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    • 专利摘要:
    The invention discloses a transparent, colored, aluminum-based aluminum silicate glass ceramic and its use, said glass-ceramic having a Y-light transmission of 2.5% to 10% and a spectral transmission T (at 465 nm) by more than 1.0%.
    公开号:FR3070386A1
    申请号:FR1857697
    申请日:2018-08-28
    公开日:2019-03-01
    发明作者:Evelin Weiss；Martin Spier；Matthias Bockmeyer；Thomas Zenker；Klaus Schonberger；Johannes Stinner；Oliver Hochrein；Uwe Martens；Michael Bug
    申请人:Schott AG；
    IPC主号:
    专利说明:

    Glass-ceramic based on transparent, colored aluminum silicate and lithium, and its use
    The invention relates to a glass ceramic based on transparent, colored aluminum silicate and lithium, according to the preamble of claim 1. The invention also relates to the use of such a LAS glass ceramic.
    It is known that glasses comprising the L12O-AI2O3S1O2 system can be converted into vitroceramics comprising as main crystalline phases a solid solution with a high quartz content and / or a solid solution with keatite. In the literature, the synonyms "crystal β" or "β-eucryptite" for the first type of vitroceramics and "spodumene β" for the second type are found as designations for the crystalline phases. A preferred area of application for LAS glass ceramics is their use as cooking surfaces.
    An essential property of these glass-ceramics is that in a temperature range from room temperature to about 700 ° C they have an extremely low coefficient of thermal expansion 0120/700, which is commonly less than 1.5 10 ' 6 / K. Glass ceramics which have a solid solution with a high quartz content as their main crystalline phase have in the range of their operating temperatures as cooking surfaces even lower expansion coefficients, for example, usually around 0 ± 0 , 3 · 10 ' 6 / K, while those of vitroceramics which comprise as main crystalline phase a solid solution with keatite are situated around 0.8 10' 6 / K at 1.510 ' 6 / K. The two types of glass ceramics also differ in terms of their average crystallite sizes. Glass-ceramics comprising a solid solution with a high quartz content can be produced in transparent or colored-transparent forms, because of their relatively small size of crystallites, usually less than 50 nm. If keatite is the main phase, the average crystallite sizes are commonly greater than 100 nm, and the glass-ceramics are translucent to opaque, due to the resulting light scattering. However, there are also transparent keatite phases, described for example in DE 10 2014 226 986 Al or FR 3 002 532 Al.
    Due to the low thermal expansion at their surface temperatures, LAS glass ceramics have excellent resistance to temperature differences and very high stability against temperature variations, as well as excellent dimensional stability.
    The industrial production of LAS glass ceramics is familiar to the skilled person. It first comprises the melting and refining of the initial glass which can be crystallized from a mixture composed of fragments of glass and pulverulent mixed raw materials, at temperatures usually between 1,550 ° C. and 1,700 ° C. The refining agents used are usually arsenic oxide and / or antimony oxide or - in particular for environment-friendly refining - tin oxide. To improve the quality of the bubbles, it is also possible to use high temperature refining above 1,700 ° C. After melting and refining, the glass commonly undergoes hot shaping by casting, pressing or by means of rolling or floating in order to produce plates.
    In a subsequent heat treatment operation, the initial glass is converted by controlled crystallization to the glass ceramic article. Ceramization takes place in a two-stage heat treatment process, in which a first nucleation takes place at a temperature between 680 ° C and 800 ° C to generate nuclei, usually composed of a solid solution of ZrCh / TiCh. With a subsequent rise in temperature, the solid solution with a high quartz content grows on these nuclei at the crystallization temperature of 800 ° C to 950 ° C.
    At the maximum production temperature, the microstructure of the glass ceramic is homogenized, and at this stage the optical, physical and chemical properties are established. If desired, the solid solution with a high quartz content can then also be converted into a solid keatite solution. Conversion to a solid keatite solution takes place when the temperature rises in a temperature range from about 950 ° C to 1250 ° C. The conversion is accompanied by an increase in the coefficient of thermal expansion of the glass ceramic, and in general the continued growth of the crystals results in a scattering of light, associated with a translucent to opaque appearance. The conversion increases the crystallinity and the glass-ceramics become more resistant.
    It is possible to color glass-ceramics by adding colored oxides such as V2O5, CoO, NiO, Fe2O3, CnCL, CeCh, alone or in combination, in order to produce, for example, black cooking surfaces having a defined transmission profile. .
    Also in the case of colored glass-ceramics, a distinction is made between transparent, translucent and opaque glass-ceramics. As regards the former, they are often qualified as colored transparencies, in contrast to non-colored transparent glass-ceramics, which are said to be transparent. The transparency and the color transmitted are decisive for the optical quality of colored transparent glass-ceramics. Transparency means that the glass-ceramic must have a relatively high light transmission in the visible region and also a low light diffusion (appearance of haze). The light transmission, measured in the CIE color system as light transmission Y (D65, 2 °), frequently also referred to as t v is or brightness, must therefore, on the one hand, be equal or greater to a minimum value, in order to allow a sufficient vision of the underlying displays when the plate is in operation, and, on the other hand, not to exceed a maximum value, in order to leave invisible the internal part of the plate when is off, and therefore allow the realization of a dark front face effect, whether in combination with a color compensation filter or without such a filter. The transparent glass ceramic must have an annoying light scattering which is weak to zero, so that the vision of the articles and illuminated displays is not distorted. The indications of the displays which are below the ceramic hob must be clear, with clear contours and must be visible practically without haze.
    One way to achieve the low light scattering is by means of a high density of nuclei, leading to the solid solution with high quartz content which grows by having a size of crystallites lying below the range of lengths d wave of visible light. The average crystallite size of the solid solution with a high quartz content is normally in the range of 20 nm to 50 nm. A high density of nuclei requires sufficient quantities of nucleating agents and also sufficient nucleation times during ceramization.
    If the objective is to obtain the best results in terms of high visibility of the displays arranged below in conjunction with a reduced view of the interior of the plate, the requirement is to form a curve profile as flat as possible in the visible light transmission region (380 nm - 780 nm). In this case, the transmissibility of neutral light, which is well distributed, is desired in particular for the wavelengths of the spectrum between 450 nm and 700 nm. Since displays in colors other than red are becoming more and more important in baking trays, a very wide variety of different transmission profiles have been outlined in the prior art, but all have one drawback or another and / or are performed at a disadvantage.
    DE 10 2008 050 263 A1 describes transparent, colored glass-ceramic cooking surfaces having a spectral transmission of> 0.1% in the visible light region for wavelengths> 450 nm, but having a maximum transmission of the 2.5% light in the visible region.
    DE 10 2009 013 127 A1 describes transparent, colored glass-ceramic cooking surfaces having a light transmission of up to 5% in the visible region and having a spectral transmission of> 0.1% in the visible light region for wavelengths> 450 nm, but does not lead to products transmitting a neutral color.
    DE 10 2012 105 576 Al and DE 10 2012 105 572 Al describe vitroceramic plates having values t v îs> 2.5% and having very variable values at wavelengths in the range from 420 to 480 nm which have a great importance for the color transmitted.
    WO 2012/001300 Al discloses cooktops ceramic or glass having a value t v is at least 2.3% up to a very high value of 40% and at least 0.6% in transmission the range of 420 nm - 480 nm, in combination with a covering medium, but does not lead to products transmitting a neutral color.
    EP 1 465 460 A1 describes a cooking surface which, with a thickness of 3 mm, has Y values (D65) of 2.5% - 15%. Arsenic is contained in the embodiments of this document.
    WO 2010/137000 A1 described vitroceramics which, in a thickness of 3 mm, have a light transmission of 1.5% to 5% and a spectral transmission of> 0.5% at wavelengths between 450 and 480 nm. These transmissions are carried out using cobalt oxide.
    WO 2010/136731 A1 also relates to the display capacity of cooking surfaces, and claims vitroceramics which, with a thickness of 4 mm, have a spectral transmission of between 0.2 and 4% anywhere in the region between 400 and 500 nm.
    For economical production of glass ceramics, it is desirable to use a low melting temperature and a low Va transformation temperature of the initial glasses. In addition, the glass must not exhibit devitrification during shaping, which means that it does not form destructive crystals, adversely affecting the mechanical strength of the initial glasses and of the glass-ceramics produced from them. -this.
    An object of the invention is to provide glass-ceramics based on transparent, colored aluminum silicate and lithium, which ensure effective visibility of the displays arranged below in conjunction with a reduced view of the interior of the plate and a minimum chromatic shift of the colors of the display across the cooking surface, in other words as much as possible undistorted visibility of the display colors red, green, blue and therefore also white and other colors.
    It is also an object of the invention to find uses for articles produced from LAS glass-ceramics.
    The present glass-ceramics must meet the requirements of the various applications with regard, for example, to chemical resistance, mechanical resistance, transmission, temperature stability and long-term stability with respect to variations in their properties (such as, for example, thermal expansion, transmission, the appearance of tensions).
    They must also have qualities of an economic manufacture and respectful of the environment.
    These objects are achieved by a glass ceramic based on transparent, colored aluminum silicate and lithium, according to claim 1 and by its use according to claim 11.
    The various requirements set out are satisfied by the transparent, colored, environmentally friendly, aluminum silicate-lithium glass ceramic of the invention, which, while having the usual properties required of a suitable glass ceramic as that coating surface, has special transmission properties and was produced without certain constituents harmful to the environment.
    Consequently, the glass ceramic of the invention has a light transmission, measured in the CIE system as light transmission Y (D65, 2 °) of at least 2.5%, preferably more than 2 , 5%, more particularly preferably at least 3.5% and very particularly preferably at least 4.5%, and at most 10%, preferably at most 7.5% and more particularly 5%. The values are measured with the standard illuminant D65, 2 ° observer angle for a sample of polished ceramic glass 4 mm thick.
    The glass ceramic of the invention has a spectral transmission τ at 465 nm of more than 1.0%, preferably more than 1.2%. The values are measured on a sample of polished ceramic glass 4 mm thick.
    In addition, in the glass ceramic of the invention, these two transmission properties have a certain relationship with one another. Consequently, according to the invention, the difference (Y (D65, 2 °) - τ (at 465 nm)) does not exceed 3%, preferably is less than 3%.
    The glass ceramic of the invention having these properties is a glass ceramic based on aluminum silicate and lithium having a V2O5 content of 55 ppm to 200 ppm and an Fe2O3 content of 450 ppm to 1000 ppm, with a Fe2O3 ratio / V2Os (both in ppm or% by weight) from 3 to 9, preferably from 5 to 7. The content of V2O5 is preferably at least 100 ppm, and preferably is at most 200 ppm. The Fe2O3 content is preferably at least 700 ppm. The ppm unit also relates to parts by weight.
    The glass ceramic of the invention is free from cobalt oxide, nickel oxide and chromium oxide. The expression "free from" the stated components means that the cobalt oxide, if present, is only present at a concentration not exceeding 10 ppm (expressed as CoO); that nickel oxide, if present, is only present at a concentration not exceeding 20 ppm (expressed as NiO); and that chromium oxide, if present, is only present at a concentration not exceeding 20 ppm (expressed as CnCL).
    Consequently, the glass-ceramic of the invention combines a light transmission which allows, on the one hand, an effective visibility of the displays arranged below, and on the other hand, a reduced view of the interior of the plate, with a color transmissibility which is such that not only red but also other colors, such as green, are transmitted, in conjunction with a very neutral, i.e. undistorted, transmission of color and brightness, in other words a transmission of light which is unaltered or barely changed despite passing through the ceramic hob.
    The LAS glass ceramic of the invention preferably has a transmission in the red spectral region, that is to say in the range from 610 nm to 650 nm, which is increased compared to the transmission of the materials usually used for display with red displays. This is advantageous because, since LED displays are fitted with an ever increasing number of LEDs, the specific power supply by LED is reduced for a given connection power.
    Preferably, therefore, the glass ceramic of the invention has a spectral transmission τ at 630 nm of 10.9% ± 3.8%, more particularly preferably of 10.9% ± 2.5%, even more more particularly preferred of 10.9% ± 2.0%, very particularly preferably of 10.9% ± 1.5%. These values are measured on a sample of ceramic glass, polished, 4 mm thick. The value 10.9% ± 3.8% should be understood as the range from 7.1% to 14.7%.
    The glass ceramic of the invention has an environmentally friendly composition. This means that in addition to being free of the coloring oxides cobalt oxide, nickel oxide and chromium oxide, the glass ceramic is also technically free of the refining agents arsenic oxide and antimony oxide, apart from the presence of inevitable impurities in raw materials. As impurities, the arsenic oxide and antimony oxide components (expressed as AS2O3 and Sb2O3, respectively) are present in amounts which are in total less than 1000 ppm, preferably less than 400 ppm.
    In a LAS glass ceramic the oxides L12O, AI2O3 and S1O2 are necessary constituents of the solid solution.
    To this end, the L12O content is preferably at least 3.0% by weight. It is preferably at most 4.2% by weight, because higher contents may possibly lead to devitrification in the production process. An L12O content of at least 3.2% by weight is preferred; and an L12O content of at most 4.0% by weight is preferred.
    In order to avoid high viscosities due to the initial glass and to suppress the tendency to devitrification during shaping, the content of Al 2 O 3 is preferably at most 23% by weight. It is preferably at least 19% by weight. An Al2O3 content of at least 20% by weight is preferred; and an AI2O3 content of at most 22% by weight is preferred.
    The content of S1O2 is preferably at most 69% by weight, since S1O2 considerably increases the viscosity of the glass, and higher contents would lead to unprofitable melting and shaping conditions. The content is preferably at least 60% by weight. An S1O2 content of at least 62% by weight is preferred; an S1O2 content of at most 67% by weight is preferred.
    As optional components, MgO, ZnO and P2O5 can be present, and in this case they can be incorporated into the solid solution with high quartz content.
    If ZnO is present, the ZnO content is preferably limited to 2.2% by weight at most, otherwise there is a risk of formation of undesirable crystalline phases such as gahnite. A ZnO content of at least 1% by weight is preferred.
    If MgO is present, the MgO content is preferably limited to 1.5% by weight, otherwise there is too great an increase in the coefficient of thermal expansion of the glass ceramic. An MgO content of at least 0.1% by weight is preferred; an MgO content of at most 1.3% by weight is preferred.
    If P2O5 is present, the P2O5 content is preferably limited to a maximum of 3% by weight, otherwise there may be a decrease in the resistance to acids. A P2O5 content of at most 0.1% by weight is preferred. Preferably P2O5 is absent, except for possible impurities.
    The glass-ceramic preferably comprises Na2O and / or K2O at a total concentration of at least 0.2% by weight. The glass ceramic preferably comprises Na2O and / or K2O at a total concentration of at most 1.5% by weight. The glass-ceramic may also comprise oxides of alkaline earth metals, and more precisely SrO and / or CaO, at concentrations preferably limited to a total of at most 4% by weight, and / or BaO, preferably limited to a concentration not exceeding 3% by weight.
    In the ceramic glass, the oxides of alkali metals mentioned and the oxides of alkaline earth metals mentioned promote the formation of a smooth surface layer, enriched in these components and deprived of L12O. This contributes to the chemical resistance of the glass ceramic.
    The glass ceramic may also include B2O3, specifically limited to a concentration preferably not exceeding 2% by weight.
    B2O3, the alkali metal oxides mentioned and the alkaline earth metal oxides mentioned improve the fusibility and the resistance to devitrification during the forming of the raw glass. At rates higher than those stated, the thermal expansion may be increased and there may be a detrimental effect on the crystallization behavior during the conversion of the raw glass to the glass ceramic.
    The B2O3 content is preferably at most 1% by weight, and particularly preferably B2O3 is not included, except for the presence of possible impurities.
    A BaO content of at least 1.0% by weight is preferred; a BaO content of at most 2.8% by weight is preferred.
    The total amount of SrO and / or CaO is preferably at least 0.2% by weight; the total amount of SrO and / or CaO is preferably at most 1% by weight.
    The total amount of Na2O and / or K2O is preferably at least 0.4% by weight; the total amount of Na2O and / or K2O is preferably at most 1.2% by weight.
    The glass ceramic includes preference T1O2 at a minimum concentration of 2.5% by weight. The glass ceramic comprises a minimum concentration of 0.5% by weight. preference ZrO 2 at a The glass ceramic comprises a minimum concentration of 0.05% by weight. preference SnO 2 at a
    These three components serve as nucleating agents.
    The glass ceramic preferably comprises a maximum of 4% by weight of T1O2, since higher levels may adversely affect the resistance to devitrification.
    The glass ceramic preferably comprises a maximum of 2% by weight of ZrCh, since larger quantities can compromise the melting behavior of the mixture during the production of glass and can adversely affect the resistance to devitrification during shaping. , as a result of the formation of crystals containing ZrCh.
    The glass ceramic comprises less than 0.6% by weight of SnCh, since larger amounts may affect the resistance to devitrification.
    A TiCh content of at least 2.8% by weight is preferred; a T1O2 content of at most 3.5% by weight is preferred.
    A ZrCh content of at least 1% by weight is preferred; a ZrCh content of at most 1.8% by weight is preferred.
    An SnCh content of at least 0.1% by weight is preferred; an SnCh content of at most 0.4% by weight is preferred, a content of at most 0.3% by weight is more particularly preferred.
    It is particularly preferred that the total sum of the contents of T1O2, Zr02 and SnCh does not exceed 5.5% by weight.
    According to a preferred embodiment, the transparent, colored LAS glass ceramic comprises as main components the following components (in% by weight on an oxide basis):
    Li 2 O 3.0 - 4.2
    Na 2 O + K 2 O 0.2-1.5
    MgO 0 - 1.5
    CaO + SrO
    0-4
    BaO
    ZnO
    Al2O3
    0 to 2.2
    19-23
    SiO 2
    - 69
    T1O2
    ZrO 2
    SnO 2
    P 2 O 5
    2,5-4
    0.5-2
    0.05 - <0.6
    - 3
    B2O3
    0-2 and also the stated quantities of V2O5 from 50 ppm to 250 ppm and Fe 2 O3 from 500 ppm to 1000 ppm, with a Fe2O3 / V2O5 ratio (both in% by weight) of 3 to 9, as well as, optionally, additions of chemical refiners, such as CeCh and refining additives such as sulfates, chlorides, fluorides in total amounts of up to 2.0% by weight .
    Glass ceramic preferably consists essentially of the stated components, in the stated proportions. By the expression "consists essentially of ..." it is meant that these components are included at a rate of at least 98% by weight in the glass ceramic.
    The water content of the crystallizable glasses for the production of glass-ceramics is preferably between 0.015 and 0.06 mole / l, depending on the choice of the raw materials of the mixture and the operational conditions during the melting. This corresponds to values β-ΟΗ from 0.16 to 0.64 mm ' 1 . When converting to glass ceramic, there is a change in the IR band, which is used for the determination of the water content. As a result, due to the measurement process, the β-ΟΗ value of the glass ceramic increases by a factor of about 1.6, without any concomitant change in the water content. This increase as well as the method for determining the β-ΟΗ values are described for example in EP 1 074 520 Al.
    According to another preferred embodiment, the transparent, colored LAS glass ceramic comprises as main components the following components (in% by weight on an oxide basis):
    Li 2 O 3.2 to 4.0 Na 2 O + K 2 O 0.4 - 1.2 MgO 0.1 - 1.3 CaO + SrO 0.2 - 1 BaO 1.5 to 2.8 ZnO 1 - 2.2 A1 2 Ü3 20 - 22 SiO 2 62-67 TiO 2 2.8-3.5 ZrO 2 1-1.8 SnO 2 0.1-0.4 P 2 O 5 0 - 0.1 B 2 O 3 0 - 1
    and also, optionally, refining additives such as sulfates, chlorides, fluorides, in total amounts of up to 1.0% by weight.
    Glass ceramic preferably consists essentially of the stated components, in the stated proportions. By the expression "consists essentially of ..." it is meant that these components are included at a rate of at least 98% by weight in the glass ceramic.
    If SnO 2 is present as a nucleating agent, the glass-ceramic can also be refined using SnO 2 . To this end, the compound is present in the proportions indicated above. Its refining effect can be accentuated by the refining additives mentioned above.
    To achieve a very good refining effect in conjunction with the required bubble qualities and the desired tank flow rates, it may be advantageous to carry out a refining at high temperature above 1,700 ° C., preferably above 1,750 ° C. In this case, a bubble quality of less than 2 bubbles / kg is obtained in the glass ceramic (measured for bubble sizes greater than 0.1 mm in one dimension).
    A large number of compounds of elements such as, for example, the alkali metals Rb and Cs, or of elements such as Mn and Hf, are common impurities in the raw materials of the mixture which are used industrially. Other compounds, such as those of the elements W, Nb, Y, Mo, Bi and rare earths, for example, can similarly be included in small proportions.
    The transparent, colored aluminum and lithium silicate glass ceramic usually comprises as the main crystalline phase a solid solution with a high quartz content. The average size of the crystallites is preferably less than 50 nm.
    The LAS glass ceramic of the invention preferably has a light scattering, reported as the total haze value for the standard illuminant C, determined according to ASTM D1003 - 13, of less than 20%, preferably less than 15 %, for 3.5 mm.
    The thermal expansion, measured between 20 ° C and 700 ° C, for this type of LAS glass ceramic with solid solution with high quartz content, is preferably established at values of less than 1 · 10 ' 6 / K, preferably of (0 ± 0.3) 10 ' 6 / K.
    The glass ceramic based on aluminum silicate and lithium, comprising as the main crystalline phase a solid solution with a high quartz content, can be converted, in a usual manner known to a person skilled in the art, into a glass ceramic comprising as the main crystalline phase a solid keatite solution. Due to the usually larger average crystallite size, more than 120 nm, this converted glass ceramic is translucent or opaque. The glass ceramic comprising as the main crystalline phase a solid solution with a high quartz content can also be converted into a glass ceramic comprising as the main crystalline phase a solid keatite solution so that its size of crystallites remains sufficiently small, so that the glass ceramic is transparent. A glass ceramic of this type, comprising a solid keatite solution, usually exhibits thermal expansion, measured between 20 ° C. and 700 ° C., from 0.8 · 10 ' 6 / K to 1.5 · 10' 6 / K, preferably more than 1 · 10 ' 6 / K to 1.5 · 10- 6 / Κ.
    The preferred geometry for the glass ceramic of the invention or for articles produced therefrom is in the form of plates. The plate preferably has a thickness of 2 mm to 20 mm, as this opens the way to important applications. In smaller thicknesses, the mechanical resistance is reduced; greater thicknesses are less economical, due to the greater consumption of material. Except for use as safety glass, where high mechanical strengths are an important factor, the thickness chosen is therefore generally less than 6 mm. In the case of use as a cooking surface, the preferred thicknesses chosen are from 2 mm to 6 mm. For usual standard cooking surfaces, sizes of up to 0.5 m 2 are usually preferred. For larger projects, with color displays for example, or if the cooking surface is configured at the same time as a work surface and includes other functions in addition to the cooking function, these functions being defined more in detail when the possible applications as a cooking surface are outlined, preference is given to formats larger than 0.5 m 2 and even larger than 0.8 m 2 .
    Particular shaping processes for plate-like geometry are, in particular, rolling and floating.
    The ceramic hob and articles preferably produced therefrom not only may be flat in shape, but may also have been subjected to three-dimensional molding. For example, chamfered, angled or curved plates can be used. The plates can be at right angles or have other shapes, and in addition to the flat areas, they can include three-dimensional molded areas, for example woks, or laminated strips or areas in the form of elevations or depressions, respectively. The geometric molding of the plates is carried out at the stage of hot forming, by means of textured shaping rollers, for example, or by subsequent hot forming on the initial glasses, by means of burners or by falling under the effect of gravity, for example. Ceramization is carried out using ceramic support molds in order to avoid uncontrolled variations in the geometric shape.
    The ceramic hob and articles preferably produced therefrom may be smooth on both sides or may have roughness on one side.
    Owing to the favorable thermal and optical properties linked to the low thermal expansion and to the optimized transition profile, and also by virtue of the other properties, in particular the mechanical properties, there are numerous applications which can be satisfied advantageously.
    The transparent, colored vitroceramic articles of the invention find application in the form of a cooking surface, more particularly a cooking surface coated on the underside, or a coated cooking surface on the face and cut-out, called reserves for lighting in the cold zone, that is to say in the indication / display zone, and / or in the hot zone, in other words in the cooking zone , with a covering means, or a cooking surface comprising a so-called diffusion layer, which distributes the light uniformly from below the cooking surface towards the observer, or a cooking surface comprising a so-called filter chromatic compensation, applied in coated or printed form or fixed by adhesion. In addition, such an application can take the form of a cooking surface in one of the versions set out above with capacitive sensor structures, applied in bonded, printed or pressure applied form, for control and regulation operation. In addition, such an application can take the form of a cooking surface in one of the embodiments set out above, with one or more hole (s) for adjustment knobs, gas burners, exhaust systems. smoke (called bottom suction systems) or other functional modules, optionally made with a flat facet on one or more edge (s).
    In addition, such an application can take the form of a cooking surface in one of the versions set out above, having a transmission, defined by the value Y (D65, 2 °), which is increased / modified locally in the display area and / or hot area. This transmission value Y (D65, 2 °) can be increased locally by up to 50%, preferably up to 30%, particularly preferably up to 25%, compared to the basic transmission or nominal transmission of the substrate.
    In a particularly preferred embodiment, the transmission is increased locally by up to 5%, more particularly up to 2.5%, compared to the basic transmission.
    In one embodiment of the invention, the transmission can also be reduced locally by 4%, preferably by 3%, compared to the basic transmission of the substrate.
    The reduction of the basic transmission can be carried out by coating or by a film or by intrinsic local modification of the material.
    In particular embodiments, vitroceramics can find an application for cooking appliances provided with sensors intended to measure the temperature of a cooking vessel. Sensors of this type can be arranged, for example, directly in the cooking container or above the cooking container, or can detect the temperature of the base of the cooking container by means of IR sensors.
    Such IR sensors preferably operate at a wavelength> 1 µm, preferably> 1,500 nm. In a preferred embodiment, such sensors operate at a wavelength of 3 - 5 µm. The cooking surface therefore has a corresponding transmission in the relevant wavelength range. Ways to ensure this include either local cutting in the covering means or sufficient transparency of the covering means in the relevant wavelength range.
    In other particular embodiments, vitroceramics can find an application for cooking appliances provided with a wireless data connection. This data connection can be used to integrate the cooking appliance with a smoke hood, with a central control unit for household appliances, or other for the functional control of the cooking appliance. Data connections can be made using IR sensors or from radio links in the GHz range, for example Wifi, Bluetooth.
    Preferably, such IR sensors operate at a wavelength of 0.9 - 1 µm, preferably 930 - 970 nm. The cooking surface therefore has a corresponding transmission in the relevant wavelength range. Ways to ensure this include either local cutting in the covering means or sufficient transparency of the covering means in the relevant wavelength range.
    In other particular embodiments, glass-ceramics can find an application for cooking appliances provided with contactless control technology. Such controls operate, for example, using capacitive sensor technology, IR sensors or even ultrasonic sensors.
    In other particular embodiments, glass-ceramics may find application for cooking appliances having segment-based and / or LED-based display elements and / or graphic display elements. These graphic display elements can have a single color or multiple colors. Preferred monochrome graphic displays are white. Display elements of this type are preferably designed with a system of capacitive touch sensors.
    In other particular embodiments, vitroceramics can find an application for cooking appliances with a minimum of decoration of the upper face. In one embodiment, only one or more brand logo (s) and the on / off switch are located on the upper side. In this case, the decorative function for marking cooking zones, for example, is fulfilled entirely by lighting elements.
    In addition, glass-ceramics are used in conjunction with a functional coating on the upper side.
    These functional top coatings can be applied to improve scratch resistance, to facilitate cleaning ability, to improve visibility of displays, to prevent the formation of destructive reflections, to minimize fingerprints and / or to minimize noise caused by moving the cooking vessels.
    In a particular embodiment, the surface can be polished or have a stochastic structure.
    In addition, the transparent, colored glass-ceramic articles according to the invention can find use as glazing for a fireplace / covering or covering for a closed chimney, cover in the lighting sector and as optional safety glass in a laminated system, as a support plate or oven cover. In the ceramic, solar or pharmaceutical industry or in medical technology, they are particularly suitable for production processes under conditions of high purity, as furnace coatings in which physical or chemical coating processes are carried out , or as chemical resistant laboratory equipment. In addition, they find use as a glass ceramic article for high temperature or extremely low temperature applications, as oven windows for combustion ovens, as a heat shield for the isolation of hot environments. , as covers for reflectors, headlights, projectors, photocopiers, for applications with thermomechanical exposure, such as in night vision devices, or as a cover for heating elements, in particular as a cooking surface or frying, as a household appliance article, as a heating element cover, as a printed circuit substrate, as a UV protection article, as an architectural facade plate or as a component of an electronic device.
    The present invention is explained in more detail with the aid of the following examples.
    In the case of embodiments A1 to A6, the initial glasses were melted from raw materials customary in the glass industry, at temperatures of approximately 1,620 ° C., for 4 hours. Once the molten mixture was poured into crucibles made of a refractory material with a high quartz content, the molten masses were poured into PtRh20 crucibles comprising a crucible coating made of silica glass, and they were homogenized by stirring. for 60 minutes at temperatures of 1600 ° C. After this homogenization, the glasses were refined at 1,640 ° C for 3 hours. Parts were then cast with dimensions of about 170 x 120 x 25 mm 3 and allowed to cool in a cooling oven, from an initial temperature of 640 ° C to room temperature. The castings were divided into the sizes required for studies and for ceramization.
    The samples of embodiments A7 to Ail were melted industrially with the use of the parameters usually used for LAS glass ceramics refined in tin.
    The samples were ceramized using the ceramization program described briefly below.
    Table 1, for examples A1 to A11 which are exemplary embodiments, and examples C1 to C8, which are comparative examples, shows the compositions and the properties of the initial crystallizable glasses and the properties of the glass-ceramic produced from the glasses .
    Due to the typical impurities present in the raw materials of the industrial mixture used, the compositions do not give a total of exactly 100.0% by weight. Typical impurities, although not deliberately introduced into the composition, are compounds of Mn, Rb, Cs, Hf or the like, if not used as refiners, of Cl and F, which usually do not represent more than 0.1% by weight. They are frequently entrained by the raw materials for the components concerned for example, Rb and Cs by the raw materials Na or K, or Hf by the raw material Zr.
    Transmission measurements were made on polished plates 4 mm thick, using illuminant C, 2 °. The transmission values reported are those at the selected wavelengths, namely at 465 nm, at 470 nm and at 630 nm, and also the transmission of light. The terms “light transmission” and “Y brightness” correspond to the same measured parameter, measured as Y (D65, 2 °) according to DIN 5033 in the CIE color system. The difference t v îs - T465, i.e. Y 1465, is also reported.
    The ceramization program was as follows:
    a) Heating from room temperature to 600 ° C in 5 minutes.
    b) Raising the temperature from 600 ° C to a nucleation temperature T nu ci between 700 ° C and 750 ° C at a heating rate of 50 K / min, maintaining this temperature T nu ci for 5 minutes.
    bl) Raising the temperature to a crystallization temperature T cr i S t between 780 ° C and 820 ° C at a heating rate of 12 K / min, maintaining this temperature T cr i S t for 8 minutes.
    c) Raising the temperature of T cr i S t to a maximum temperature T max between 910 ° C and 950 ° C at a heating rate of 20 K / min, maintaining this temperature T max for 7 minutes.
    d) cooling to about 800 ° C at 10 K / min, then rapid cooling to room temperature.
    Table 1
    % in weight al A2 A3 A4 AT 5 A6 A7 AT 8 A9 Al2O3 20.5 20.5 20.5 20.5 20.5 20.5 20.6 20.57 20.63 BaO 2.31 2.31 2.3 2.29 2.3 2.3 2.31 2.3 2.3 CaO 0,420 0.42 0.42 0.42 0.42 0.42 0.41 0.41 0.41 CoO - - - - - - - - - Cr 2 O 3 - - - - - - - - - F - - - - - - - - - Fe 2 O 3 (ppm) 940 940 920 910 810 710 890 887 895 HfO 2 0,025 0,025 0,025 0,025 0,025 0,025 0,024 0,024 0,024 K 2 O 0.24 0.25 0.24 0.24 0.24 0.25 0.27 0.26 0.26 Li 2 O 3.91 3.91 3.89 3.92 3.91 3.95 3.8 3.8 3.79 MgO 0.32 0.31 0.31 0.32 0.32 0.31 0.3 0.3 0.3 MnO 2 0,018 0,023 0,029 0,019 0,018 0,018 0,018 0,018 0,018 MoO3 - - - - - - - - - Na 2 O 0.6 0.61 0.6 0.59 0.6 0.59 0.62 0.62 0.62 Nb 2 O 5 - - - - - - - - - NiO - - - - - - - - - P 2 O 5 0,029 0,029 0,029 0,029 0,029 0,029 0.062 0,061 0,063 Sb 2 O 3 - - - - - - - - - SiO 2 65.1 65.1 65.1 65.2 65.2 65.2 65.14 65.2 65.15 SnO 2 0.27 0.27 0.27 0.26 0.27 0.26 0.27 0.26 0.26 SrO 0,018 0,018 0,018 0,018 0,018 0,018 0,029 0,028 0,028 TiO 2 3.19 3.18 3.2 3.17 3.17 3.18 3.11 3.11 3.09 V 2 O 5 (ppm) 170 150 140 190 180 180 140 131 139 ZnO 1.54 1.56 1.55 1.54 1.56 1.56 1.51 1.5 1.49 ZrO 2 1.42 1.42 1.42 1.41 1.42 1.41 1.39 1.39 1.38 Fe 2 O3 / V 2 O5 5,529 6,267 6.571 4,789 4.5 3,944 6,357 6,771 6,439 Y (D65, 2 °) [%] 4,125 3,307 5,347 2.6 3.1 2.8 4.1 5.2 4,416 τ to 470 [%] 1.8 1.3 2.5 0.94 1.22 1.12 1.67 2.3 1,793 τ to 465 [%] 1.8 1.3 2.5 0.95 1.23 1.13 1,670 2.3 1.78 τ to 630 [%] 10.17 8.64 12.4 7.19 8.16 7.6 10.2 12.4 10.8 Difference Y (D65, 2 °) τ to 465 [%] 2,325 2.0068 2.8471 1.65 1.87 1.67 2.43 2.9 2.6369
    Table 1 continued
    % in weight A10 Garlic Cl C2 C3 C4 C5 C6 C7 C8 Al2O3 20.61 20.9 20.2 20.3 19.3 19.3 20.9 20.3 20.3 20.9 BaO 2.31 2.03 2.41 2.36 0.8 0.8 2.3 2.6 2.6 2.23 CaO 0.14 0.41 0.36 0.44 0.42 0.5 0.5 0.43 CoO - - 0,027 - -Cr 2 O 3 - -0,032 - -F - - 0.14Fe 2 O 3 (ppm) 882 830 900 1400 2000 2000 2000 850 850 900 HfO 2 0,025 0,026 0,025 0,024 K 2 O 0.27 0.24 0.21 0.21 0.2 0.2 0.27 Li 2 O 3.79 3.81 3,830 3.85 3.5 3.5 3.71 3.8 3.8 3.82 MgO 0.3 0.3 0.19 0.35 1.1 1.1 0.37 0.4 0.4 0.29 MnO 2 0,018 0,019 0,022 0,023 0.25 0,025 MoO 3 - - <0.005 <0.005 - -Na 2 O 0.62 0.6 0.57 0.61 0.59 0.6 0.6 0.6 Nb 2 O 5 - - - 0,011 NiO - - <0.001 <0.001 P 2 O 5 0,0600.11 0.086 Sb 2 O 3 - - <0.01 <0.01 SiO 2 65.15 65.2 65.8 65.4 68.86 68.86 65.14 65.5 65.5 65 SnO 2 0.27 0.26 0.3 0.32 0.2 0.2 0.24 0.29 0.29 0.25 SrO 0,029 0,037 0,003 0,0040,021 TiO 2 3.1 2.96 3.02 2.96 3.1 2.7 3.1 2.9 2.9 3.13 V 2 O 5 (ppm) 138 190 200 400 400 400 260 300 250 230 ZnO 1.5 1.53 1.41 1.45 1.6 1.6 1.5 1.5 1.5 1.53 ZrO 2 1.39 1.48 1.39 1.35 1.8 1.8 1.34 1.3 1.3 1.4 Fe 2 O 3 / V 2 Os 6,391 4,368 4.5 3.5 5 5 7,692 2,833 3.4 3,913 Y (D65, 2 °) [%] 4,574 4.2 3.5 1.3 15 42.5 26.7 4.5 6.0 2.2 τ to 470 [%] 1,877 1.3 1.9 0.03 3 17.7 11.2 0.67 τ to 465 [%] 1,854 1.3 2 0,023 2.7 16.7 11.8 1.1 1.6 0.67 τ to 630 [%]11.25 10.75 4.6 32.36 63.3 43.76 A.D. A.D. 6.62 DifferenceY (D65, 2 °) - τ to 465 [%] 2.7204 2.9 1.5 1,277 12.3 25.8 14.9 3.4 4.4 1.53
    a.d. = no data
    Examples C1 to C8 in Table 1 are comparative glass-ceramics outside the scope of the invention.
    Although Cl has a difference (Y - τ (at 465 nm)) of <3%, the transmission characteristics are nonetheless achieved by adding CoO.
    Likewise, C2 has a difference (Y - τ (at 465 nm)) of v 3 but the values of the transmission in the visible region are so low that, with the exception of the red displays, no other color is visible . This is due to the addition of Cr2O3, which significantly reduces transmission in the visible region.
    Examples C3 to C5 all have a difference (Y - τ (at 465 nm)) of> 3%, partly due to regions with very high transmission values, which can be attributed to so-called iron over-coloring.
    C6 and C7 have a light transmission Y (D65, 2 °) of 2.5 - 10% and a spectral transmission τ (at 465 nm)> 1.0%. However, their difference (Y (D65, 2 °) - τ (at 465 nm)) is also> 3%.
    C8, although having a difference (Y (D65, 2 °) - τ (at 465 nm)) <3%, nevertheless has a low light transmission Y (D65, 2 °) of 2.2% and a low spectral transmission - τ (at 465 nm) of 0.67%.
    The exemplary embodiments A1 to A11 illustrate the fact that the vitroceramics of the invention combine the transmission properties of a light transmission Y (D65, 2 °) of 2.5 10%, of a spectral transmission of τ (at 465 nm)> 1.0% and a difference (Y (D65, 2 °) - τ (at 465 nm)) of <3% and therefore make it possible, on the one hand, to effectively see the displays arranged below and, on the other hand, a reduced view of the interior of the hob and also a color transmissibility which is such that not only red but also colors such as green are transmitted and the color and brightness transmitted are very neutral, in other words undistorted, which means a light transmission which is unaltered or practically unaltered despite the passage through the glass ceramic plate. The exemplary embodiments, as a preferred embodiment, also exhibit high transmission in the red spectral region, as shown by a spectral transmission τ at 630 mm of 10.9% ± 3.8%.
    The initial glasses of the glass-ceramics of the invention have low melting and shaping temperatures and can be produced from inexpensive raw materials. They have a high resistance to devitrification. They can be converted into 5 ceramic hobs in short ceramization times.
    The vitroceramics of the invention therefore have economical and environmentally friendly manufacturing properties, the latter being due to the omission of environmentally harmful raw materials arsenic oxide, antimony oxide, cobalt and chromium oxide. The vitroceramics of the invention meet the requirements of various applications. They therefore have good chemical resistance, high mechanical resistance, the desired transmission properties, a light to no light scattering, a high temperature resistance and a great long-term stability with regard to variations in their properties (such as, for example, thermal expansion, transmission, appearance of stresses).
    权利要求:
    Claims (13)
    [1" id="c-fr-0001]
    1. Glass ceramic based on aluminum and lithium silicate, transparent, colored, characterized by an AS2O3 and / or Sb2O3 content worth in total from 0 to <1000 ppm, a V2O5 content from 55 ppm to 200 ppm, an Fe2O3 content of 450 ppm to 1,000 ppm, with a Fe2O3 / V2O5 ratio (both in% by weight) of 3 to 9, and with the absence, apart from impurities, of CoO, NiO and CnCh, and also by the following transmission qualities:
    Y (D65, 2 °) 2.5 - 10%
    T (at 465 nm)> 1.0% with a difference (Y (D65, 2 °) - τ (at 465 nm)) of <3%.
    [2" id="c-fr-0002]
    2. Vitroceramic based on aluminum silicate and lithium according to claim 1, characterized by
    Y (D65, 2 °)> 2.5 - 10%
    T (at 465 nm)> 1.2% with a difference (Y (D65, 2 °) - τ (at 465 nm)) of <3%.
    [3" id="c-fr-0003]
    3. Vitroceramic based on aluminum and lithium silicate according to claim 1 or 2, characterized by
    T (630 nm) of 10.9% ± 3.8%, preferably 10.9% ± 2.5%, more particularly preferably 10.9% ± 2.0%, even more particularly preferred 10.9% ± 1.5%.
    [4" id="c-fr-0004]
    4. Glass ceramic based on aluminum silicate and lithium according to any one of the preceding claims, characterized in that it comprises the following components in% by weight, on an oxide basis
    Li 2 O 3.0 - 4.2 Na2Û + K2O 0.2 - 1.5 MgO 0 - 1.5 CaO + SrO 0 - 4 BaO 0 - 3
    ZnO 0 - 2.2 Al2O3 19 - 23 SiO 260 - 69 T1O2 2.5 - 4 ZrO 20.5 - 2 SnO 20.05 - <0.6 P 2 O 50 - 3 B2O3 0 - 2
    as well as optional additions of chemical refiners such as CeCh and refining additives such as sulfates, chlorides, fluorides in total amounts of up to 2.0% by weight.
    [5" id="c-fr-0005]
    5. Glass ceramic based on aluminum silicate and lithium according to claim 4, characterized in that it comprises the following components in% by weight, on an oxide basis
    Li 2 O 3.2 - 4.0 Na2Û + K2O 0.4 - 1.2 MgO 0.1 - 1.3 CaO + SrO 0.2 - 1 BaO 1.5 - 2.8 ZnO 1 - 2.2 Al2O3 20 - 22 SiO 262 - 67 T1O2 2.8 - 3.5 ZrO 21 - 1.8 SnO 20.1 - 0.4 P 2 O 50-0.1 B2O3 0 - 1
    and also, optionally, refining additives such as sulfates, chlorides, fluorides, in total amounts of up to 1.0% by weight.
    [6" id="c-fr-0006]
    6. Vitroceramic based on aluminum silicate and lithium according to any one of the preceding claims, characterized in that the SnCh content is from 0.05 to 0.4% by weight, preferably from 0.05 to 0 , 3% by weight, more particularly preferably 0.05 to 0.2% by weight.
    [7" id="c-fr-0007]
    7. Vitroceramic based on aluminum and lithium silicate according to any one of the preceding claims, characterized by a Fe2O3 / V2O5 ratio (both in% by weight) of 5 - 7.
    [8" id="c-fr-0008]
    8. Vitroceramic based on aluminum silicate and lithium according to any one of the preceding claims, characterized by an Fe2O3 content of 700 ppm to 1000 ppm.
    [9" id="c-fr-0009]
    9. Vitroceramic based on aluminum silicate and lithium according to any one of the preceding claims, characterized by a V2O5 content of 100 ppm to 200 ppm.
    [10" id="c-fr-0010]
    10. Glass ceramic based on aluminum and lithium silicate according to any one of the preceding claims, characterized in that as the main crystalline phase it comprises a solid solution with a high quartz content.
    [11" id="c-fr-0011]
    11. Glass-ceramic plate consisting of a glass-ceramic according to at least any one of the preceding claims, characterized by a thickness of 2 mm to 20 mm.
    [12" id="c-fr-0012]
    12. Use of an article which comprises a ceramic hob according to any one of claims 1 to 11 as a cooking surface, as a glazing for a chimney / covering or covering for a closed chimney, a cover in the sector of lighting and as an optional safety glass in a laminated system, as a support plate or furnace coating, in the ceramic, solar or pharmaceutical industry or in medical technology, for production processes in high purity conditions, as furnace linings in which physical or chemical coating processes are carried out, or as chemical resistant laboratory apparatus, as glass ceramic article for high temperature or extremely high temperature applications low temperatures, as oven windows for combustion ovens, as a heat shield for the insulation of hot environments, as covers for reflectors, headlights, projectors, photocopiers, for applications involving thermomechanical exposure, such as in night vision devices, or as a cover for heating elements, in particular as as a cooking or frying surface, as a household appliance article, as a heating element cover, as a printed circuit substrate, as a UV protection article, as an architectural facade plate or as a component of an electronic device.
    [13" id="c-fr-0013]
    13. Use as a cooking surface according to claim 12, wherein the cooking surface takes the form of a coated cooking surface on the underside and / or a coated cooking surface on the underside and cutouts, called reserves for lighting in the cold zone, that is to say in the indication / display zone, and / or in the hot zone, in other words in the cooking zone, with a covering means, and / or a cooking surface comprising a so-called diffusion layer, which distributes the light uniformly from below the cooking surface towards the observer, and / or a cooking surface comprising a so-called chromatic compensation filter, applied in coated or printed form or fixed by adhesion, and / or of a cooking surface with transparent or opaque capacitive sensor structures, applied in glued form, printed or applied by pressure, for op control and regulation ventilation, and / or a cooking surface comprising one or more hole (s) for adjustment knobs, gas burners, smoke evacuation systems (called bottom extraction systems) ) and / or other functional modules, and / or comprising a planar facet on one or more edge (s), and / or a cooking surface having a transmission, defined by the value Y (D65, 2 °) , which is increased / changed locally in the display area and / or the hot area.
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    同族专利:
    公开号 | 公开日
    JP2019043842A|2019-03-22|
    US20190062201A1|2019-02-28|
    DE102018101423A1|2019-02-28|
    CN109422462A|2019-03-05|
    ES2804277T3|2021-02-05|
    DE202018100558U1|2018-02-15|
    KR20190024799A|2019-03-08|
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    法律状态:
    2019-08-22| PLFP| Fee payment|Year of fee payment: 2 |
    2020-08-21| PLFP| Fee payment|Year of fee payment: 3 |
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    DE102017119914.4|2017-08-30|
    DE102017119914|2017-08-30|
    DE102018101423.6A|DE102018101423A1|2017-08-30|2018-01-23|Colored transparent lithium aluminum silicate glass-ceramic and its use|
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