US20090018007A1 - Lithium-aluminosilicate glass with short glazing times - Google Patents

Lithium-aluminosilicate glass with short glazing times Download PDF

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US20090018007A1
US20090018007A1 US11/688,104 US68810407A US2009018007A1 US 20090018007 A1 US20090018007 A1 US 20090018007A1 US 68810407 A US68810407 A US 68810407A US 2009018007 A1 US2009018007 A1 US 2009018007A1
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glass
weight
lithium
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Friedrich Siebers
Ulrich Schiffner
Wolfgang Schmidbauer
Klaus Schonberger
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Schott AG
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    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

Definitions

  • glasses from the L 2 O—Al 2 O 3 —SiO 2 system can be converted into glass ceramics with high-quartz mixed crystals or keatite mixed crystals as main crystal phases.
  • the invention relates to a lithium-aluminosilicate glass that can be converted with short glazing times of less than 2.5 hours, preferably less than 100 minutes, into a transparent glass ceramic with high-quartz mixed crystals as a prevailing crystal phase and in this case is without visually disruptive light scattering (turbidity) or inherent color.
  • a key property of these glass ceramics is that in a temperature range from room temperature up to about 700° C., they have an extremely low thermal expansion coefficient ⁇ 20/700 ⁇ 1.5 ⁇ 10 ⁇ 6 /K. These glass ceramics are therefore used in transparent form as, e.g., fire protection glass, fireplace door windows, cookware, and cooking surfaces, as well as substrate material for wafer stages or for mirror supports for telescopes and for reflectors in beamers.
  • transparent glass ceramics In numerous applications of transparent glass ceramics, the latter are required in flat form, for example in the form of panes, as windows for fireplaces, for fire protection glazings, cooking surfaces with colored bottom coating and for display purposes.
  • the production of such flat glass from the glass melt, which is used as a starting glass for the production of glass ceramics, is usually carried out by rolling and recently also by floating.
  • a low melting point and a low processing temperature V A are desired; on the other hand, the glass must show no devitrification during shaping, i.e., no disruptive crystals should form that impair the resistance in the starting glasses and the glass ceramics that are produced therefrom.
  • the last contact of the glass melt is with the debiteuse that is made of noble metal (usually Pr/Rh) before the glass is formed by the rolling and is cooled.
  • the starting glass is produced via conventional glass manufacturing processes.
  • typically arsenic oxide and/or antimony oxide is (are) used as a refining agent.
  • These refining agents are compatible with the required glass ceramic properties and result in good bubble qualities in the melt.
  • SnO 2 is used as a refining agent in particular in connection with high-temperature refining above 1700° C.
  • the glass After the melting and refining, the glass usually undergoes hot forming by rolling, pouring, pressing or, recently, floating. Then, the starting glass is converted into the glass-ceramic article by controlled crystallization.
  • This glazing is carried out in a two-stage temperature process, in which nuclei, usually from ZrO 2 /TiO 2 mixed crystals, are produced first by nucleation at a temperature of between 600 and 800° C. Also, SnO 2 can be involved in the nucleation. In the case of subsequent temperature increase, the high-quartz mixed crystals in these nuclei grow at the crystallization temperature of 800 to 900° C. If desired, the high-quartz mixed crystals can then also be converted into keatite mixed crystals.
  • the conversion into keatite mixed crystals is carried out with a temperature increase in a temperature range of about 900 to 1200° C.
  • glass ceramics with keatite mixed crystals as a main phase are translucent or opaque and have a white color shade, which can be altered by the addition of colored oxides.
  • the thermal expansion coefficient of the glass ceramic is increased, and the transparency is reduced by the light scattering that is associated with the enlargement of the crystals.
  • Transparency means that the glass ceramics are to have high light transmission in the visible range as well as low light scattering (turbidity).
  • the low light scattering is achieved via a high nuclear density, which has the effect that the sizes of the growing high-quartz mixed crystals lie below the wavelength range of visible light.
  • the mean crystallite size of the high-quartz mixed crystals is in the range of 20 to 80 nm.
  • a high nuclear density requires sufficient contents of nucleating agents as well as sufficient nucleation times during the glazing.
  • the inherent color of transparent glass ceramic plates can have various causes.
  • the coloring element Fe is contained as a contaminant.
  • the use of refining agents Sb 2 O 3 and CeO 2 results in a low inherent color.
  • the described brownish-yellow inherent coloring of the transparent glass ceramics is based to a decisive extent on electronic transfers to color complexes, which absorb in the area of the visible light and in which the components that are necessary for the nucleation, the Ti ion, is involved. The most frequently absorbing color complex is the formation of adjacent Fe and Ti ions between which electronic charge-transfer transitions take place.
  • Sn/Ti complexes also produce an inherent color.
  • the Fe/Ti color complexes result in a red-brown discoloration, and the Sn/Ti color complexes result in a yellow-brown discoloration.
  • the formation of these adjacent color complexes takes place as early as during cooling of the starting glass and in particular during later glazing of the glass ceramics.
  • the ions are still dispersed uniformly, and during cooling, at high temperatures and during glazing, they preferably accumulate in a clustered manner.
  • the inherent color is thus quite considerably intensified compared to the starting glass.
  • the transparent flat glasses and in particular the glass ceramics that are produced therefrom obtain a clear inherent color, which greatly increases with the thickness.
  • the glazing of the lithium-aluminosilicate glasses that consist of glass ceramics usually takes place in roller passage kilns or tunnel kilns. To avoid rough spots of the plates during the glazing, it is necessary that this kiln have a very good temperature homogeneity such that the top and bottom of the plates of the starting glasses crystallize simultaneously. Otherwise, process-induced distortions result. Because of these high requirements and the associated high acquisition costs of the glazing kiln, it is economically advantageous if the kilns can be run with high throughputs, i.e., that the total glazing time is kept as short as possible. This results in the conflict of purpose, however, that the starting glasses have to have a sufficient amount of nucleating agents so that in the conversion into the glass ceramic, no light scattering on large crystallites takes place (Tyndall Effect).
  • nucleating agent TiO 2 minimum contents of the nucleating agent TiO 2 are necessary, since this nucleating agent can be replaced only disadvantageously in the case of melts and devitrification by the alternative nucleating agent ZrO 2 . This means that the desired quick glazing times and short nucleation times with the TiO 2 contents required for this purpose result in an enhanced inherent color.
  • the reduction of the Fe content is a measure that is economically usable only to a certain extent.
  • a certain amount of Fe 2 O 3 in the batch always develops through the industrially available raw materials of the batch for the production of the glass and by wear and tear from system parts for the production and homogenization of the batch. Based on the costs for extremely pure raw materials and special plant design measures, it is economically no longer justifiable to reduce the Fe 2 O 3 content below about 50 ppm in transparent glass ceramics.
  • the Fe 2 O 3 content is usually on the order of magnitude of about 100 to 500 ppm.
  • U.S. Pat. No. 4,438,210 describes attempts to reduce the Fe/Ti color complex.
  • transparent glass ceramics with low inherent color are obtained, which contain 2-6% by weight of TiO 2 and 0-2% by weight of ZrO 2 as nucleating agents and up to about 0.1% by weight of Fe 2 O 3 as contaminants, by the component MgO essentially being omitted.
  • JP 03-23237 A describes the production of transparent glass ceramics without inherent color. These glass ceramics avoid the addition of TiO 2 as nucleating agents and are based on a mixed nucleation by ZrO 2 /SnO 2 .
  • the SnO 2 contents that are necessary for this purpose are more than 1% by weight. In the case of these high SnO 2 contents, however, the devitrification resistance of the glass deteriorates. In the area of shaping, in the case of viscosities around the processing temperature V A of 10 4 dPas, a disruptive Sn-containing crystal phase crystallizes out. Thus, it results in an unreliable reduction of the strength of the glasses and the glass ceramics produced therefrom. Also, it has been shown that high SnO 2 contents result in a strong application of action of the glass melts on the noble-metal components, such as stirrers and electrodes. As a result, the service life of the noble-metal components is shortened.
  • a glass ceramic that is also TiO 2 -free is described preferably for applications in fire protection glazing, which has the addition of Nd 2 O 3 in contents of 0.2-1% by weight to stain over the inherent color produced by Fe ions.
  • the glass ceramics are germinated by 3-7% by weight of ZrO 2 . With these high ZrO 2 contents, however, the devitrification resistance of the glass deteriorates in the area of the shaping at viscosities around the processing temperature V A . It crystallizes out ZrO 2 (baddeleyite) as a disruptive crystal phase.
  • U.S. Pat. No. 4,093,468 describes the use of Nd 2 O 3 for the staining over of the color hue produced by the Fe/Ti color complex.
  • transparent glass ceramics almost without inherent color are known, which contain TiO 2 as a nucleating agent in contents of 0.5-6% by weight, a content of Fe 2 O 3 with contamination up to 500 pm, and which are stained over by the addition of 0.03-0.75% by weight of Nd 2 O 3 .
  • This patent specification describes that, in contrast to the conventional staining agents such as Co, Se, Cu, Cr, Mn, Ni, and V, Nd 2 O 3 is especially well suited to neutralize the color hue produced by the Fe/Ti color complex.
  • the patent specification does not provide any indication as to how to achieve a high transparency, i.e., low turbidity and high light transmission, within short glazing times, by optimizing the nucleating agents.
  • the examples of this patent contain disadvantageous nucleating agent combinations, thus high TiO 2 contents or nucleating agent concentrations that are too low. Owing to the deficient use of the alkalis Na 2 O and K 2 O, the glasses, moreover, have an insufficient devitrification resistance. No assessment is made on the influence of the refining agent on the formation of the Fe/Ti color complex.
  • the object of the invention is to find a lithium-aluminosilicate glass
  • the contents of the nucleating components TiO 2 , ZrO 2 , and SnO 2 have to be kept within relatively narrow limits. In this case, however, certain minimum contents of these compounds are necessary to produce nuclei in high density in the desired short glazing times of less than 2.5 hours, preferably less than 100 minutes during the nucleation, so that after the high-quartz mixed crystals are grown, transparent glass ceramics can be produced without turbidity. With the high nuclear density, the mean crystallite size of the high-quartz mixed crystals remains limited to values of ⁇ 80 nm, by which a disruptive light scattering is avoided. For an effective nucleation, minimum contents of TiO 2 and ZrO 2 are necessary.
  • turbidity (English: haze) is to be less than 1%, preferably less than 0.5% (measured for a 3.6 mm-thick plate with polished surfaces on both sides). According to ASTM D 1003, turbidity is the proportion, in percentage, of the transmitted light, which deviates from the irradiated light beam on average by more than 2.5°.
  • nucleating agents ZrO 2 , TiO 2 and SnO 2 if certain conditions are maintained.
  • the nucleation action of SnO 2 and TiO 2 is approximately the same, and thus these two components can be considered together.
  • the nucleating action of ZrO 2 is clearly greater. Therefore, combinations of the nucleating agents ZrO 2 and (TiO 2 +SnO 2 ), which lie in a straight line in a corresponding diagram ( FIG. 1 ), can be produced with identical nucleating action.
  • a lower boundary line for the minimum contents of the nucleating agents is produced:
  • ZrO 2 ⁇ 0.87(TiO 2 +SnO 2 )+3.65.
  • nucleating agents in % by weight
  • the upper limit is also shown in FIG. 1 .
  • the sum of the TiO 2 and SnO 2 contents is not to exceed 2.7% by weight, however, since these components are involved in the formation of the Fe/Ti and Sn/Ti color complexes for the inherent color.
  • the content of SnO 2 is not to exceed 4% by weight, since otherwise, in the case of shaping near the processing point V A , it results in an undesirable devitrification in the form of an Sn-containing crystal phase.
  • the equivalent holds true for the content of ZrO 2 in which an upper limit of ⁇ 2.5% by weight is to be maintained, so that devitrification in the form of a ZrO 2 -containing crystal phase (baddeleyite) does not result. This is expressed by the upper devitrification limit that is to be below the processing temperature V A .
  • the acceptable range of the nucleating agent contents can be defined in a diagram ( FIG. 1 ).
  • the minimum contents of 1.3% by weight, and for ⁇ SnO 2 +TiO 2 the minimum contents of 1.3% by weight are necessary to ensure a low turbidity (haze) of less than 1%.
  • the disruptive inherent color that is based on Fe/Ti and/or Sn/Ti color complexes is reduced by additions of Nd 2 O 3 in contents of 50-4000 ppm. Below 50 ppm of Nd 2 O 3 , the action is no longer reliable, and above 4000 ppm, either the transmission of the glasses is poor (with excessive Fe 2 O 3 contents) or the inherent color of the Nd ion is disruptive. Contents of 100 to 4000 ppm and in particular 200 to 3000 ppm of Nd 2 O 3 are preferred. An upper limit for the N 2 O 3 content of less than 2000 ppm is quite especially preferred. The Nd 2 O 3 contents are necessary to achieve the goal, according to the invention, of a reduction of the inherent color of the floated flat glasses and the transparent glass ceramics that are produced therefrom by staining over.
  • Nd Additions of Nd have the advantage that this element of the red-brown coloring is especially readily counteracted by Fe/Ti or this element of the yellow-brown coloring is especially readily counteracted by Sn/Ti complexes.
  • the color point that is measured in the various color systems, such as, e.g., in the CIE color system or the CIELAB (in short, lab) color system is readily shifted in the direction of the achromatic point by Nd.
  • the Nd has a great number of characteristic absorption bands, which make possible a clear labeling. In the conversion into the transparent glass ceramic, these absorption lines are changed only slightly.
  • the labeling of the glass or the transparent glass ceramic that is produced therefrom can therefore be detected very easily with commercially available spectrometers. This allows the manufacturer of the original product to recognize his product and also ensures the simplified assignment of product liability in the event of damage or loss. A differentiation of transparent glass ceramics of various manufacturers is otherwise possible only via expensive analytical measuring methods, as they are available only in a few special laboratories.
  • the characteristic absorption lines for the Nd also make possible a detection and separation in preparation processes during recycling of old cullets that consist of lime-sodium glass.
  • the addition of Nd for labeling is especially advantageous because of the characteristic absorption lines and the property thereof to fluoresce into infrared. Because of the above-mentioned properties, it is possible to keep cullets—originating from transparent glass ceramic that, because of the low inherent color, can be easily confused with, e.g., normal window panes from low-melting lime-sodium glass—from being incorporated into their preparation process and remelted. The danger exists in that unmelted remnants are formed by the high melting points of the lithium aluminosilicate glasses (and glass ceramics) compared to those of lime-sodium glasses.
  • the lithium-aluminosilicate glasses according to the invention are to contain less than 400 ppm, preferably less than 200 ppm, of Fe 2 O 3 . Higher contents have the effect that even higher contents of the staining agent Nd are required to neutralize the color hue Fe/Ti. This results in lower light transmission and a visually observable gray hue.
  • the contents of Fe 2 O 3 can be minimized to an economically justifiable extent; smaller contents than about 50 ppm are no longer economical because of the high costs of Fe-free raw materials of the batch.
  • Additions of CoO in a total amount of up to 50 ppm to the Nd additive are advantageous to adjust the color point of the transparent glass ceramic more precisely in the direction of the achromatic point.
  • the Nd additive by itself does not shift the color point exactly in the direction of the achromatic point, such that this slight correction may be advantageous.
  • An amount of CoO from 1 to 50 ppm is preferred.
  • an upper limit for the CoO of 40 ppm, in particular 30 ppm cannot be exceeded.
  • other staining agents such as, e.g., Cr, Ni, V, Cu, Mn, and Ce can also be added. The total amount should not exceed 100 ppm.
  • the oxides Li 2 O, Al 2 O 3 and SiO 2 are components of the high-quartz and/or keatite mixed crystal phases that are necessary within the preferred limits indicated in the claims.
  • a minimum content of Li 2 O of 3% by weight is in general necessary, but Li 2 O contents of more than 4.5% by weight during the production process often result in an undesirable devitrification.
  • a content of 3.2 to 4.3% by weight of Li 2 O leads to especially good results.
  • the Al 2 O 3 content is limited in the case of a preferred minimum content of 19% by weight to preferably a maximum 25% by weight, in particular 24% by weight.
  • the SiO 2 content is preferably to be at most 69% by weight, in particular 68% by weight, since this component greatly increases the viscosity of the glass.
  • higher contents of SiO 2 are disadvantageous for the melting of the glasses and with respect to the temperature stress during shaping.
  • the minimum content of SiO 2 is preferably to be 55% by weight, in particular 60% by weight.
  • MgO, ZnO and P 2 O 5 can be incorporated in the crystal phases as additional components. Because of the problem of forming undesirable crystal phases such as Zn spinel in the glazing, the ZnO content is limited to values of at most 2.5% by weight, preferably at most 2.0% by weight. The MgO content is limited to at most 2.0% by weight, preferably up to 1.5% by weight, since it otherwise unreliably increases the expansion coefficients of the glass ceramic. For low inherent color, MgO contents of less than 0.8% by weight and especially of less than 0.6% by weight are advantageous. A minimum MgO content of 0.1% by weight is generally required, so that the thermal expansion of the glass ceramic does not drop to negative values of below 0.3 ⁇ 10 ⁇ 6 /K.
  • alkalis Na 2 O and K 2 O to alkaline-earths CaO, SrO, and BaO as well as B 2 O 3 improve the meltability and the devitrification behavior of the glass during shaping.
  • the contents have to be limited, however, since these components essentially remain in the residual glass phase of the glass ceramic and increase the thermal expansion in an unreliable way. Also, higher contents can impair the crystallization behavior in the conversion of the glass into the glass ceramic and have a disadvantageous effect on the temperature resistance of the glass ceramic.
  • the sum of the alkalis Na 2 O+K 2 O is to be at least 0.2% by weight, preferably at least 0.3% by weight.
  • the addition of P 2 O 5 can be up to 3% by weight and is preferably limited to 1.5% by weight.
  • the addition of P 2 O 5 is advantageous for the devitrification resistance, but higher contents have a disadvantageous effect on the acid resistance.
  • the glasses according to the invention are refined with use of the refining agents arsenic oxide and/or antimony oxide that are conventional for glasses from the Li 2 O—Al 2 O 3 —SiO 2 system.
  • SnO 2 can be added in particular in connection with a high-temperature refining >1700° C. as an alternative and/or in combination in amounts of up to 0.3% by weight.
  • Other refining additives such as, e.g., CeO 2 , sulfate compounds, chloride compounds, and fluoride compounds can be added to the glass melts.
  • the total content of the refining agent and additives is not to exceed 2% by weight.
  • the water content of the glasses according to the invention is usually between 0.015 and 0.06 mol/l, depending on the selection of the raw materials of the batch and the process conditions in the melts. This corresponds to ⁇ OH values of 0.16 to 0.64 mm ⁇ 1 .
  • the glass according to the invention preferably has a composition (in % by weight based on oxide) of:
  • Nd 2 O 3 100-4000 ppm CoO 0-40 ppm optionally with the additions of chemical refining agents such as As 2 O 3 , Sb 2 O 3 , and CeO 2 and optionally additional refining additives, such as, for example, sulfate compounds, chloride compounds, and fluoride compounds in total amounts of up to 2% by weight.
  • chemical refining agents such as As 2 O 3 , Sb 2 O 3 , and CeO 2
  • additional refining additives such as, for example, sulfate compounds, chloride compounds, and fluoride compounds in total amounts of up to 2% by weight.
  • the Nd content is converted into an oxide base (Nd 2 O 3 ), whereby the type of Nd additive in the batch is not limited to the indicated oxide
  • the glass has a composition, in % by weight based on oxide, of:
  • the glass ceramic plate contains As 2 O 3 as a refining agent, optionally with additional refining additives such as sulfate, chloride and fluoride compounds in total contents of up to 1% by weight and is plained without the refining agents Sb 2 O 3 and SnO 2 .
  • SnO 2 As a refining agent in combination with a high-temperature refining above 1700° C., it is possible to eliminate the refining agents As 2 O 3 and Sb 2 O 3 that are disadvantageous from environmental standpoints and to obtain devitrification-stable starting glasses (OEG ⁇ V A ) with good bubble qualities. Since, however, Sn forms a colored Sn/Ti complex with Ti, an amount of 0.1 to 0.3% by weight of SnO 2 is preferred for refining.
  • the lithium-aluminosilicate glass according to the invention is typically characterized by a processing temperature V A under 1350° C. to promote the meltability of the glass and to limit the thermal stress on the system components during shaping.
  • the upper devitrification temperature OEG is below the processing temperature V A .
  • the thermal expansion coefficient ⁇ 20/700 is to deviate no more than 0.5 ⁇ 10 ⁇ 6 /K from the zero expansion.
  • the deviation is preferably to be less than 0.3 ⁇ 10 ⁇ 6 /K.
  • a preferred embodiment of the invention consists in that, in addition to the low turbidity, a low inherent color and a high light transmission are also to be provided.
  • the transparent glass ceramic then has a turbidity with a haze-value of ⁇ 1%, preferably ⁇ 0.5% (with a 3.6 mm thickness), in transmission at a 4 mm thickness via a variegation of colors in the CIELAB color system of C* ⁇ 3.5 and a light transmission (brightness) Y of >80%, preferably >85%.
  • This combination of properties is possible with the low Fe 2 O 3 contents that are matched to one another according to the invention, the limitation of the contents of the staining agent Nd 2 O 3 to less than 2000 ppm and CoO to less than 20 ppm in combination with the specifically defined contents of the nucleating agents TiO 2 , SnO 2 and ZrO 2 .
  • the lithium-aluminosilicate glasses according to the invention can be converted by an additional temperature treatment at temperatures of between about 900 and 1200° C. into a keatite mixed crystal-containing glass ceramic.
  • Glass ceramics of this type have a higher temperature resistance, but at the expense of an increase in the thermal expansion coefficient, which is to be less than 1.5 ⁇ 10 ⁇ 6 /K between room temperature and 700° C. Because of the crystal growth that accompanies the conversion, they have a translucent to opaque-white appearance.
  • the turbidity is generally >50% in haze values.
  • the transparent, colorless glass ceramic with high-quartz mixed crystals that is produced from the lithium-aluminosilicate glass by glazing according to the invention is used as fire protection glass, fireplace door windows, oven door windows, in particular for a pyrolysis oven, and covers for high-power lights.
  • a colored cooking surface with the required light transmission can be produced from the transparent glass ceramic.
  • the latter in translucent or opaque form is preferably used as a cooking surface or as a cover panel in microwave ovens.
  • compositions and properties of the lithium-aluminosilicate glasses are cited in Table 1.
  • glasses 1 to 8 are glasses according to the invention and glasses 9 and 10 are comparison glasses that are outside of this invention.
  • the comparison glass No. 10 was taken from U.S. Pat. No. 4,093,468 (Example B).
  • Table 1 shows the compositions of the starting glasses Nos. 1 to 8 according to the invention and the starting glasses 9 and 10 for the comparison examples.
  • the properties in the vitreous state such as, e.g.: transformation temperature Tg, processing temperature V A , upper devitrification limits OEG, thermal expansion between room temperature and 300° C., as well as the density, are also cited.
  • the upper devitrification limit is below the processing temperature V A .
  • the Fe 2 O 3 contents produced by the raw material contaminants are cited in the compositions.
  • the water content of the glasses is 0.03-0.05 mol/l, corresponding to ⁇ OH values of 0.32 to 0.53 mm ⁇ 1 .
  • the starting glasses of Table 1 were melted and plained from the raw materials, common in the glass industry, at temperatures of about 1620° C. After melting in crucibles that consist of sintered silica glass, the melts were poured into the Pt/Rh crucible with an inside crucible made of silica glass and homogenized at temperatures of 1550° C. for 30 minutes while being stirred. After standing at 1640° C. for 2 hours, castings of about 140 ⁇ 100 ⁇ 30 mm in size were poured and cooled in an annealing furnace, beginning from about 660° C. to room temperature. The castings were divided into the sizes required for the tests and for the glazing.
  • Glazing Program 1 (Total Time 147 Minutes):
  • Glazing Program 2 (Total Time 96 Minutes):
  • Tables 2 and 3 show the properties of the transparent glass ceramics with high-quartz mixed crystals as the prevailing crystal phase, which were produced with the glazing programs 1 or 2.
  • Examples 9 and 10 or 19 and 20 are comparison ceramics outside of the invention.
  • the transmission measurements were made on polished plates with a thickness of 4 mm and with standard illuminant C, 2°.
  • the color coordinates x and y in the CIE system are cited.
  • the glass ceramics according to the invention confirm the advantageous action of the Nd feedstock and optionally in addition Co for reducing the disruptive inherent color.
  • the Yellowness Index according to Standard ASTM 1925/70 (77, 85) is, like the variegation of colors C*, a measurement of the inherent color. High values of the light transmission (brightness) Y are also achieved.
  • the turbidity was measured with standard illuminant C on 3.6 mm-thick plates that are polished on both sides and with a commercial “haze-guard plus” measuring device of the BYK-Gardner Company and characterized by the haze value.
  • some examples with the glazing program 3 were converted into translucent glass ceramics with keatite mixed crystals as the prevailing crystal phase, and their properties as well as phase contents and crystal sizes were determined (Table 4).
  • the maximum temperatures T max in the production are indicated in the table.
  • the light transmission Y and the IR transmission at 1600 nm were measured on 3.6 mm-thick plates.
  • the color values L*, a* and b* were determined in remission (incident light) on 3.6 mm-thick polished plates with the Mercury 2000 measuring device (Datacolor Company, Lawrenceville, USA), standard illuminant C, 2°.
  • the haze values of the examples (polished plates, 3.6 mm thick) are more than 90%.
  • FIG. 1 shows a plot of the nucleating agent concentration of the glass ceramics according to the invention and the comparison ceramics (starting glasses 9, 10) within the indicated limits.
  • FIG. 2 shows the transmission spectra of the glass ceramic of Example 8 according to the invention and the comparison glass ceramic of Example 9.
  • the comparison example shows the disruptive coloring associated with a high Yellowness Index and the variegation of colors C*.
  • the glass ceramic according to the invention shows the characteristic absorption bands of the Nd ion, which are also extremely well suited for labeling the glass ceramic plates according to the invention.
  • the Nd 2 O 3 addition also simplifies the recyclability of the glass ceramic by optical cullet-separating processes based on the absorption bands and the infrared fluorescence of the Nd ion.
  • FIG. 3 shows the color coordinates of the glass ceramics 11 to 18 according to the invention and the comparison glass ceramic of Example 19 in the CIELAB system.
  • the comparison glass ceramic of Example 20 cannot be usefully categorized owing to its high turbidity (milky appearance).
US11/688,104 2006-03-20 2007-03-19 Lithium-aluminosilicate glass with short glazing times Abandoned US20090018007A1 (en)

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US20070232476A1 (en) * 2006-03-20 2007-10-04 Friedrich Siebers Transparent glass ceramic plate that has an opaque, colored bottom coating over the entire surface or over part of the surface
US20110111160A1 (en) * 2008-07-14 2011-05-12 Hideki Kawai Glass Substrate for Information Recording Medium and Information Recording Medium
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US8518565B2 (en) * 2008-07-14 2013-08-27 Konica Minolta Opto, Inc. Glass substrate for information recording medium and information recording medium
US8722215B2 (en) * 2008-07-14 2014-05-13 Hideki Kawai Glass substrate for information recording medium and information recording medium
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CN101269910A (zh) 2008-09-24
US8685873B2 (en) 2014-04-01
EP1837312A1 (fr) 2007-09-26
EP1837312B2 (fr) 2015-07-22
EP1837312B1 (fr) 2010-05-26
ATE469106T1 (de) 2010-06-15
US20120302422A1 (en) 2012-11-29
DE502006007025D1 (de) 2010-07-08
JP5367952B2 (ja) 2013-12-11

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