[go: up one dir, main page]

WO2003053873A2 - Verres a phases separees - Google Patents

Verres a phases separees Download PDF

Info

Publication number
WO2003053873A2
WO2003053873A2 PCT/EP2002/014659 EP0214659W WO03053873A2 WO 2003053873 A2 WO2003053873 A2 WO 2003053873A2 EP 0214659 W EP0214659 W EP 0214659W WO 03053873 A2 WO03053873 A2 WO 03053873A2
Authority
WO
WIPO (PCT)
Prior art keywords
glass
matrix
glasses
phase
glass according
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.)
Ceased
Application number
PCT/EP2002/014659
Other languages
German (de)
English (en)
Other versions
WO2003053873A3 (fr
Inventor
Ulrich Peuchert
Karine Seneschal
Bianca Schreder
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
Carl Zeiss AG
Original Assignee
Carl Zeiss AG
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 Carl Zeiss AG, Schott Glaswerke AG filed Critical Carl Zeiss AG
Priority to AU2002361192A priority Critical patent/AU2002361192A1/en
Publication of WO2003053873A2 publication Critical patent/WO2003053873A2/fr
Publication of WO2003053873A3 publication Critical patent/WO2003053873A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight

Definitions

  • the present invention relates to a phase-separated optical glass and a method for producing such a glass.
  • the present invention further relates to optical elements, in particular a glass fiber and an optical amplifier, produced from the phase-separated glass according to the invention, and to a method for producing such a glass fiber.
  • Phase separated glasses have long been known in the art.
  • sodium borosilicate glasses are produced in which the sodium and boron compounds can be dissolved out of the glass and the silicate residue is then used to produce quartz glass by sintering at relatively low temperatures.
  • Fluorine-tarnished glasses are also used to produce white lamp glasses.
  • Glass ceramics that is, glasses with a glassy matrix and crystallites enclosed therein, are an exception.
  • the prior art mentions several glass ceramics which are used as optical glasses.
  • US 5,483,628 and US 5,537,505 describe glass ceramics for optical waveguides.
  • WO 99/05071 and WO 99/28255 also describe transparent glass ceramics, which can also be doped with rare earth compounds.
  • glass ceramics have some disadvantages.
  • the crystallites enclosed in the matrix can cause transmission losses due to scattering mechanisms at the phase boundaries.
  • glass fibers can be drawn from such materials only with difficulty and, depending on the crystallite size, these generally have only poor mechanical resistance. It is assumed that the crystallites or their phase boundaries form a kind of predetermined breaking points.
  • Glass ceramics are also usually produced by tempering a green glass body. Reheating after tempering for fiber drawing can therefore change the crystal properties, such as the crystallite size and distribution, and change the properties of the glass ceramic.
  • Heavy metal glasses such as tellurium oxide glasses (see, for example, EP 0 858 976), bismuth oxide glasses (see, for example, EP 1 127 858 A1) or antimony oxide glasses (WO 99/51537) have also been proposed as materials for optical amplifiers in the recent past, which are characterized by have a wide gain.
  • such heavy metal oxide glasses have the disadvantage that they have a significantly higher refractive index of n 2 than the standard SiO 2 Have fibers of the telecommunications network, so that when connecting such amplifier fibers with the usual SiO ⁇ fibers, the so-called splicing, problems occur at the phase boundaries due to scattering losses and reflections.
  • novel optical glasses which do not have the problems of the prior art.
  • novel glasses are to be provided which can be used as materials for optical amplifiers.
  • phase-separated optical glass which comprises an SiO 2 -based matrix and at least one type of discrete regions embedded in the matrix, the discrete regions embedded in the matrix having a composition different from the matrix, and these regions are essentially not crystalline.
  • FIG. 1 shows emission spectra of samples from the examples and comparative examples.
  • FIG. 2 shows transmission spectra of two Er-doped antimony silicate glasses.
  • Figures 3 to 5 show greatly enlarged photographic images of glasses according to the invention.
  • “essentially crystalline” means that less than 10% by volume, preferably less than 5% by volume, more preferably less than 1% by volume and very particularly preferably that no crystallites in the matrix According to a preferred embodiment of the present invention, there are also no crystallites in the matrix.
  • optical glasses or glasses of optical quality are understood to mean glasses with defined linear and / or nonlinear optical properties, which are usually melted from high-purity starting components.
  • passive and active optical glasses are understood to mean those which have as little or no interaction with the incident light and which have defined linear optical properties, such as transparency, refractive index, Abbe number, etc. Such passive optical glasses can be used, for example, as optical lenses be applied.
  • active glasses are understood to mean glasses which have a defined interaction with incident light, such as non-linear optical properties, frequency doubling, stimulated emission, etc. Such active optical glasses can be used, for example, as core material of optical amplifiers, as laser resonator material, etc. Of course, active optical glasses generally also have defined passive properties.
  • the glass according to the invention is preferably transparent.
  • matrix means the continuous phase of the phase-separated optical glass according to the invention and stands in contrast to the areas embedded in the matrix in which it is preferably not continuous, but discontinuous or discrete areas within the matrix. “Continuous” in this context means that essentially all areas of the silicate phase are connected to one another and that only in exceptional cases is a silicate “droplet” completely enclosed by the other phase.
  • two or more different types of regions can also be present in the matrix. These areas can be homogeneous or in turn have further discrete areas with a composition different from the matrix and / or the first discrete areas.
  • crystallites can also be present in the amorphous regions, provided that these regions are still essentially crystal-free, as defined above.
  • the areas embedded in the matrix preferably have a spherical or droplet-like shape.
  • the regions also have a shape deviating from a spherical shape.
  • ellipsoidal regions are present in the matrix in the glass according to the invention.
  • the glass according to the invention preferably has a binodal phase distribution.
  • the mixture tends to form or contain discrete spherical particles.
  • the phase boundaries are equally sharp from the start of particle formation and during their growth. A phase separation takes place in that centers form in the metastable state and droplets form as a result of the growth of these centers, the composition of the matrix and droplets being defined from the start and remaining essentially constant at a constant temperature.
  • a spinodal arrangement of the phases can also be present in the phase-separated glass.
  • These systems tend to form phases with non-spherical particles that are highly interconnected.
  • the phase boundary is rather diffuse at the beginning of the phase separation and becomes clearer with increasing phase separation.
  • interconnected phases are defined from the start, with the differences in the phase compositions and the volume of the phases increasing over time.
  • Such spinodal arrangements can be converted into binodal arrangements.
  • the size of the discrete areas embedded in the matrix is preferably matched to the properties of the light irradiated during later use.
  • the discrete particles preferably have a size such that no unintended interactions occur when light is irradiated.
  • a clouding of a glass can occur through various mechanisms. With a particle diameter that is larger than the wavelength of the radiated light, the glass can be clouded by refraction and / or reflection. Light scattering can take place with a particle diameter which is approximately equal to the wavelength. If the particle diameter is smaller than the wavelength, the glass is transparent.
  • the areas embedded in the matrix have a smaller diameter than the wavelength of the incident light.
  • the average discrete regions embedded in the matrix have a diameter of at most 100 nm, particularly preferably at most 50 nm, and preferably at least 1 nm.
  • the regions embedded in the matrix have a diameter of preferably at most 25 nm, more preferably at most 20 nm, particularly preferably at most 10 nm.
  • the transmission spectra of two glasses according to the invention which have the same composition but differ in the diameter of the regions embedded in the matrix.
  • the maximum transmission of the glass, which have embedded areas with a larger diameter is deteriorated compared to the glass, which have embedded areas with a smaller diameter.
  • the diameter of the regions embedded in the matrix is in a range from 10 to 100 nm, preferably 20 to 50 nm.
  • glasses of this embodiment can be used as an intensity filter.
  • the matrix and embedded areas have a different refractive index n.
  • the difference in the refractive index between the matrix and the embedded regions can also be sufficiently small so that, even when larger particles are present, there is essentially no clouding of the glass due to light refraction and / or reflections at the phase boundaries.
  • the phase-separated optical glass according to the invention preferably comprises the following composition (in mol%):
  • Heavy metal oxide 0-80 Silicon dioxide is preferably present in an amount of 30 to 75 mol%. In this area, the maximum strength of the glass composition is usually obtained.
  • Oxides of elements which are selected from the group of oxides of the elements Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, W, Ti, Zr, Cd and / or In can also be present.
  • Additional oxides can be included to adjust physicochemical or optical properties or to reduce the tendency to crystallize.
  • At least one further classic network-forming component such as B 2 O 3 , Al 2 O 3 , GeO 2 , etc. is preferred.
  • components can be present in the glass according to the invention which bring about stabilization of the glassy phase against crystallization, such as Al 2 O 3 , Z ⁇ O and Li 2 O. These components are preferably present in a total proportion of Al 2 O 3 + ZnO + Li 2 O of 0.1 to 20 mol%.
  • Lithium oxide can be added to the glass composition according to the invention in a proportion of preferably 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, in order to improve the phase separation and to prevent crystallization of the regions embedded in the matrix , Furthermore, the addition of Li 2 O may be preferred, since it can enlarge the glass formation areas in glasses containing heavy metal oxide.
  • the glass according to the invention can contain fluorine in a proportion of 0.01 to 20 mol%, preferably 0.1 to 10 mol%, to improve the phase separation.
  • Zinc oxide can be used to regulate particle size. Zinc oxide can occur both in the matrix phase and in the embedded areas. It is believed to change the surface tension of the embedded areas. If zinc oxide or ZnO is present in a proportion of at least about 0.4 mol%, this can result in smaller embedded areas. The addition of zinc oxide is particularly preferred if lithium oxide is present in a content of at least 0.2 mol%.
  • Phosphate or phosphorus compounds can support phase separation in some glass compositions. In the case of such glass compositions, the addition of phosphate is therefore particularly preferred. Phosphorus oxides also differ from the silicate matrix in terms of their physical properties and therefore tend to form a separate phase. If there are other compounds in the melt which are more compatible with the phosphate phase than with the silicate phase, these can form the regions different from the silicate matrix together with the phosphate phase. It is assumed that this process can also be used to enrich compounds in the areas other than the silicate matrix, which would just be soluble in the silicate matrix without the addition of phosphate.
  • the matrix is preferably a multicomponent system, with at least three components preferably being present side by side in the matrix.
  • the matrix contains silicon dioxide, aluminum oxide and potassium oxide, where potassium oxide can be replaced by other alkali metals and / or alkaline earth metals or can be present in a mixture with these.
  • the phase-separated optical glass according to the invention also contains discrete regions embedded in the matrix, which have a different composition from the matrix and which are essentially non-crystalline.
  • the composition according to the invention preferably contains a further compound which forms the main constituent of the regions embedded in the matrix.
  • a further compound which forms the main constituent of the regions embedded in the matrix.
  • part of the SiO 2 will also dissolve in the regions embedded in the matrix, just as part of the compound, which forms the main constituent of the regions embedded in the matrix, will also dissolve in the matrix.
  • the further oxides which may be present can be distributed over both phases and can serve to stabilize and / or improve the physical properties of the matrix and / or of the regions embedded in the matrix.
  • the molar fraction of the matrix components is greater than the molar fraction of the components which form the regions embedded in the matrix, for example the molar fraction of SiO 2 is 50 to 80 mol%, more preferably 60 to 70 Mol%, the molar proportion of the component which forms the main constituent of the regions embedded in the matrix, at 50 to 20 mol%, more preferably at 40 to 30 mol%.
  • the regions embedded in the matrix preferably comprise at least one heavy metal compound.
  • the proportion of the heavy metal compound in the glass composition is preferably at least 1 mol% on an oxide basis, more preferably at least 5 mol% on an oxide basis, particularly preferably at least 10 mol% on an oxide basis, and preferably at most 80 mol% on an oxide basis, more preferably at most 70 mol% on an oxide basis, particularly preferably at most 60 mol% on an oxide basis.
  • a heavy metal compound is preferably selected from a group of compounds which is selected from compounds of antimony, molybdenum, tellurium, tungsten, arsenic, bismuth, tantalum, lanthanum, niobium and / or mixtures of these compounds. It is further preferred that the heavy metal compounds are heavy metal oxides. Compounds of these elements differ in molecular size and other physical properties from the silicate matrix, so that there is a tendency for phase separation in a silicate matrix.
  • the glass according to the invention particularly preferably contains at least one heavy metal compound which is selected from compounds of antimony, molybdenum, tellurium, tungsten and / or mixtures of these compounds.
  • These heavy metals in particular have a significantly lower bond strength to oxygen atoms compared to silicon. In the form of oxides, they have a much lower melting point than silicon dioxide. For these reasons, it is assumed that these heavy metal oxides are only poorly miscible, ie not compatible, with silicon dioxide in the molten state. As a result, discrete phases are formed when the starting compositions are melted in the liquid phase. When they cool down, these segregated phases remain and form a phase-separated glass.
  • the glass according to the invention contains antimony oxide.
  • the addition of boric acid to the glass composition deteriorates the phase separation.
  • the addition of boron oxide or boric acid to the glass composition is therefore not preferred according to this embodiment of the present invention.
  • the glass according to the invention according to this embodiment therefore preferably comprises only small amounts of at most 10 mol% and very particularly preferably essentially no boron oxide.
  • BaO can also deteriorate the phase separation in glasses containing antimony oxide, and BaO is therefore preferably also present in a proportion of at most 10 mol% according to this embodiment of the present invention, more preferably the glass according to the invention contains essentially no BaO ,
  • the expression “essentially none” means that this component is at most present as an impurity and is not added to the starting glass composition as an additional component.
  • the glass according to the invention contains tellurium oxide and / or bismuth oxide.
  • the glass according to the invention further comprises at least one rare earth compound in a content of 0.005 to 10 mol%, more preferably 0.01 to 5 mol%.
  • the rare earth compound is preferably at least one oxide which is selected from oxides of Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu. Oxides of the elements Er, Pr, Tm, Nd and / or Dy are particularly preferred.
  • Sc and / or Y compounds can also be contained in the glass.
  • the rare earth compounds used are one or more so-called “optically active compounds”, “optically active compounds” being understood to mean those which lead to the glass according to the invention being stimulated to be emitted are capable if the glass is excited by a suitable pump source.
  • At least two rare earth compounds in a total amount of 0.01 to 15 mol% can also be used.
  • Glasses with optically active rare earth ions can be codoped with optically inactive rare earth elements, for example to increase the emission lifespan of the glass.
  • it can be coded with La and / or Y.
  • it can, for example, also be codoped with other optically active rare earth compounds, such as Yb.
  • Sc and / or Y compounds can also be present in the glass according to the invention.
  • other rare earth ions such as Tm
  • other wavelength ranges can be developed, such as the so-called S band between 1420 and 1520 nm in the case of Tm.
  • sensitizers such as Yb, Ho and Nd can be added in an appropriate amount, for example 0.005 to 8 mol%.
  • the content of each individual rare earth compound is preferably from 0.005 to 8 mol% on an oxide basis.
  • rare earth compounds accumulate preferentially in the discrete areas embedded in the matrix, provided that these are areas containing heavy metal oxide. It is assumed that the rare earth compounds also dissolve in the silicate matrix only when these areas are supersaturated.
  • the areas embedded in the matrix can contain, in addition to the heavy metal oxide compound and possibly the rare earth compounds, further oxides, for example alkali and / or alkaline earth compounds and / or portions of network formers, such as SiO 2 , Al 2 O 3 .
  • further oxides can therefore usually dissolve both in the matrix and in the regions embedded in the matrix and they can also be present in both phases at the same time.
  • these additional oxides can be used to stabilize against crystallization.
  • the phase-separated glass according to the invention is used as an optically active glass of an optical amplifier.
  • the addition of at least one component such as B 2 0 3 , Al 2 0 3 , Ge0 2 , etc. is particularly preferred.
  • oxides of W and or Ga can serve to increase the D ⁇ value, ie to broaden the emission cross section.
  • the addition of alkali oxides is particularly advantageous if the glass is to be used for planar optical amplifiers using the ion exchange technique.
  • Li 2 0 as a glass component is advantageous according to this embodiment if an optical amplifier with particularly good efficiency is to be generated in the L-band.
  • the present invention further relates to a method for producing the phase-separated optical glass according to the invention, which comprises the steps of mixing the starting composition and melting these starting components.
  • phase separation is preferably carried out solely by the starting composition of the components. According to the present invention, it is preferably not necessary to introduce special tempering steps in order to cause the at least two phases to separate.
  • Demixing can occur, for example, in the case of glasses containing antimony oxide even at high temperatures of greater than 1000.degree.
  • the heavy metal oxides also dissolve to a certain extent in the silicate phase, even if the majority of the heavy metal oxides form the discrete areas embedded in the matrix, and that Si0 2 also to a certain extent also in the heavy metal oxide-containing areas Phase solves. Therefore, depending on the solubility of the respective heavy metal oxide from the silicate matrix used may be preferred according to certain embodiments to add larger proportions of heavy metal oxide compounds to the starting mixture than is present later as a separate phase in the glass according to the invention.
  • the heavy metal compound in cases in which La 2 0 3 , Nb 2 0 5 , Ta 2 0 5 , Sb 0 3 , W0 3 , and / or mixtures thereof are used as the heavy metal compound in the glass according to the invention, the heavy metal compound preferably has a proportion of 1 to 60 mol% of the starting batch. In cases in which Mo0 3 , Bi 2 ⁇ 3, Te0 2 and / or mixtures thereof are used as the heavy metal compound in the glass according to the invention, the heavy metal compound preferably has a proportion of 1 to 80 mol% of the starting mixture.
  • fluorides preferably alkali and / or alkaline earth fluorides
  • the fluorides NaF, CaF 2 , AIF 3 and / or mixtures thereof are particularly preferably added to the mixture.
  • the starting components of the glass according to the invention are preferably predried before melting, since even a lower moisture content generally worsens the active and passive optical properties of glasses and, for example, can lead to shorter fluorescence lifetimes for glasses containing Er.
  • melt by blowing in preferably dry oxygen, so-called 0 2 -bubbling.
  • Drying of the melt can also be achieved by adding some of the starting components to the batch as bromides.
  • the starting components In front- up to 25 mol% of the alkali and / or alkaline earth compounds and / or of Al 2 0 3 can preferably be added in the form of bromides.
  • the glass After melting, the glass may be annealed prior to molding in accordance with one embodiment of the present invention.
  • the glass according to the invention is cooled to room temperature after molding. It is preferred according to the invention that the glasses are relatively quick, i.e. with cooling rates of preferably at least 5 K h, more preferably of at least 10 K / h. Such cooling rates, which are fast for optical glasses, can result in a smaller diameter of the regions embedded in the matrix, which is preferred according to some embodiments of the present invention.
  • a larger diameter of the regions embedded in the matrix may be desired, so that, according to these embodiments, slower cooling rates are preferred.
  • the glass is quenched, i.e. cooled very quickly to room temperature.
  • Larger glass volumes can be quenched by water cooling and or roller cooling.
  • water cooling is generally not required in such glass products in order to achieve rapid cooling rates.
  • Tempering or tempering the glasses near the melting point of the heavy metal oxide generally did not lead to any optical change in the glasses according to the invention. However, if the glass is heated to a temperature above the melting point of the areas embedded in the matrix warms, the heavy metal oxide-rich areas can melt, which in some glasses can lead to crystallization when the sample cools. According to the invention, the glasses according to the invention are therefore preferably no longer heated to a temperature above the melting temperature of the heavy metal oxide after the production.
  • phase-separated glass according to the invention can be used particularly advantageously as optically active glass for an optical amplifier. Since glasses according to the invention can also be warped into fibers, for example, single-mode fibers can be produced with a rare earth-doped core for optical fiber amplifiers.
  • FIG. 1 shows emission spectra of glasses according to the invention and not according to the invention for use as optically active glass for an optical amplifier.
  • the glasses each have emission spectra of different widths, with the widest possible emission spectrum being preferred since this leads to a widened gain of the optical amplifier and optical amplifiers with a wide gain are desired in telecommunications.
  • the first type (type A) has the narrowest and therefore the most unfavorable emission band.
  • These glasses are compositions in which there are no two-phase glasses or in which the glass has crystallites in a proportion of> 10% by volume. In the case of erbium doping, these glasses have a pink color.
  • glasses of the second type have a much wider emission band.
  • These glasses are phase-separated glasses according to the invention according to one embodiment, which are essentially not crystalline. These glasses are usually yellowish in color.
  • FIG. 1 thus shows that the phase-separated glasses according to the invention can achieve almost the same width of the emission spectrum as that of a pure antimony oxide glass, but at the same time its disadvantages, such as the difficult manufacture, can be avoided.
  • a “glass in glass” in which different functionalities can be achieved in one material and these functionalities could not be present simultaneously in a homogeneous glass.
  • the ones shown in FIG. 1 Glasses according to the invention have, for example, the following combination of properties:
  • the phase-separated glass according to the invention has a longer fluorescence lifetime ⁇ than the glasses from the comparative examples.
  • the glasses according to one embodiment of the invention have fluorescence lifetimes ⁇ of> 3 ms, preferably> 5 ms.
  • the fluorescence lifetime ⁇ is the time at which the intensity of the fluorescence has dropped to 37% of the maximum intensity after the excitation light has been switched off.
  • the present invention thus also relates to a glass fiber which comprises the glass according to the invention.
  • a glass fiber which comprises the glass according to the invention.
  • a double or triple crucible one or more outer glass jackets can also be applied to the fiber core simultaneously during the fiber drawing process.
  • Such a glass fiber for an optical amplifier preferably has a core with a thickness of 1 to 15 ⁇ m and one or more glass jackets, so that an outer diameter of, for example, about 125 ⁇ m results.
  • the glass according to the invention macroscopically has a refractive index which corresponds approximately to that of a conventional SiO 2 -based glass or is of the same order of magnitude.
  • the glasses according to the invention macroscopically have a refractive index of ⁇ ⁇ 1.7 at 1300 nm. This low refractive index makes it possible, for example, for an amplifier fiber made from the glass according to the invention to be connected to the silicate glass fibers of the telecommunications network for optical amplifiers with little technical problems or outlay using methods customary in the prior art.
  • Silicate glasses can also be selected for the coats.
  • a cladding of an optical fiber should have physical properties similar to the core of an optical fiber. Since the glass according to the invention has the same macroscopic properties as a silicate glass, when using the glass according to the invention as the core glass of a glass fiber, the cladding glasses can also be of silicatic origin. This has the considerable advantage that the antimony oxide-containing shells required for homogeneous antimony oxide-containing glasses can be avoided, which are not advantageous for reasons of environmental protection and with regard to undesired crystallization. For example, crystallization-stable lead silicate glasses can be used as cladding glasses.
  • the glass compositions given in the table below became glasses of the examples according to the invention and the glasses similar examples produced.
  • High-purity raw materials were used.
  • Anti-monoxide was dried to reduce the water content.
  • all the glasses were melted in silica glass crucibles at about 1500 ° C.
  • the silica glass crucible was arranged in an inductively heated platinum crucible. Dry oxygen was introduced into the melted mixture at 1550 ° C. for about 90 minutes.
  • the molten glass composition was ⁇ A hour at about 1500 ° C allowed to stand before it was poured into pre-heated graphite molds.
  • the samples were cooled uniformly at 450 ° C. for half an hour and cooled to room temperature at a rate of 15 K / h.
  • the glasses of Examples A to L according to the invention all have the advantageous properties of an emission curve of type B, fluorescence lifetimes ⁇ of> 5 ms and a refractive index n at 1300 nm of approximately 1.6.
  • the glasses from Examples B, C, D and F could be annealed at 700 ° C. without a significant change in the properties, such as, for example, separation of the phases.
  • the heavy metal oxide content can be varied within a wide range, as examples A to F show. Furthermore, various other components can be contained in the glass according to the invention without the optical properties of the glass being impaired.
  • the color of the glass can give an indication of the internal structure of the glass.
  • Erbium (Er) usually dissolves in a phase containing heavy metal oxide in a yellowish color, whereas in the absence of a phase containing heavy metal oxide it dissolves in the silicate phase to form a pink or pink color.
  • the color of the glass thus gives a first rough indication of whether the phase-separated glass according to the invention is present or not.
  • the glass from example L which is colored strongly pink, but nevertheless has an emission curve of type B.
  • This glass contains a relatively high proportion of erbium, and it is suspected that not all erbium oxide was able to dissolve in the heavy metal oxide-containing phase and therefore remains in the silicate phase and gives it its pink color, which gives the yellow color to the heavy metal-containing ones Phase covered.
  • this exemplary embodiment is less preferred since the fluorescence lifetime ⁇ is deteriorated to a value below 5 ms compared to the other examples. This is attributed to concentration quenching due to the high Er concentration.
  • the glass from comparative example 1 is a pure antimony oxide glass which was melted in a closed system.
  • the glass from comparative example 2 is an Er-doped silicate glass without heavy metal oxide.
  • compositions of the glasses from comparative examples 3 and 4 contain boron oxide in different contents. Both glasses only have an emission spectrum of type A, i.e. these glasses are only less suitable as glasses for optical amplifiers. Furthermore, the fluorescence lifetime ⁇ is deteriorated compared to that of the silicate glass from Comparative Example 2.
  • the glass from comparative example 5 contains no boron oxide, it still has only one type A emission curve. This behavior is attributed to the presence of barium oxide in the glass.
  • FIG. 3 shows the edge area of a two-phase glass, in which the areas different from the matrix can be clearly recognized as dark areas. In this case, the areas have a diameter of approximately 10 to 20 nm.
  • FIG. 4 shows the recording of a glass which was produced by quenching the melt in water. The areas which contain antimony oxide and which are different from the matrix can be seen in dark areas and have a diameter of about 5 to 10 nm.
  • FIGS. 5 a to c show photographic images of TEM microscopic images in different magnifications. The areas different from the matrix can also be clearly seen in these figures and have a diameter of approximately 10 to 20 nm.
  • the 5c, the finer structuring contained is an artifact of the measurement and not due to the glass structure.

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)
  • Glass Melting And Manufacturing (AREA)

Abstract

Verre optique à phases séparées et procédé de fabrication d'un verre de ce type. La présente invention concerne en outre des éléments optiques fabriqués à l'aide dudit verre à phases séparées, en particulier une fibre optique et un amplificateur optique, ainsi qu'un procédé de fabrication d'une fibre optique de ce type.
PCT/EP2002/014659 2001-12-21 2002-12-20 Verres a phases separees Ceased WO2003053873A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002361192A AU2002361192A1 (en) 2001-12-21 2002-12-20 Phase-separated glasses

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001163553 DE10163553B4 (de) 2001-12-21 2001-12-21 Phasenseparierte Gläser und deren Verwendung
DE10163553.2 2001-12-21

Publications (2)

Publication Number Publication Date
WO2003053873A2 true WO2003053873A2 (fr) 2003-07-03
WO2003053873A3 WO2003053873A3 (fr) 2004-03-04

Family

ID=7710570

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/014659 Ceased WO2003053873A2 (fr) 2001-12-21 2002-12-20 Verres a phases separees

Country Status (3)

Country Link
AU (1) AU2002361192A1 (fr)
DE (1) DE10163553B4 (fr)
WO (1) WO2003053873A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014134097A1 (fr) * 2013-02-28 2014-09-04 Corning Incorporated Articles en verre feuilleté avec gainages à phases séparées et leurs procédés de formation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006012869B4 (de) * 2006-03-21 2010-09-23 Schott Ag Optische Faser für einen Hochleistungs-Faserlaser, seine Herstellung sowie Hochleistungs-Faserlaser, umfassend die optische Faser

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5483628A (en) 1994-11-25 1996-01-09 Corning Incorporated Transparent glass-ceramics
US5537505A (en) 1994-11-25 1996-07-16 Corning Incorporated Transparent glass-ceramics
EP0858976A2 (fr) 1997-02-14 1998-08-19 Nippon Telegraph and Telephone Corporation Verre de tellurite, amplificateur optique et source de lumière
WO1999005071A1 (fr) 1997-07-24 1999-02-04 Corning Incorporated Vitroceramique transparente a base de fluorure de lanthane
WO1999028255A1 (fr) 1997-12-02 1999-06-10 Corning Incorporated Combinaison d'elements des terres rares et d'halogenures dans des verres a oxyhalogenures
WO1999051537A1 (fr) 1998-04-08 1999-10-14 Corning Incorporated Verre renfermant de l'antimoine, dope aux terres rares
EP1127858A1 (fr) 1998-10-20 2001-08-29 Asahi Glass Company Ltd. Verre amplificateur de lumiere, milieu amplificateur de lumiere et milieu amplificateur de lumiere a revetement de resine

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8713698D0 (en) * 1987-06-11 1987-07-15 British Telecomm Glass compositions
JPS63260837A (ja) * 1987-04-16 1988-10-27 Asahi Glass Co Ltd 紫外線遮断ガラス
CA2030748C (fr) * 1989-12-22 2000-08-15 Marcella Rose Backer Fibre optique guide-ondes avec revetement externe en dioxyde de titane et silice; procede de fabrication
JP2505686B2 (ja) * 1992-05-28 1996-06-12 俊則 国府 赤色光透過性白色オパ―ルガラスおよびその製造方法
JPH05341338A (ja) * 1992-06-11 1993-12-24 Matsushita Electric Ind Co Ltd 非線形光学ガラスおよびその製造方法
DE69614721T2 (de) * 1995-11-14 2002-07-04 Corning Inc., Corning Getrennte phasen aufweisende nichtkristalline opalgläser
DE19610433C2 (de) * 1996-03-16 1999-01-07 Univ Schiller Jena Lumineszierendes Glas und Verfahren zur Herstellung und Anwendungen dieses Glases
US6268303B1 (en) * 1998-07-06 2001-07-31 Corning Incorporated Tantalum containing glasses and glass ceramics

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5483628A (en) 1994-11-25 1996-01-09 Corning Incorporated Transparent glass-ceramics
US5537505A (en) 1994-11-25 1996-07-16 Corning Incorporated Transparent glass-ceramics
EP0858976A2 (fr) 1997-02-14 1998-08-19 Nippon Telegraph and Telephone Corporation Verre de tellurite, amplificateur optique et source de lumière
WO1999005071A1 (fr) 1997-07-24 1999-02-04 Corning Incorporated Vitroceramique transparente a base de fluorure de lanthane
WO1999028255A1 (fr) 1997-12-02 1999-06-10 Corning Incorporated Combinaison d'elements des terres rares et d'halogenures dans des verres a oxyhalogenures
WO1999051537A1 (fr) 1998-04-08 1999-10-14 Corning Incorporated Verre renfermant de l'antimoine, dope aux terres rares
EP1127858A1 (fr) 1998-10-20 2001-08-29 Asahi Glass Company Ltd. Verre amplificateur de lumiere, milieu amplificateur de lumiere et milieu amplificateur de lumiere a revetement de resine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014134097A1 (fr) * 2013-02-28 2014-09-04 Corning Incorporated Articles en verre feuilleté avec gainages à phases séparées et leurs procédés de formation
US9393760B2 (en) 2013-02-28 2016-07-19 Corning Incorporated Laminated glass articles with phase-separated claddings and methods for forming the same
US10259739B2 (en) 2013-02-28 2019-04-16 Corning Incorporated Laminated glass articles with phase-separated claddings and methods for forming the same

Also Published As

Publication number Publication date
DE10163553B4 (de) 2008-01-17
DE10163553A1 (de) 2003-07-17
AU2002361192A1 (en) 2003-07-09
WO2003053873A3 (fr) 2004-03-04

Similar Documents

Publication Publication Date Title
DE69600652T2 (de) Durchsichtige Glaskeramik
DE60105978T2 (de) Lichtverstärktes glas und verfahren zu dessen herstellung
DE69504461T2 (de) Durchsichtige Glaskeramik
DE69824460T2 (de) Tellurit-Glas, optischer Verstärker und Lichtquelle
DE69106795T2 (de) Quarzglas dotiert mit einem seltenen erde-element und verfahren zu deren herstellung.
EP2072477B1 (fr) Verre de coeur dans un système de verre alcali-zinc-silicate pour un conducteur lumineux à fibres optiques et conducteur lumineux à fibres optiques doté de ce verre de coeur
DE69920251T2 (de) Lichtverstärkendes glas, lichtverstärkendes mediumund harzbeschichtetes lichtverstärkendes medium
DE102009010701B4 (de) Optisches Glas
DE102007008300B4 (de) Bleifreies optisches Glas der Schwerflint- und Lanthanschwerflintlage sowie dessen Herstellung und Verwendung
EP3782961B1 (fr) Verres hautement transmissifs à résistance élevée à la solarisation, leur utilisation et procédé pour les produire
DE69331300T2 (de) Verfahren zur Abscheidung aus der Gasphase von einem Fluorid-Glasfilm auf einem Substrat
DE10294076B4 (de) Verfahren zur Herstellung eines Bismutoxid-haltigen Glases und Verwendung des Verfahrens
DE10139904A1 (de) Optische Telluritgläser für Lichtwellenleiterverstärker und Oszillatoren sowie Verfahren zu ihrer Herstellung
DE3103771C2 (de) Infrarotstrahlendurchlässige Glasfasern und Verfahren zu deren Herstellung
DE4444844C2 (de) Glaskeramik-Materialien insbesondere für Laser und optische Verstärker, die mit Elementen der Seltenen Erden dotiert sind, und Verfahren zu ihrer Herstellung
DE10141105C1 (de) Optisches Farbglas und seine Verwendung
EP1544176B1 (fr) Verre alumino-boro-silicaté et procédé de fabrication de lentilles à gradient d'indice exemptes de cristaux
WO2004074197A1 (fr) Verre contenant de l'oxyde de bismuth, son procede de production et son utilisation
DE102009047511A1 (de) Hochbrechendes und hochtransparentes optisches Glas
DE60201399T2 (de) Optisch verstärkendes Glas und Lichtwellenleiter
EP1425250A1 (fr) Verres a l'oxyde de bismuth contenant de l'oxyde de germanium
DE112021002188T5 (de) Optisches glas
DE69807706T2 (de) Glaszusammensetzung und optische vorrichtung daraus hergestellt
DE69828172T2 (de) Transparente lanthanfluorid-glaskeramiker
DE10163553B4 (de) Phasenseparierte Gläser und deren Verwendung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP