• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a partially crystallized glass plate, whose linear coefficient of thermal expansion is in a range from 20 to 40.10-7 / K, and whose chemical composition comprises the following constituents, varying within the weight limits hereinafter defined: SiO2 55-70% Al203 12-25% Li2O 1-2% K2O 0- <3% Na2O 0- <3% Li2O + Na2O + K2O 1- <7% RO 2-10% (where RO = MgO + CaO + SrO + BaO + ZnO) TiO2 0-5% ZrO2 0, 1-3%.
    公开号:FR3020359A1
    申请号:FR1453866
    申请日:2014-04-29
    公开日:2015-10-30
    发明作者:Kamila Plevacova；Emmanuel Lecomte
    申请人:Eurokera SNC；
    IPC主号:
    专利说明:

    [0001] The invention relates to the field of glass plates, in particular used in induction cooking devices, as door panels or oven panes, or as chimney inserts. The aforementioned applications require plates having a high thermomechanical resistance, in particular excellent resistance to thermal shock, as well as resistance to corrosive atmospheres at high temperatures. The object of the invention is to propose glass plates which are particularly well adapted to these applications. For this purpose, the subject of the invention is a partially crystallized glass plate, the linear thermal expansion coefficient of which is in a range from 20 to 40 × 10 -7 / K, the chemical composition of which comprises the following constituents; varying within the following weight limits: SiO2 55-70% Al2O3 12-25% Li2O 1-2% K2O 0- <3% Na2O 0- <3% Li2O + Na2O + K20 1- <7% RO2 -10% (where RO = Mg0 + Ca0 + Sr0 + Ba0 + ZnO) TiO2 0-5% ZrO2 0.1-3%.
    [0002] The inventors have been able to demonstrate that the partial crystallization of a glass having such a composition makes it possible to obtain a material with high thermomechanical and chemical resistance. The material is in the form of a glass containing within it a certain proportion of crystals. The crystals advantageously have an average size of at most 1 μm, especially 500 nm and even 100 nm so that the plate is sufficiently transparent.
    [0003] Preferably, the plate comprises crystals of 13-quartz structure within the glass in order to adjust the linear coefficient of thermal expansion in the desired range. The coefficient of linear thermal expansion of the plate is preferably in a range from 25 to 38.10-7 / K, especially from 30 to 35.10-7 / K. The coefficient of linear thermal expansion is measured according to ISO standard 7991: 1987 between 20 and 300 ° C. The chemical composition of the plate according to the invention preferably comprises (or consists essentially of) the following constituents, varying within the weight limits defined below: 50% 55-70%, especially 65-70% Al 2 O 3 12-25% especially 18-21% B203 0-0.5%, especially 0 1-2% Li2O, especially 1.2-1.8% K20 0- <3%, especially 0-2% Na20 0- <3% , in particular 0-2% Li 2 O + Na 2 O + K 2 O <5% CaO 0-10%, especially 0-5% MgO 0-5%, especially 1-4% 5r0 0-5%, in particular 0-3% BaO 0-5%, in particular 0-2% ZnO 0-5%, especially 1-3% RO 2-10% (where RO = Mg0 + Ca0 + Sr0 + Ba0 + ZnO) TiO2 0-3%, in particular 0, 5-3% ZrO 2 0.1-3%, especially 0.3-2% SnO 2 0-1%, in particular 0.2-1% AS 2 O 3 + Sb 2 O 3 <0.1%. The expression "essentially consists of" must be understood in that the aforementioned oxides constitute at least 96% or even 98% of the weight of the glass.
    [0004] Silica (SiO 2) is the main forming oxide of glass. High levels will help increase the viscosity of the glass beyond what is acceptable, while too low levels will increase the coefficient of thermal expansion. Alumina (Al 2 O 3) also contributes to increasing the viscosity of the glass and decreasing its coefficient of expansion. Its effect is beneficial on Young's modulus. The alkaline earth oxides (particularly CaO lime) as well as barium oxide (BaO) are useful for facilitating glass melting and refining by their high temperature viscosity reducing effect. The alkali oxides, and more particularly the sodium hydroxide Na 2 O and potassium hydroxide K 2 O have the drawback of increasing the coefficient of thermal expansion, so that their content is limited. The Li 2 O content is advantageously at most 1.5%. Low levels of lithium oxide also allow the use of economic lithium carriers containing coloring impurities, for example iron oxide, such as spodumene, lithic feldspars, petalite, or cullet. glass or glass ceramic composition adapted to the realization of hobs. This last point is particularly advantageous in the case of plates having a high light transmission and colorless (clear plates). The composition of the glass may comprise other components. They may be refining agents, in a content generally of at most 1% or 2%, especially chosen from sulphates, halogens (especially chlorine), sulphides (especially zinc sulphide), oxides of arsenic, antimony, iron, tin, cerium, vanadium, or any of their mixtures. The refining agents are used to rid the molten glass of all gaseous inclusions. Among these agents, tin oxide is particularly preferred, and its mass content is advantageously in a range from 0.1%, especially 0.2%, to 0.6%, especially 0.5%. The chemical composition of the plate according to the invention is preferably such that the sum of the weight contents of arsenic oxide and antimony oxide is at most 0.1%, in particular is zero. The chemical composition of the plate according to the invention preferably comprises tin oxide SnO 2 in a weight content of at most 1%. They may also be coloring agents, such as oxides of iron, cobalt, vanadium, copper, chromium, nickel, selenium or sulphides. In most applications, particularly for plates used as door panels or oven panes or as chimney inserts or as fire resistant glazings, the content of coloring agents will be as low as possible so that the plate is colorless and has the highest possible light transmission. The coloring agents will then be present, if any, only as impurities, in trace form. The iron oxide content present as impurity in most raw materials is preferably at most 400 ppm (1 ppm = 0.0001%), in particular 200 ppm and even 100 ppm. The partially crystallized glass plate preferably has a thickness in a range of 1 to 8 mm, especially 2 to 6 mm, or even 2 to 4 mm. Its lateral dimensions are typically from 30 cm to 200 cm, in particular from 50 cm to 150 cm. The plate according to the invention preferably has a light transmission factor (according to EN 410) of at least 50%, in particular 60% and even 70% or 80%, or even 85% or 90%. Such values are particularly valuable in the case of plates used as oven doors, fireplace inserts, fireproof glazing, to ensure the best possible visibility to users. The subject of the invention is also a process for obtaining a plate according to the invention, comprising a step of melting the glass, a step of forming said glass in the form of a plate, then a crystallization step. The melting is typically performed in refractory furnaces using burners using as the oxidizer air or, better, oxygen, and as a fuel of natural gas or fuel oil. Resistors of molybdenum or platinum immersed in the molten glass may also provide all or part of the energy used to obtain molten glass. Raw materials (silica, spodumene, petalite, etc.) are introduced into the furnace and undergo, under the effect of high temperatures, various chemical reactions, such as decarbonation, melting reactions as such. The invention makes it possible to obtain clear plates by using economic lithium carriers containing coloring impurities. The mixture of raw materials therefore preferably contains at least one material selected from spodumene, petalite, a lithiferous feldspar or vitroceramic cullet used as a hob, or cullet master glass of such a glass-ceramic. The maximum temperature reached by the glass is typically at least 1500 ° C., especially between 1600 and 1700 ° C. The forming of the plate glass can be done in known manner by rolling the glass between metal or ceramic rollers, by drawing (upward or downward) or by floating, technique of pouring the molten glass on a bath of water. molten tin.
    [0005] The crystallization step preferably involves a thermal cycle involving a rise in temperature to a crystallization temperature preferably within a range of 850 to 1000 ° C, especially 900 to 960 ° C. The choice of temperatures and / or crystallization times, to be adapted to each composition, makes it possible to adjust the coefficient of thermal expansion of the material obtained by varying the nature and the quantity of crystals. Preferably, the thermal cycle comprises a rise to a temperature of between 650 ° C. and 850 ° C. for a period of 5 to 60 minutes and then a rise to a temperature of between 850 and 1000 ° C. for a period of 5 to 60 minutes. . Another object of the invention is an induction cooking device comprising at least one plate according to the invention and at least one inductor. It is preferable that the glass plate is able to conceal the inductors, the electrical wiring, as well as the control and control circuits of the cooking device. For this purpose it is possible to provide a portion of the surface of the plate (the one which in the cooking device is located with respect to the elements to be concealed) with a coating deposited on and / or under the plate, said coating having the ability to absorb and / or reflect and / or diffuse light radiation. The coating can be deposited under the plate, that is to say on the surface facing the internal elements of the device, also called "lower face", and / or on the plate, that is to say opposite higher. The coating may be an organic-based layer, such as a layer of paint, resin or lacquer, or a mineral-based layer, such as an enamel or a metal layer or an oxide, nitride, oxynitride, oxycarbide of a metal. Preferably, the organic layers will be deposited on the lower face, while the mineral layers, including enamels, will be deposited on the upper face. The various internal elements of the cooking device may also be concealed by an opaque sheet disposed between them and the plate, for example a sheet of mica. Alternatively or cumulatively, the composition of the glass may comprise coloring agents such as iron oxide, present as impurity in most raw materials, cobalt oxide, chromium oxide, copper oxide, vanadium oxide, nickel oxide, or selenium. The total weight content of coloring agents is normally at most 2%, or even 1%. The introduction of one or more of these agents can lead to obtaining a dark glass plate, very low light transmission (typically at most 3%, especially 2% and even 1%), which will have the advantage to conceal the inductors, the electrical wiring, and the control and control circuits of the cooking device.
    [0006] In addition to the glass plate and at least one inductor (preferably three or even four and even five), the cooking device may comprise at least one light emitting device, at least one control and control device, the assembly being included in a box. One, the or each light-emitting device is advantageously chosen from light-emitting diodes (for example forming part of 7-segment displays), liquid crystal (LCD) and light-emitting diode (OLED) displays, fluorescent displays (VFD). The colors seen through the plate are various: red, green, blue, and all possible combinations, including yellow, purple, white. These light-emitting devices may be purely decorative, for example visually separate different areas. of the plate. Most often however they will have a functional role by displaying various useful information for the user, including 20 indication of the heating power, temperature, cooking programs, cooking time, areas of the plate exceeding a temperature predetermined. The control and control devices generally comprise sensitive keys, for example of the capacitive or infrared type. The set of internal elements is usually attached to a box, often metal, which is therefore the lower part of the cooking device, normally hidden in the worktop or in the body of the stove. Another object of the invention is a domestic oven door comprising at least one plate according to the invention, in particular as a glass plate intended to be closest to the enclosure of said oven.
    [0007] The oven door according to the invention preferably comprises an inner glass plate and an outer glass plate, these two plates forming the two outer main flat faces of the door, so that one door is mounted on the oven , the inner glass plate is closest to the oven enclosure, and the outer plate is closest to the user. The oven door according to the invention preferably comprises at least one intermediate glass plate 10 located between the inner glass plate and the outer glass plate, and separated from each of the latter by at least one air gap. A preferred door comprises three or four glass plates, and thus one or two intermediate glass plates. At least one glass plate, in particular an intermediate glass plate, is advantageously coated with a low-emissive layer, in particular a layer of an electroconductive transparent oxide (TC0), such as, for example, the oxide of doped tin, especially fluorine or antimony. The presence of such layers makes it possible to reduce the heat exchange between the glass plates, thus contributing to improving the thermal insulation of the door. Another object of the invention is a chimney insert comprising at least one glass plate according to the invention. The invention finally relates to a fire resistant glazing comprising at least one glass plate according to the invention. The following exemplary embodiments illustrate the invention without limiting it.
    [0008] Glasses having the chemical compositions shown in Table 1 were melted and shaped into a plate. The plates obtained were then partially crystallized by subjecting them to a thermal cycle characterized by rapid heating up to 590 ° C., then rising to 820 ° C. at a rate of 10 ° C./min, and finally rising to a temperature of 10 ° C. at 930 ° C at a rate of 20 ° C / min followed by holding for 6 minutes at this temperature.
    [0009] Table 1 below indicates for each example, in addition to the chemical composition expressed in percentages by weight, the liquidus temperature, the temperatures corresponding to a viscosity of 104 and 1013 poises (1 poise = 0.1 Pa. $) Noted respectively. and 113, as well as the coefficient of linear thermal expansion (CTE) for glass as well as for partially crystallized glass. The coefficients of linear thermal expansion are measured according to ISO 7991: 1987 between 20 and 300 ° C.20 1 2 SiO2 67.0 66.9 A1202 19.6 19.6 Na2O 0.2 1.3 K20 0.2 1.6 Li20 1.5 1.5 MgO 1.2 3.0 BaO 0.8 0.8 CaO 4.2 0 TiO2 2.6 2.6 ZrO2 0.8 0.8 ZnO 1.6 1.6 Sn02 0.3 0.3 Liquidus (° C) <1350 1310 14 (° C) 1344 1351 113 (° C) 724 700 CTE (10-7 / ° C) 43 44 Crystallized glass CTE (10-7 / ° C) ) 34 37 Table 1
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Partially crystallized glass plate, the coefficient of linear thermal expansion of which is in a range from 20 to 40.10-7 / K, and the chemical composition of which comprises the following constituents, varying within the weight limits defined below: SiO 2 55 -70% A1203 12-25% Li20 1-2% K20 0- <3% Na2O 0- <3% Li2O + Na2O + K20 1- <7% RO
    [0002]
    2-10% (where RO = MgO + CaO + SrO + BaO + ZnO) TiO 2 0-5% ZrO 2 0.1-3%. 2. A plate according to claim 1, whose chemical composition is such that the sum of the weight contents of arsenic oxide and antimony oxide is at most 0.1%, in particular is zero.
    [0003]
    3. Plate according to one of the preceding claims, the chemical composition of which comprises tin oxide SnO2 in a weight content of at most 1%.
    [0004]
    4. Plate according to one of the preceding claims, comprising within the crystal crystals 13-quartz structure.
    [0005]
    5. Plate according to one of the preceding claims, which has a light transmittance of at least 50%, especially 80%.
    [0006]
    6. A method for obtaining a plate according to one of the preceding claims, comprising a glass melting step, a step of forming said plate glass, and a crystallization step.
    [0007]
    7. Induction cooking device comprising at least one plate according to one of claims 1 to 5 and at least one inductor.
    [0008]
    8. Domestic oven door comprising at least one plate according to one of claims 1 to 5, in particular as a glass plate intended to be closest to the enclosure of said furnace.
    [0009]
    Chimney insert comprising at least one glass plate according to one of claims 1 to 5.
    [0010]
    10. Fire resistant glazing comprising at least one glass plate according to one of claims 1 to 5.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    TWI414502B|2008-05-13|2013-11-11|Corning Inc|Rare-earth-containing glass material and substrate and device comprising such substrate|
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    FR2971387B1|2011-02-04|2014-08-08|Saint Gobain|COATING HEATING ELEMENT|
    EP3572382A1|2012-02-24|2019-11-27|PPG Industries Ohio, Inc.|Lithium containing glass with high oxidized iron content and method of making same|
    FR2988465B1|2012-03-20|2014-03-14|Eurokera|OVEN DOOR|FR3040766B1|2015-09-08|2018-07-27|Eurokera S.N.C.|WORK PLAN IN VITROCERAMIC|
    CN107037073B|2017-05-22|2019-11-08|东旭科技集团有限公司|A kind of measuring method of glass liquidus temperature|
    US10917942B2|2017-07-31|2021-02-09|Samsung Electronics Co., Ltd.|Structure, planar heater including the same, heating device including the planar heater, and method of preparing the structure|
    法律状态:
    2015-04-04| PLFP| Fee payment|Year of fee payment: 2 |
    2015-10-30| PLSC| Search report ready|Effective date: 20151030 |
    2016-04-20| PLFP| Fee payment|Year of fee payment: 3 |
    2017-04-21| PLFP| Fee payment|Year of fee payment: 4 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1453866A|FR3020359B1|2014-04-29|2014-04-29|PARTIALLY CRYSTALLIZED GLASS PLATE|FR1453866A| FR3020359B1|2014-04-29|2014-04-29|PARTIALLY CRYSTALLIZED GLASS PLATE|
    US15/307,268| US20170050880A1|2014-04-29|2015-04-28|Partially crystallised glass plate|
    JP2016565179A| JP6633543B2|2014-04-29|2015-04-28|Partially crystalline glass plate|
    PCT/FR2015/051148| WO2015166183A1|2014-04-29|2015-04-28|Partially crystallised glass plate|
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    CN201580023208.8A| CN106573825B|2014-04-29|2015-04-28|Partially crystallized glass sheet|
    KR1020167029884A| KR20160146746A|2014-04-29|2015-04-28|Partially crystallised glass plate|
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