 2 .
  • the maximum proportion of Si0 2 of 25 mol% should not be exceeded, because Si0 2 leads to increased glass transition temperatures and viscosities of the glass and to the reduction of the refractive index.
  • the glass of the present invention preferably contains B 2 O 3 in a content of preferably at least 18 mol%, more preferably at least 19 mol% and / or preferably at most 34 mol%, more preferably at most 30 mol%, most preferably at most 25 mole%.
  • the strong network-forming properties of B 2 O 3 increase the stability of the glasses against crystallization and chemical resistance.
  • the sum amount of the oxides B 2 O 3 and SiO 2 (B 2 O 3 + SiO 2 ) is at least 20 mol%, more preferably at least 25 mol%, more preferably at least 30 mol%, more preferably at least 35 mol%.
  • the addition of both components is preferred, so that no segregation of the glass occurs.
  • the sum amount of the oxides B 2 O 3 and SiO 2 is preferably at most 60 mol%, more preferably at most 55 mol%, more preferably at most 50 mol%, and most preferably at most 45 mol%. If the sum content exceeds 60 mol%, the desired high refractive index can no longer be achieved.
  • the ratio of the content of B 2 O 3 to the sum of the contents of B 2 O 3 and SiO 2 (B2O3 / B2O3 + S1O2) is at least 0.5 to provide optimum conductivity of the glass when the glass is melted by high frequency heating, as below described, to ensure.
  • the glass according to the invention preferably also contains Al 2 O 3 in a content of preferably at least 1 mol%, more preferably at least 3 mol%, even more preferably 4 mol% and / or preferably at most 1 mol%, more preferably at most 10 mol%, most preferably at most 9 mol%.
  • the ratio of the content of SiO 2 to the content of Al 2 O 3 is preferably at least 1.5, preferably at least 2.0 and / or preferably at most 6.0, more preferably at most 3.5.
  • the ratio of the content of SiO 2 to the sum of the contents of B 2 O 3 and Al 2 O 3 is at most 2.0, more preferably at most 1.5.
  • the glass contains all three components SiO 2 , B 2 O 3 and Al 2 O 3 . If all three components are present, in particular in the abovementioned ratios to one another, the glass has a particularly high degree of crosslinking and thus a particular stability against devitrification, in particular during reheating. The addition of all three components is advantageous because they crosslink differently in the glass and thus ensure a particularly high stability against devitrification.
  • the sum of alkali metal oxides R 2 O, selected from the group consisting of Li 2 O, Na 2 O, K 2 O, Rb 2 O and / or Cs 2 O, in the glass according to the invention is 0 to 10 mol%.
  • the value of at most 5 mol% should not be exceeded according to preferred embodiments otherwise devitrification may occur after a rewarming process.
  • the addition of at least one alkali metal oxide, in particular Na 2 O, in a content of at least 0.1 mol% is preferred because alkali metal oxides are used to optimize the melting behavior, ie they act as a flux.
  • they contribute to lowering the transformation temperature T g and can be used to finely adjust the Abbe number.
  • the glass is free of Li 2 O and / or Cs 2 O.
  • Cs 2 O in the glass system according to the invention lead to Entgla- solution.
  • Li 2 O lowers the refractive index and is therefore not preferred as a component in the glass.
  • the glass is preferably Li 2 O-free.
  • the glass according to the invention may optionally contain one or more alkaline earth metal oxides, selected from the group consisting of MgO, CaO, SrO, and / or BaO.
  • the proportion of the individual component should not exceed 10 mol%, preferably 7 mol%, particularly preferably 6 mol%.
  • the glass of the present invention may contain MgO, CaO, SrO or BaO in a content of at least 0.5 mol%, preferably at least 1 mol%.
  • Alkaline earth metal oxides contribute to a steep viscosity curve. The maximum proportion of 10 mol% should not be exceeded, as higher proportions in the glass lead to devitrification, especially during reheating.
  • the glass according to the invention may have a ZnO content of at most 10 mol%, preferably at most 7 mol%, particularly preferably at most 5 mol%. ZnO contributes to the desired viscosity-temperature behavior ("short" glass) in the viscosity range from 10 7 ' 6 to 10 13 dPas.
  • the glass has a content of divalent oxides RO (which is understood to mean alkaline earth metal oxides and ZnO) of less than 5 mol% or even is free of RO.
  • RO divalent oxides
  • the sum amount R 2 O + RO is less than 5 mol%, preferably at most 4 mol%.
  • the glass contains one or more further components in a content of 0.01 to 20 mol%, preferably in a content of at least 0.03, more preferably at least 0.1 mol%, most preferably 0.3 mol% and / or preferably at most 10 mol%, more preferably at most 7 mol%, more preferably at most 8 mol%, preferably at most 4 mol%.
  • Such other components serve to stabilize the glass against devitrification, ie crystallization or segregation, especially during reheating. Furthermore, with such components, the fine adjustment of the optical layer can take place.
  • the other components are preferably selected from the group consisting of La 2 0 3 , Nb 2 0 5 , Gd 2 0 3 , Ga 2 0 3 , Y 2 0 3 , Yb 2 0 3 , Ti0 2 , Zr0 2 , Hf0 2nd , Ge0 2 , Te0 2 , Se0 2 , Ce0 2 , W0 3 , As 2 0 3 and / or Ta 2 0 5 .
  • Each of these components may be individually present in a single content of at least 0.01 mole percent, preferably at least 0.05 mole percent, unless otherwise specified below.
  • the glass according to the invention preferably contains at least 3, more preferably at least 4, of the abovementioned further components.
  • the glass according to the invention may have a La 2 O 3 content of at least 0.01 and / or at most 6 mol%, preferably at most 5 mol%, more preferably at most 4 mol%.
  • W0 3 and / or Nb 2 0 5 may be present in proportions of at least 0.01 and / or in each case at most 6 mol%, preferably 5 mol%, particularly preferably at most 4 mol% in the glass.
  • These components can be used to adjust the optical position. However, they lead in larger proportions to higher viscosity of the glass.
  • the glass can contain Ti0 2 . It may be present in a content of at least 0.01 mol%, preferably at least 0.2 mol%, more preferably at least 0.5 mol% and / or at most 6 mol%, preferably at most 3 mol%, most preferably at most Be contained 2 mol%.
  • Ti0 2 has a positive effect on a high refractive index and increases the stability of the glass during reheating. However, the component leads to increased T g and viscosities. It can also lead to an increase in the dispersion of the glass and the transmission of the glass by absorption in the UV range adversely affect. A content of more than 6 mol% is therefore not preferred.
  • Zr0 2 is preferably present in small amounts in the glass according to the invention, for example at least 0.01 mol%, more preferably 0.04 mol% and / or preferably at most 2 mol%, more preferably at most 1 mol%, on most preferably at most 0.05 mol%.
  • ZAC trough Zr0 2 can be entered from the tub material into the glass in small quantities in the melt.
  • the glass is free of Zr0 2 .
  • the glass contains at least one of the components TiO 2 or ZrO 2 , preferably both components.
  • the sum amount of TiO 2 + ZrO 2 should preferably be at least 0.04 mol%, more preferably at least 0.1, particularly preferably 0.2 mol% and / or preferably at most 5 mol%, more preferably at most 3 mol% and most preferably at most 2 mol%.
  • These components can act as nucleations and are therefore not preferred at higher levels than stated, since they can lead to crystallization of the glass with increasing amount.
  • the glass may further contain GeO 2 , preferably in a content of at least 0.01 mol%, more preferably at least 0.5 mol% and / or at most 5 mol%.
  • Germanium oxide has an advantageous effect on the stability of the glass during reheating. It is nevertheless less preferred to add larger amounts of germanium oxide, since this component is very expensive.
  • glass is free of GeO 2 .
  • Ta 2 O 5 may be present in an amount of at least 0.01 mol%, preferably at least 0.05 mol%, more preferably at least 0.1 mol% and / or at most 3 mol%, preferred at most 2 mol%, most preferably at most 1 mol% may be contained in the glass. Glass is preferably free of Ta 2 0 5 .
  • Gd 2 0 3 may be present in the glass in a content of at least 0.04 mol%, preferably at least 0.05 mol% and / or at most 2 mol%, preferably at most 1 mol% in the glass. This component has a small absorption band in the visible range, the glass is therefore preferably free of Gd 2 0 3rd
  • the glass may further contain Ga 2 O 3 , preferably in a content of at least 0.01 mol% and / or at most 5 mol%.
  • the sum amount of Al 2 O 3 + Ga 2 O 3 is at most 1 1 mol%, more preferably at most 10 mol%.
  • HfO 2 can be present in the glass in a content of at least 0.01 mol%, preferably at least 0.03 mol%, particularly preferably at least 0.04 mol% and / or at most 1 mol%, preferably at most 0.5 mol% im Glass, more preferably at most 0.25 mol% may be contained.
  • This component can be added to adjust the refractive index and the Abbe number and, together with other other components, stabilizes the glass to such an extent that the glass does not segregate in a rewarming process such as recompression.
  • the glass may contain TeO 2 , preferably in an amount of at least 0.5 mol%, preferably at least 1 mol%, more preferably at least 2 mol% and / or preferably at most 10 mol%, more preferably at most 6 mol% %.
  • Ceria can be included in the glass to adjust the oxidation state.
  • CeO 2 may preferably be contained in a proportion of at most 1 mol%, preferably at most 0.5 mol%, more preferably at most 0.25 mol%. However, since this component leads to a slight discoloration of the glass, the glass is preferably Ce0 2 - free.
  • the glass according to one embodiment may contain As 2 O 3 , preferably in a content of at most 0.2 mol%, more preferably at most 0.1 mol% and / or preferably at least 0.05 mol%, more preferably at least 0 , 02 mol%, more preferably at least 0.01 mol%.
  • This component works alone or together with a refining agent mentioned below as a refining agent, but also serves to maintain the correct redox state of Bi 2 0 3rd
  • the glass according to the invention may contain conventional refining agents in small amounts.
  • the sum of the added refining agents is at most 1.0 mol%, more preferably at most 0.5 mol%.
  • refining agent at least one of the following components may be contained in the glass according to the invention (in mol%):
  • inorganic peroxides for example zinc peroxide, lithium peroxide and / or alkaline earth peroxides can be used.
  • the glass consists of 91 mol%, preferably 95 mol%, of the components Bi 2 O 3 , Al 2 O 3 , SiO 2 , B 2 O 3 and R 2 O, in particular Na 2 O.
  • the glass according to the invention is preferably at least 95 mol%, more preferably at least 98 mol%, of the components Bi 2 O 3 , Al 2 O 3 , SiO 2 , B 2 O 3 , La 2 0 3 , Ta 2 0 5 , Ti0 2 , Zr0 2 , Hf0 2 , Ge0 2 and R 2 0, in particular Na 2 0.
  • the glass according to the invention preferably consists of at least 90 mol%, more preferably at least 95 mol%, most preferably 99 mol%, of the abovementioned components.
  • the glass according to the invention is also preferably free from other components not mentioned in the claims, ie according to such an embodiment the glass consists essentially of said components.
  • the expression "consisting essentially of” means that other components are present at most as impurities, however, the glass composition is not intended to be added as a single component.
  • the glasses are free of components not mentioned above.
  • the glass according to the invention is preferably free of coloring components, such as V, Cr, Mn, Fe, Co, Ni and / or Cu and / or optically active, such as laser-active components, such as Pr, Nd, Sm, Eu, Tb, as optical glass. Dy, Ho, Er and / or Tm.
  • the glass is preferably free of harmful components such as oxides of Pb, Cd, Tl and Se.
  • the invention further relates to high-index glasses having an improved pure transmission ⁇ , in particular in the range of ⁇ ( ⁇ , ⁇ ) to ⁇ ( ⁇ , ⁇ +400 nm) and / or in particular after reheating.
  • ⁇ is the pure transmission in the pass range or the pure transmissivity of the pass range understood and below ⁇ ( ⁇ , ⁇ ), the wavelength above the pass or passage range of the glass begins, ie the range in which the pure transmission ⁇ , ⁇ not below becomes.
  • the change of the pure transmission ⁇ , of the glass in the wavelength range from ⁇ ( ⁇ ⁇ ) to ⁇ ( ⁇ , ⁇ +400 nm) is at most 2%, preferably at most 1%, more preferably at most 0.9%.
  • the glass according to the invention preferably has a net transmittance ⁇ , ⁇ at 600 nm and / or 700 nm of at least 95%, more preferably at least 98%.
  • the inventors have found that for glasses with a high Bi 2 O 3 content, ie a content of at least 40 mol%, the transmission of the glasses in the range of ⁇ ( ⁇ , ⁇ ) to ⁇ ( ⁇ , ⁇ +400 nm ), ie, after reaching the net transmittance ⁇ , ⁇ at a wavelength ⁇ ( ⁇ , ⁇ ), the pure transmission in the direction of longer wavelengths decreases again slightly up to ⁇ ( ⁇ , ⁇ +400 nm).
  • Cr has an absorption band in the above range, this band does not explain the width of the "belly" over the large wavelength range or the degradation of transmission after reheating
  • Cr it is believed that an interaction of the polyvalent Cr interacts with the bi-ion of the glass and Cr intervenes in the redox mechanism of the Bi, leading to an additional degradation of the transmission, an effect which appears to occur especially in high-bismuth oxide glasses.
  • the glass of the present invention preferably has a Cr content of at most 4 ppm, preferably at most 3 ppm, more preferably at most 2 ppm.
  • Figure 1 shows the pure transmission curves of a glass according to the invention according to Example 1 in a variant with conventional raw materials and a Cr content of 6 ppm (solid line), and a variant with a Cr content of less than 2 ppm (dashed line).
  • the glasses of the present invention also contain at most 3 ppm of a platinum component, more preferably at most 2 ppm, and most preferably less than or at most 1 ppm.
  • the glasses according to the invention are preferably melted in a Pt-free melt aggregate, such as, for example, in a quartz or ZAC trough.
  • the preferred low levels of platinum components allow a UV Edge position of less than or equal to (x c ) 440 nm which is a special feature for glasses with the described high refractive index layers.
  • fluorine and fluorine-containing compounds tend to evaporate during the melting and melting processes, thereby making it difficult to accurately adjust the glass composition.
  • the glass according to the invention is therefore preferably also fluorine-free.
  • the invention further relates to a glass which has an absorption edge ⁇ 5 of at most 440 nm, preferably at most 430 nm, more preferably at most 425 nm.
  • the glass according to the invention has good chemical resistance.
  • the glasses of the invention have abnormal relative partial dispersions AP g F from 0 to 60 x 10 "4, of at measuring samples from cooling with a cooling rate of about 20 K / h to the glasses of the invention have thermal expansion coefficients cc 2 o-3oo of at most 1. 1 x 10 "6 / K, more preferably at most 10 x 10 " 6 / K, thereby avoiding problems with thermal stress in the further processing and the joining technique Moreover, the combination of crystallization stability and viscosity temperature profile of the glasses according to the invention can provide a virtually problem-free thermal (Further -) Allow treatment (pressing or re-pressing and so-called "hotrolling") of the glasses. In particular, these glasses for near-net shape processing, such.
  • the viscosity temperature profile and processing temperature of the inventive Glasses are preferably adjusted so that such endgeometrienahe or endkon- forming hot forming is possible with sensitive precision machines.
  • the present invention furthermore relates to the use of the glasses according to the invention for the application areas of imaging, projection, telecommunications, optical communications technology, mobile drive and laser technology.
  • the invention furthermore relates to optical elements pressed from the glasses described, in particular produced by blank pressing, and to a process for producing optical elements by means of blank pressing of the glasses described.
  • optical elements comprising the glass according to the invention.
  • Optical elements may in particular be lenses, aspheres, prisms and compact components.
  • the term "optical element” also includes preforms or preforms of such an optical element, such as, for example, spheres, gobs, precision gobs and the like.
  • the present invention furthermore relates to a method for producing the glasses according to the invention, comprising the step of direct inductive heating of the mixture with an alternating electromagnetic field and / or oxidative melting of the glass.
  • Coupling the melt to an alternating electromagnetic field in particular in the form of a high-frequency field, is understood to mean that the energy input into the melt through inductive coupling is greater than the energy output from the melt due to the heat dissipation. Only then is it possible to heat or maintain the melt by means of high-frequency (HF) heating.
  • HF high-frequency
  • the molar ratio of B 2 O 3 to the sum of SiO 2 and B 2 O 3 is preferably at least 0.5. This ratio is particularly necessary for low-alkali or alkali-free glasses to ensure coupling capability to high frequency. Furthermore, the low viscosity of the highly bismuth oxide-containing glass is advantageous for a melt with HF heating.
  • the method preferably further comprises the step:
  • the crucible is preferably made of aluminum.
  • a skull crucible allows a melt in its own material, so that a particularly pure glass can be obtained.
  • the mixture can be melted both batchwise and continuously in the aggregate.
  • the method preferably further comprises the steps
  • Further processing can either be done conventionally (in platinum) or with particularly aggressive glasses in a second system with HF heating, which is used for lautering.
  • the following examples show preferred glasses according to the invention and are not intended to limit the scope of protection thereof.
  • the raw materials for the oxides are weighed, one or more refining agents, such as. B. Sb 2 O 3 , added and then mixed well.
  • the glass batch is melted down at about 900 ° C. in a continuous smelting unit and oxygen is bubbled, ie oxygen is introduced into the melt, then refined (920 ° C.) and homogenized.
  • a casting temperature of about 890 ° C the glass can be cast and processed to the desired dimensions.
  • temperatures in the large-volume, continuous aggregate can be lowered by at least about 100 K, and the material can be processed in an end geometry-oriented pressing process.
  • All the glasses according to the invention have a Cr content of less than 2 ppm, a glass transition temperature T g of less than or equal to 420 ° C., a refractive index n d of at least 2.05, an Abbe number Od in the range of at least 10 to at most 21, an absorption edge ⁇ 5 of at most 430 nm, can be processed well, reheated to a temperature above T g and are very resistant to acids and alkalis. Furthermore, none of the glasses according to the invention has a deterioration of the transmission of the glass in the wavelength range from ⁇ ( ⁇ , ⁇ ) to ⁇ ( ⁇ , ⁇ +400 nm) of more than 0.9% and a pure transmission of at least 95%. All transmissions were measured on glass samples having a thickness of 10 mm.
  • WET means a test with reheating the glass for at least 20 minutes, preferably 2 hours, to a temperature at which the glass has a viscosity of 10 9 dPas and WET (T 2 ) testing with reheating the glass to a temperature at which the glass has a viscosity of 10 5 dPas.
  • the abbreviation "b.” Means that this test was passed, ie that the glass did not show devitrification or haze after the test
  • the abbreviation "nb” means that this test was failed, ie that the glass was deflagrated during reheating or after the test had a turbidity. The rewarming tests do not take place under non-oxidizing conditions, but under normal atmosphere (air).

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Glass Compositions (AREA)
  • Glass Melting And Manufacturing (AREA)

Abstract

La présente invention concerne un verre optique à indice de réfraction élevé contenant de l'oxyde de bismuth ainsi que la fabrication et l'utilisation d'un tel verre. Elle décrit un verre optique hautement transmissif qui a la composition suivante (en % molaire sur la base de l'oxyde): Bi2O3 au moins 40, ∑ SiO2+B2O3+Al2O3 20-59, R2O 0-10, RO 0-30, d'autres composants 0,01-20. Les verres présentent une valeur de réfraction (nd) de 1,9 ≤ nd ≤ 2,2 et un nombre d'Abbe de 10 ≤ vd ≤ 21 et une température de transformation (Tg) d'au maximum 480 °C.
PCT/EP2012/057176 2011-04-21 2012-04-19 Verre optique à indice de réfraction élevé Ceased WO2012143452A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201280019510.2A CN103502165B (zh) 2011-04-21 2012-04-19 高折射率的光学玻璃
KR1020137030854A KR20140025481A (ko) 2011-04-21 2012-04-19 고굴절율 광학 유리
JP2014505629A JP6113714B2 (ja) 2011-04-21 2012-04-19 高屈折率光学ガラス

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE102011018655.7 2011-04-21
DE102011018655 2011-04-21
DE102011018703.0 2011-04-26
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US11319243B2 (en) 2018-01-17 2022-05-03 Corning Incorporated High refractive index optical borate glass

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US11319243B2 (en) 2018-01-17 2022-05-03 Corning Incorporated High refractive index optical borate glass

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JP6113714B2 (ja) 2017-04-12
CN103502165A (zh) 2014-01-08

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