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WO2025089764A1 - Procédé de détermination de déformation par bombage de verre à glace, procédé de fabrication de verre le mettant en œuvre, et verre fabriqué au moyen dudit procédé de fabrication - Google Patents

Procédé de détermination de déformation par bombage de verre à glace, procédé de fabrication de verre le mettant en œuvre, et verre fabriqué au moyen dudit procédé de fabrication Download PDF

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Publication number
WO2025089764A1
WO2025089764A1 PCT/KR2024/016123 KR2024016123W WO2025089764A1 WO 2025089764 A1 WO2025089764 A1 WO 2025089764A1 KR 2024016123 W KR2024016123 W KR 2024016123W WO 2025089764 A1 WO2025089764 A1 WO 2025089764A1
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Prior art keywords
glass
ion exchange
curvature
plate glass
layer
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Korean (ko)
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최용규
이지인
고세영
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University Industry Cooperation Foundation of Korea Aerospace University
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University Industry Cooperation Foundation of Korea Aerospace University
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Priority claimed from KR1020240144869A external-priority patent/KR20250058695A/ko
Application filed by University Industry Cooperation Foundation of Korea Aerospace University filed Critical University Industry Cooperation Foundation of Korea Aerospace University
Publication of WO2025089764A1 publication Critical patent/WO2025089764A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface

Definitions

  • the present invention relates to a method for manufacturing curved glass having a chemical strengthening effect and an intended curvature, and to chemically strengthened curved glass manufactured by the method.
  • the present invention relates to chemically strengthened plate glass having a controlled curvature radius, manufactured by a method for determining an ion exchange temperature and a holding time capable of implementing an arbitrary curvature radius, including cases where the curvature radius has a very large value for a given thickness of plate glass, in order to simultaneously control chemical strengthening performance and the curvature radius.
  • the plate glass that is the target of the chemical strengthening process is broadly classified into the NCS composition of the Na 2 O-CaO-SiO 2 series and the NAS composition of the Na 2 O-Al 2 O 3 -SiO 2 series, and in detail, it includes a wide variety of composition ratio changes. Furthermore, depending on the application field, not only are the shapes such as thickness, area, and aspect ratio different, but the curvature radius required before and after chemical strengthening may also be different. In the past, in most cases, the bending deformation was implemented through hot forming, and then ion exchange was performed to maintain the shape and impart the chemical strengthening effect, so the method of setting the ion exchange process conditions to maintain the initially given bending deformation was applied. The chemical strengthening cases for plate glass will be explained separately.
  • an ion exchange process may be required to impart a chemical strengthening effect through ion exchange to flat or curved plate glass, but to actually maintain the curvature radius of the plate glass within an allowable range.
  • Another example is a process that changes the radius of curvature of a given sheet glass to a significant size by controlling the ion exchange process conditions. Since the change in the radius of curvature caused by ion exchange in sheet glass is affected by a wide variety of factors, the ion exchange conditions that can obtain the desired radius of curvature have been set through a trial and error process of simple and repeated attempts so far, and the greatest concern is securing conditions in which no additional curvature occurs during the ion exchange process.
  • the time dependence of the change in the radius of curvature of the sheet glass that occurs during the heat treatment process for ion exchange is presented in the form of a formula by utilizing the mutual diffusion coefficient determined by the composition of the sheet glass and the ion exchange temperature and the thickness of the sheet glass.
  • the ion exchange process for chemical strengthening can be largely divided into the immersion method and the non-immersion method, and the immersion method, which immerses the target glass in a molten alkali salt to cause ion exchange, is commercially applied (Varshneya, International Journal of Applied Glass Science 9(2018) 140). Since the target glass is immersed in a molten alkali salt, it may cause undesirable deformation in a situation where ion exchange occurs differently on both sides of the target glass. Meanwhile, various ion exchange processes can be used to intentionally provide different ion exchange effects depending on the location of the target glass.
  • the composition of the molten alkali salt can be formed differently depending on the location of the glass or implemented through masking (Findakly, Optical Engineering 24(1985) 244).
  • a method of inducing alkali ions to move and diffuse in the thickness direction by applying an electric field in the thickness direction can also be applied (Shaisha, Journal of the American Ceramic Society 64(1981) 278).
  • the non-immersion method is a process in which a slurry or paste containing an alkaline salt is prepared and applied to a glass surface to perform ion exchange in a dry manner.
  • the diffusion coefficient may vary depending on the difference in the composition of the salt, and this may result in a difference in not only CS (compressive stress) but also DOL (depth of layer).
  • the DOL can be increased or decreased according to the different diffusion coefficients in glass (Hassani, Journal of Non-Crystalline Solids 515(2019) 143), and for other alkali salts except for K, it has been reported that the CS can be lowered with or without a difference in the diffusion coefficient (Lyu, CeramicsInternational 46(2020) 1697).
  • different ion exchange characteristics can be effectively imparted by controlling the thickness and position of the coating film, the composition of the salt, etc.
  • different ion exchange effects can be imparted by any method or process for performing ion exchange in addition to the above-mentioned methods.
  • CS and DOL surface compressive stress and depth of layer
  • the present invention provides a relationship that can express the size of bending deformation of plate glass occurring during an ion exchange process as a function of the thickness of the plate glass and the ion exchange temperature and time, and thereby aims to provide plate glass that is chemically strengthened while having a controlled curvature.
  • a method for determining a bending deformation of plate glass wherein, in a temperature range in which elastic deformation occurs, a radius of curvature of the plate glass corresponding to the bending deformation of the plate glass is determined based on the Stoney relation, wherein the first layer and the second layer included in the Stoney relation are set to be a value obtained by integrating a concentration distribution up to an ion exchange depth layer after ion exchange of glass including alkali, and an effective diffusion length, which is a depth calculated to have the same area under the assumption that the same surface concentration is the same according to the depth, and a thickness of the plate glass corresponding to the effective diffusion length is regarded as the first layer, and a thickness of the plate glass excluding the effective diffusion length is regarded as the second layer.
  • the diffusion coefficient in the above Stoney relationship is a value calculated by inversely calculating the diffusion depth (depth of layer) obtained after the ion exchange.
  • the above effective diffusion length is a value calculated through parameters set by considering the error range that occurs in the measurement of compressive stress and the stress that causes bending deformation, and the diffusion depth obtained after the ion exchange.
  • a method for determining the bending deformation of plate glass determines the radius of curvature of the plate glass as a simple sum of viscoelastic curvatures by reflecting the plastic curvature of the plate glass corresponding to the bending deformation of the plate glass based on an elasto-plastic strain-based relation together with the Stoney relation in a temperature range in which plastic deformation progresses, wherein the plastic strain included in the elasto-plastic strain-based relation is based on a width change that appears in the plate glass after ion exchange through a shape change caused by a structural relaxation effect due to ⁇ -relaxation.
  • the above plastic curvature is calculated as a plastic curvature that occurs under the assumption that the width change that occurs up to the ion exchange depth layer after ion exchange including alkali is formed differently depending on the alkali concentration, but the average width change that occurs up to the ion exchange depth layer is constant.
  • the above elastomeric strain is a value calculated through a relationship based on the structural relaxation effect caused by ⁇ -relaxation that occurs differently depending on the ion exchange temperature and time during ion exchange.
  • the above width change is calculated from the plastic strain among the above elastoplastic strains and the width value of the plate glass.
  • the width change is a value that gradually changes depending on the concentration from the glass surface (glass polar surface) to just before the non-ion exchange layer, and is a value calculated by averaging the width change up to the ion exchange depth layer through integration.
  • the above-mentioned non-ion exchange layer refers to the remaining layer excluding the diffusion depth from the total thickness, i.e., the layer in which ion exchange does not occur.
  • the above plastic curvature is a value calculated by assuming that the width change occurs at a thickness change from half the depth of the non-ion exchange layer to half the depth of the ion exchange layer through a simple geometric method utilizing the above width change.
  • the above viscoelastic curvature is a value calculated as a simple sum of the elastic curvature, which is the bending strain based on the above Stoney relation, and the plastic curvature, which is the bending strain based on the above elastic-plastic strain-based relation.
  • a method for manufacturing glass using the method for determining the amount of warpage deformation of plate glass according to the present invention can cause warpage deformation corresponding to the radius of curvature in the plate glass through ion exchange of glass including the alkali corresponding to the radius of curvature determined by the method for determining the amount of warpage deformation of plate glass.
  • the glass manufactured by the method for manufacturing the glass is a glass manufactured to correspond to a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width change appearing in the plate glass after ion exchange, which are derived based on the Stoney relationship and/or the elastic-plastic strain-based relationship reflecting the assumption and the settings for the first layer and the second layer.
  • the glass manufactured by the method for manufacturing the glass is glass manufactured so that bending deformation occurs corresponding to a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width change of the glass, which is derived based on a Stoney relationship in which the assumption and settings for the first layer and the second layer are reflected, and/or an elasto -plastic strain-based relationship in which the setting for the width change is reflected, in response to ion exchange occurring on a first surface among both sides of the plate glass, and a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width change of the glass, which is derived based on a Stoney relationship in which the assumption and settings for the first layer and the second layer are reflected, and/or an elasto-plastic strain-based relationship in which the setting for the width change is reflected.
  • the glass manufactured by the method for manufacturing the glass is glass manufactured so that bending deformation occurs corresponding to a preset relationship among the curvature, the compressive stress, the effective diffusion length, the alkali concentration distribution, the ⁇ -relaxation coefficient, and the width change of the glass, which is derived based on a Stoney relationship that reflects the assumption and the settings for the first layer and the second layer, and/or an elasto -plastic strain-based relationship that reflects the settings for the width change, in response to ion exchange occurring in a first region among the regions on both sides of the plate glass, and a preset relationship among the curvature, the compressive stress, the effective diffusion length, the alkali concentration distribution, the ⁇ -relaxation coefficient, and the width change of the glass, which is derived based on a Stoney relationship that reflects the assumption and the settings for the first layer and the second layer, and/or an elasto-plastic strain - based relationship that reflects the settings for the width change, in
  • a coating film is formed on the cross-section of the plate glass through a non-immersion method, and a heat treatment for ion exchange is performed to provide a chemical strengthening effect, and at the same time, the deformation of the plate glass is filmed in real time to obtain a real-time video, and the size of the warpage deformation caused by the ion exchange is analyzed to propose a relationship that relates the thickness of the plate glass and the ion exchange factor to the size of the warpage deformation.
  • the amount of warpage deformation corresponding to the ion exchange temperature and holding time can be quantitatively inferred only with the thickness of the plate glass and the temperature-dependent diffusion coefficient, and further, based on the relationship, the radius of curvature of the plate glass can be controlled by inducing ion exchange of different forms on both sides of the plate glass.
  • a relationship is provided that can determine the warpage deformation of a glass plate caused by ion exchange in relation to changes in the thickness of the glass plate, the mutual diffusion coefficient, the alkali concentration distribution, the ion exchange temperature, and the time.
  • a method for intentionally imparting different CS and DOL to a cross-section or both sides of a glass plate having an arbitrary given thickness, particularly through non-immersion ion exchange, and controlling the size of the resulting bending deformation of the glass plate by utilizing the above-mentioned relationship, and a glass plate having a controlled curvature produced thereby.
  • Figure 1 is a modified version of a concentration distribution graph by general diffusion.
  • Figure 2 shows the concentration distribution and effective diffusion length for the glass depth.
  • Figure 3 shows the stress distribution and effective stress for the glass depth.
  • Figure 4 is an example of various strain distributions caused by stress after ion exchange.
  • Figure 5 is a schematic diagram of the change in curvature caused by a change in width.
  • Figure 6 is a photograph of glass that has undergone deformation after ion exchange at different temperatures.
  • Figure 7 is a graph showing the real-time temperature measurement and glass deformation during heat treatment at 440°C for 15 minutes.
  • Figure 8 is a graph of the amount of glass deformation measured in real time according to ion exchange temperature.
  • Figure 9 is a graph of the deformation rate of glass measured in real time according to ion exchange temperature.
  • Figure 10 is a graph of glass curvature measured in real time according to ion exchange temperature.
  • Figure 11 shows the temperature-dependent diffusion coefficient of sodium alumino-silicate glass.
  • Figure 12 shows the calculation of the effective diffusion length according to the virtual ion exchange time.
  • Figure 13 shows the relevant indices of glass used in calculating the relational formula.
  • Figure 14 shows the ⁇ 0 values used in the calculations for ion exchange temperatures.
  • Figure 15 (a) shows the change in curvature over time when CS is a constant ⁇ 0 for each ion exchange temperature, and (b) shows the change in curvature over time for each actual ion exchange temperature.
  • Figure 16 shows the time-dependent curvature strain of a cross-sectional ion-exchange glass at 425°C for 15 minutes, the behavior of the curvature strain calculated by the measured CS, and the behavior of the fitting equation.
  • Figure 17 shows the change in curvature strain fitting CS according to ⁇ at different temperatures.
  • Figure 18 shows the CS measurements used for ion exchange temperature and time-dependent calculations.
  • Figure 19 (a) shows the change in curvature over time (line) when CS is ⁇ 0 at each ion exchange temperature and the curvature calculated with the measured CS (symbol), and (b) shows the change in curvature over time at each actual ion exchange temperature.
  • Figure 20 shows the expected curvature change over time at different ion exchange temperatures.
  • Figure 21 shows the predicted curvature change over time for each CS at a temperature of 425°C.
  • Figure 22 shows the expected curvature change according to DOL for each CS at a temperature of 425°C.
  • Figure 23 shows the CS, DOL, and curvature measurement values for each ion exchange condition used in calculating the effective diffusion length.
  • Figure 24 shows the effective film thickness (x-axis) calculated using the Stoney relation and the effective diffusion length (y-axis) calculated from the concentration distribution.
  • Figure 25 shows the distribution of alkali ion concentration along the depth of a cross-section of a cross-section of ion-exchange glass at 425°C for 7 minutes as measured by SEM-EDS.
  • Figure 26 compares the optical DOL measured by FSM and the chemical DOL measured by SEM-EDS.
  • Figure 27 shows a comparison of the effective diffusion length obtained from the concentration distribution area and the effective diffusion length calculated as a constant multiple of the optically measured DOL.
  • Figure 28 shows the CS, DOL, and curvature measurement values for each ion exchange condition used in calculating the effective stress.
  • Figure 29 shows the effective stress (x-axis) calculated from the stress distribution obtained from the concentration distribution and the stress (y-axis) calculated using the Stoney relation of Equation 7.
  • Figure 30 shows a comparison of the effective stress obtained from the area and the effective stress calculated as a constant multiple of the optically measured stress, assuming that the concentration distribution is identical to the stress distribution.
  • Figure 31 shows the heat treatment conditions and CS/DOL of the air/tin side of general float glass. Journal of the Australian Ceramic Society 57 (2021) 1331).
  • Figure 32 shows the amount of bending deformation according to the length of the glass.
  • Figure 33 shows the diffusion coefficients of air and tin sides of general float glass ( Journal of the Australian Ceramic Society 57(2021) 1331).
  • Figure 34 shows the change in curvature over time obtained under heat treatment conditions at 425°C for 8 hours.
  • Figure 35 shows the deformation control of general float glass under ion exchange conditions at 435°C for 12 hours.
  • Figure 36 shows the conditions for non-deformation and the difference in curvature radius on the air/tin side in general float glass.
  • Figure 37 shows the relevant parameters of soda-lime silicate glass used in stress calculations (Macrelli, International Journal of Applied Glass Science 11 (2020) 730).
  • Figure 38 shows the calculated CS values according to changes in thickness and DOL.
  • Figure 39 shows the CS change due to DOL and thickness changes.
  • Figure 40 is a graph of the amount of glass deformation measured in real time according to ion exchange temperature.
  • Figure 41 is a graph of the strain rate of glass measured in real time according to ion exchange temperature.
  • Figure 42 shows the relevant indices of glass used in calculating the relational formula.
  • Figure 43 shows the CS, DOL, and curvature measurement values used in calculations according to ion exchange temperature conditions.
  • Figure 44 is a graph of glass curvature measured in real time according to ion exchange temperature.
  • Figure 45 is a graph of the glass sintering curvature measured in real time according to ion exchange temperature.
  • Figure 46 is a graph comparing the calculated plastic curvature and the actual curvature according to ion exchange conditions.
  • Figure 47 shows photographs of glass that was deformed after ion exchange at different temperatures using LiNO 3 slurry.
  • Figure 48 is a graph of the curvature of glass measured in real time according to ion exchange temperature.
  • the method for determining the amount of bending deformation of plate glass determines the radius of curvature of the plate glass corresponding to the amount of bending deformation of the plate glass based on the Stoney relation and/or the elastic-plastic strain-based relation, wherein the first layer and the second layer included in the Stoney relation are set to be the first layer only, based on the integrated value of the concentration distribution up to the ion exchange depth layer after ion exchange of glass including alkali, and the effective diffusion length, which is the depth calculated to have the same area under the assumption that the same surface concentration is the same according to the depth, and the thickness of the plate glass excluding the effective diffusion length is regarded as the second layer, and the plastic strain included in the elastic-plastic strain relation is based on the width change that appears in the plate glass after ion exchange through the shape change caused by the structural relaxation effect by ⁇ -relaxation, and the width change that gradually changes according to the concentration in the ion exchange depth layer is averaged and regarded as one value, and the plastic
  • the diffusion coefficient in the Stoney relation is a value calculated by inversely calculating the diffusion depth (depth of layer) obtained after the ion exchange.
  • the effective diffusion length is a value calculated through parameters set in consideration of the error range that occurs for the measurement of compressive stress and the stress that causes the bending deformation, and the diffusion depth obtained after the ion exchange.
  • the plastic strain in the elastic-plastic strain-based relation is a value calculated from parameters set in consideration of the shape change that occurs due to structural relaxation, which is ⁇ -relaxation, and the concentration distribution of alkali.
  • the width change is a value calculated through parameters set according to the assumption and the plastic strain.
  • the method for determining the amount of warpage deformation of plate glass determines the radius of curvature of the plate glass corresponding to the amount of warpage deformation of the plate glass based on the Stoney relation in a temperature range in which elastic deformation progresses, wherein the first layer and the second layer included in the Stoney relation are a value obtained by integrating the concentration distribution up to the ion exchange depth layer after ion exchange of glass including alkali, and an effective diffusion length, which is a depth calculated to have the same area under the assumption that the same surface concentration is the same according to the depth, and may be set such that a thickness corresponding to the effective diffusion length depth among the thickness of the plate glass is regarded as the first layer, and a thickness of the plate glass excluding the effective diffusion length depth is regarded as the second layer.
  • a method for determining a bending deformation amount of plate glass determines a radius of curvature of the plate glass by simply summing viscoelastic curvatures by reflecting the plastic curvature of the plate glass corresponding to the bending deformation amount of the plate glass based on an elasto-plastic strain-based relation together with the Stoney relation in a temperature range where plastic deformation occurs, and the plastic strain amount included in the elasto-plastic strain-based relation may be based on a width change that appears in the plate glass after ion exchange through a shape change caused by a structural relaxation effect due to -relaxation.
  • the above plastic curvature can be calculated as the plastic curvature that occurs under the assumption that the average width change that occurs up to the ion exchange depth layer is constant up to the ion exchange depth layer.
  • the above-mentioned elastomeric strain may be a value calculated through a relationship based on the structural relaxation effect caused by ⁇ -relaxation that occurs differently depending on the ion exchange temperature and time during ion exchange.
  • the width change is calculated from the plastic strain among the elastic strains and the width value of the plate glass, and may be a value that changes depending on the concentration from the glass surface to just before the ion exchange layer, and may be a value calculated by averaging the width change up to the ion exchange depth layer through integration.
  • the above plastic curvature may be a value calculated by assuming that the width change occurs in a thickness change from half the depth of the non-ion exchange layer to half the depth of the ion exchange depth layer through a simple geometric method utilizing the above width change.
  • the viscoelastic curvature may be a value calculated as a simple sum of the elastic curvature, which is a bending strain based on the Stoney relation, and the plastic curvature, which is a bending strain based on the elastic-plastic strain-based relation.
  • a method for manufacturing glass using the method for determining the bending deformation of plate glass according to the present invention can cause bending deformation corresponding to the radius of curvature in the plate glass through ion exchange of glass including the alkali corresponding to the radius of curvature determined by the method for determining the bending deformation of plate glass.
  • the glass manufactured by the method for manufacturing the glass is glass manufactured to correspond to a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass derived based on the Stoney relationship in which the above assumptions and the settings for the first layer and the second layer are reflected, and/or the elastic-plastic strain-based relationship in which the settings for the width change are reflected.
  • the glass can be manufactured so that, in a temperature range where elastic deformation occurs, a bending deformation occurs corresponding to a preset relationship between the curvature, compressive stress, and effective diffusion length of the glass derived based on the Stoney relationship that reflects the assumption and the settings for the first layer and the second layer.
  • the glass can be manufactured to correspond to a preset relationship between the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width change that appears in the plate glass after ion exchange, which are derived based on an elasto-plastic strain-based relationship together with the Stoney relationship, in a temperature range where plastic deformation occurs.
  • the glass manufactured by the method for manufacturing the glass may be glass manufactured such that, in response to ion exchange occurring on a first surface among both surfaces of the plate glass, a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass is derived based on a Stoney relationship in which the assumption and settings for the first layer and the second layer are reflected, and/or an elasto-plastic strain-based relationship in which the setting for the width change is reflected, and in response to ion exchange occurring on a second surface among both surfaces of the plate glass, a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass is derived based on a Stoney relationship in which the assumption and settings for the first layer and the second layer are reflected, and/or an elasto-plastic strain-based relationship in which the setting for
  • the glass can be manufactured so that, in a temperature range in which elastic deformation occurs, bending deformation occurs corresponding to a preset relationship between the curvature, compressive stress, and effective diffusion length of the glass, which is derived based on the Stoney relationship that reflects the assumption and the settings for the first layer and the second layer, in response to ion exchange occurring on the first surface among both sides of the plate glass, and a preset relationship between the curvature, compressive stress, and effective diffusion length of the glass, which is derived based on the Stoney relationship that reflects the assumption and the settings for the first layer and the second layer, in response to ion exchange occurring on the second surface among both sides of the plate glass.
  • the glass can be manufactured so that, in a temperature range where plastic deformation progresses, bending deformation occurs corresponding to a preset relationship among curvature, compressive stress, and effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass, derived based on an elasto-plastic strain-based relationship in which a setting for a width change that appears in the glass after ion exchange is reflected, together with a Stoney relationship in which the assumption and the settings for the first and second layers are reflected, in response to ion exchange that occurs on the first surface of the glass among both sides, and a preset relationship among curvature, compressive stress, and effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass, derived based on an elasto-plastic strain-based relationship in which a setting for a width change is reflected, together with a Stoney relationship in which the assumption and the settings for the first and second layers are reflected, in response to a
  • the temperature range in which the above plastic deformation occurs may be a temperature range in which elastic-plastic deformation occurs, in which plastic deformation occurs together with the above elastic deformation.
  • Such glass can be manufactured by a method of controlling the curvature of the plate glass by controlling the amount of deformation due to ion exchange occurring on the first side (one side) of the two sides of the plate glass and the amount of deformation due to ion exchange occurring on the second side (the other side).
  • the glass manufactured in this way can be manufactured as glass characterized in that different ion exchanges are imparted to both sides by being manufactured according to the method of controlling the curvature of the plate glass.
  • the glass manufactured by the method for manufacturing the glass may be glass manufactured such that, in response to ion exchange occurring in a first region among the regions on both sides of the plate glass, a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass is derived based on a Stoney relationship that reflects the assumption and the settings for the first layer and the second layer and/or an elasto -plastic strain-based relationship that reflects the settings for the width change, and in response to ion exchange occurring in a second region among the regions on both sides of the plate glass, different from the first region, a bending deformation occurs corresponding to a preset relationship among the curvature, compressive stress, effective diffusion length, alkali concentration distribution, ⁇ - relaxation coefficient, and width of the glass is derived based on a Stoney relationship that reflects the assumption and the settings for the first layer and the second layer and/or an elast
  • the glass can be manufactured so that, in a temperature range in which elastic deformation progresses, bending deformation occurs corresponding to a preset relationship between the curvature, the compressive stress, and the effective diffusion length of the glass, which is derived based on a Stoney relation that reflects the assumption and the settings for the first layer and the second layer, in response to ion exchange occurring in a first region among the regions on both sides of the plate glass, and a preset relationship between the curvature, the compressive stress, and the effective diffusion length of the glass, which is derived based on a Stoney relation that reflects the assumption and the settings for the first layer and the second layer, in response to ion exchange occurring in a second region different from the first region among the regions on both sides of the plate glass.
  • the glass can be manufactured so that, in a temperature range in which plastic deformation progresses, bending deformation occurs corresponding to ion exchange occurring in a first region among the regions on both sides of the plate glass, a preset relationship among curvature, compressive stress, and effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass derived based on an elasto-plastic strain-based relationship in which a setting for a width change appearing in the plate glass after ion exchange is reflected, together with a Stoney relationship in which the assumption and the settings for the first and second layers are reflected, and a preset relationship among curvature, compressive stress, and effective diffusion length, alkali concentration distribution, ⁇ -relaxation coefficient, and width of the glass derived based on an elasto-plastic strain-based relationship in which a setting for a width change is reflected, together with a Stoney relationship in which the assumption and the settings for the first and second layers are reflected, in response to
  • first region and the second region may be regions located on the same side among both surfaces of the plate glass (for example, the first region is located on the first side and the second region is located on the second side, or conversely, the first region is located on the second side and the second region is located on the first side), or may be regions located on different sides (for example, both the first region and the second region are located on the first side, or both the first region and the second region are located on the second side).
  • the glass manufactured by the method for manufacturing the glass can be manufactured by individually applying ion exchange to a plurality of regions including the first region and the second region. For example, different ion exchanges can be applied to at least some regions among the plurality of regions, so that different bending deformations can be induced in at least some regions.
  • plate glass having one or more curvatures can be manufactured so that the curvature and compressive stress or strengthening depth or concentration distribution of alkali ions in each area have characteristics corresponding to the corresponding bending deformation.
  • the present invention provides a relational expression that can quantitatively determine the amount of warpage of an alkali-containing silicate glass plate having a flat surface by utilizing the compressive or tensile stress and the diffusion depth generated at the glass surface through ion exchange, thereby providing a curved glass plate that is chemically strengthened and has controlled warpage.
  • the relational expression is based on the Stoney relation that is applied under other conditions and/or an elasto-plastic strain-based relation that reflects the setting for the width change, and is modified to be suitable for the glass plate that undergoes ion exchange, so that the warpage deformation according to the ion exchange temperature and time can be quantitatively determined only with the thickness and diffusion coefficient of the glass plate given through calculation.
  • a non-immersion ion exchange method that is easy for location-selective ion exchange can be applied, and a slurry containing an alkali salt such as KNO 3 , LiNO 3 , a solvent of the alkali salt such as water, and a metal oxide can be utilized, and in addition, a viscosity modifier can be added, and by controlling the components in the slurry (for example, the content ratio between the alkali salt, the solvent, the metal oxide, etc.), different ion exchange effects can be imparted to both sides of the plate glass, and accordingly, the radius of curvature of the plate glass according to the ion exchange conditions can be controlled by utilizing the corresponding relationship, and a curved glass with controlled curvature having such characteristics can be produced.
  • an alkali salt such as KNO 3 , LiNO 3
  • a solvent of the alkali salt such as water
  • a metal oxide a viscosity modifier
  • Chemical strengthening is being used not only for the cover windows of existing mobile electronic devices, but also for automotive glass, pharmaceutical glass, and even for ultra-thin glass used in flexible display modules such as foldable, slideable, and rollable displays, and its application fields are continuously expanding.
  • Recently, in the case of general-purpose plate glass attempts are being made to reduce the thickness of plate glass for carbon neutrality, and as a result, chemical strengthening, which is applicable only to thin glass, has to be adopted, so the demand for the chemical strengthening process will further increase.
  • a relationship is provided for calculating the radius of curvature for warpage deformation caused by the thickness, diffusion coefficient, shape, ion exchange temperature, and time of the silicate series plate glass containing alkali ions.
  • curved glass can be implemented that can quantitatively control the radius of curvature caused before and after ion exchange of the plate glass, such as maintaining the curvature after ion exchange, increasing or decreasing the curvature.
  • different ion exchange effects can be applied to both sides of the plate glass, and a non-immersion ion exchange method can be utilized for this.
  • an alkali salt such as KNO 3 , LiNO 3 , and a solvent including water and metal oxide particles are mixed to prepare a slurry, and this is applied to the surface of the glass and heat-treated to cause ion exchange, and by controlling the mixing ratio of the slurry components, different ion exchange characteristics are exhibited selectively, and thus the amount of warpage deformation of the plate glass can be controlled.
  • curved glass characterized by simultaneous control of chemical strengthening and warpage deformation is provided.
  • a mathematical formula is proposed as a method for controlling the above-mentioned bending deformation, and a process for inducing ion exchange on one side or both sides of plate glass is implemented by utilizing the mathematical formula.
  • a mathematical formula is required that expresses the radius of curvature that occurs in the plate glass with respect to the temperature and time of the ion exchange heat treatment step.
  • the bending deformation of plate glass that occurs due to ion exchange is observed in real time and analyzed numerically, and the main idea implied by the mathematical formula is further presented as a claim.
  • This application starts from a new setting that divides the exchange layer where ion exchange occurs and the non-exchange layer where ion exchange does not occur into two layers with different physical properties in elastic deformation. That is, the thickness of each layer is characterized by changing with a certain correlation as ion exchange progresses, and the key is to numerically relate this to the change in the radius of curvature.
  • the Stoney equation is a method to calculate the compressive or tensile stress applied to two sheets of material having different coefficients of thermal expansion or other properties by relating the radius of curvature of the sheets to the thickness of each sheet when the two sheets are physically or chemically bonded with a level of strength that does not cause delamination at the interface.
  • the compressive or tensile stress that occurs elastically can be calculated by substituting the radius of curvature and the thickness of each layer, and it can be usually expressed by the following mathematical equation 1 (Stoney, Proceedings of the Royal Society of London A 82(1909) 172).
  • ⁇ represents the stress generated between the film and the substrate
  • E represents the Young's modulus of the substrate
  • v s represents the Poisson's ratio of the substrate
  • h s and h f represent the thicknesses of the substrate and the film, respectively
  • R represents the radius of curvature corresponding to the bending deformation.
  • d glass is the total thickness of the plate glass on which ion exchange is performed, and it is assumed that DOL has a value less than half of the total thickness of the plate glass.
  • the exchange layer In order for the thickness of the DOL layer inserted in mathematical expression 2 to be applied to the Stoney relation, the exchange layer must have a uniform composition and the physical properties such as Poisson's ratio and Young's modulus must be maintained the same within the thickness of the film (i.e., the thickness of the exchange layer).
  • the thickness of the exchange layer it is a well-known fact that ion exchange occurs by mutual diffusion, and the distribution of ion-exchanged ions within the DOL layer is not constant.
  • C(x,t) represents the concentration at the depth x from the surface where ion exchange occurs and at the time t when ion exchange occurs
  • C 0 represents the concentration of the corresponding alkali ion present in the plate glass before ion exchange
  • A is a constant
  • D represents the diffusion coefficient corresponding to the corresponding mutual diffusion.
  • Figure 1 is a modified version of a concentration distribution graph by general diffusion.
  • the concentration distribution graph may have different shapes depending on time, and as the depth increases from the glass surface, the concentration of the intruded alkali ions gradually converges to 0.
  • the total amount of ion-exchanged alkali ions can be quantitatively determined by calculating the area corresponding to the integral in the shape of Fig. 1.
  • the diffusion coefficient D can be approximated through inverse calculation from the diffusion depth obtained after ion exchange, and can be expressed in a simplified form by the following mathematical expression 4.
  • the area represents the total amount of alkali ions that have invaded, and the thickness at which the total amount is maintained constant at the concentration of C(0,t) at the polar surface where the maximum stress occurs can be assumed, and this is defined as the newly given effective diffusion length (d eff ).
  • the effective diffusion length since the concentration of alkali ions is the same as the concentration at the polar surface within the effective diffusion length by definition, the factor can be directly applied to the Stoney relation.
  • Figure 2 shows the concentration distribution and effective diffusion length for the glass depth.
  • Fig. 2 schematically represents the effective diffusion length that can be defined from the concentration distribution.
  • the effective diffusion length can be determined by finding the distance at which the red area representing the total amount of alkali ions that have penetrated and the blue area having the same concentration as C(0,t), which is the initial concentration at the polar surface, become equal.
  • the effective diffusion length corresponding to the thickness of the uniform exchange layer having the concentration at the polar surface can be defined from the blue area that becomes equal to the red area.
  • the effective diffusion length can be expressed by the following mathematical expression 5, and if the concentration distribution is expressed in the form of a residual function as in mathematical expression 3, it corresponds to 0.514 times the DOL. It is a matter of course that the effective diffusion length can be derived by calculating the area using a numerical analysis method even in a situation where the concentration distribution is not expressed in the form of a residual function.
  • DOL can be corresponded to the diffusion depth measured by an optical method such as a surface stress meter (FSM) (optical DOL, hereinafter collectively referred to as ‘DOL’).
  • FSM surface stress meter
  • the effective diffusion length can be derived by calculating the area using a numerical analysis method.
  • the effective diffusion length in this case can be expressed as in mathematical expression 6.
  • ⁇ is a parameter having a value between 0 and 1.
  • the corresponding ⁇ value can be set to a constant value when the actual integral area is the same, and additionally, the value can fluctuate in consideration of the error range that occurs in the measurement of CS and the stress that causes the actual bending deformation.
  • the diffusion depth obtained from the concentration distribution can be converted into an effective diffusion length, and as a result, the relationship can be utilized by dividing the film layer (or exchange layer) and the substrate layer (or non-exchange layer) having a uniform composition that satisfies the application conditions of the Stoney relationship. Therefore, the bending deformation in the glass where ion exchange is complete can be expressed as follows.
  • mathematical expression 8 includes ion exchange time and diffusion coefficient assuming elastic deformation, and since the temperature dependence of the diffusion coefficient corresponding to ion exchange occurring in glass is already well known in the field, mathematical expression 8 relates the radius of curvature and stress of the corresponding plate glass according to the ion exchange time and temperature.
  • Equation 8 deals with the case where ion exchange occurs on only one side of the glass plate, it can also deal with the more general case where ion exchange occurs on both sides of the glass plate. That is, the CS and/or DOL may or may not be formed differently on both sides of the glass plate, thereby causing curvature.
  • Equation 9 the final curvature radius that occurs due to the difference in the curvature radius that occurs on each side of the glass plate can be expressed by Equation 9 below.
  • the CS and DOL of both sides of the glass plate are the same as in mathematical expression 8, no warpage deformation will occur, and even if the CS and DOL of both sides are formed differently, the size of the overall warpage deformation of the glass plate can be determined. That is, in order to intentionally induce warpage deformation, the CS or DOL applied to each side can be made different. As a specific example, by applying a dry ion exchange process, the CS or DOL can be formed differently by applying different glass thicknesses, coating thicknesses, compositions within the coating, and heat treatment conditions.
  • mathematical expressions 7 or 9 may be utilized, and the magnitude of the bending deformation, DOL and CS occurring during single-sided or double-sided ion exchange may be determined through the relationships.
  • B is the linear network dilation coefficient (LNDC)
  • E Young's modulus
  • v Poisson's ratio
  • C(x,t) is the concentration of exchanged ions at an arbitrary depth x and ion exchange time t
  • C * (t) is the total average concentration of exchanged ions at an arbitrary time t
  • R(t) denotes the stress relaxation effect over time.
  • B can be expressed by the following mathematical expression 11.
  • V represents the volume of the glass where ion exchange occurs.
  • the change in the volume of the glass due to the total amount of ions that have invaded due to the introduction of B can be calculated, and as a result, the compressive stress caused by the invaded ions can be calculated.
  • Equation 12 when it is assumed that there is no stress relaxation effect in Equation 10, the stress can be expressed in a simplified form as in Equation 12.
  • the stress distribution obtained from the concentration distribution can be calculated by utilizing Equation 10 or 12, and consequently, ⁇ (0,t), which means the surface compressive stress, can also be calculated.
  • the CS obtained through this calculation can be utilized in Equation 7 or 9.
  • CS can be considered as a constant ⁇ 0 . That is, CS can be considered as a constant because it varies less under given ion exchange conditions than DOL and contributes less to the final radius of curvature change in Equation 8.
  • CS considered as a constant can be the surface compressive stress measured from an optical measuring device after ion exchange is performed at an appropriate ion exchange temperature and time. Therefore, CS measured after ion exchange can be utilized as a constant term in Equation 8.
  • Figure 3 shows the stress distribution and effective stress for the glass depth.
  • Figure 3 schematically represents the effective stress that can be defined from the stress distribution.
  • CS can be regarded as effective stress (CS eff ). It can be easily inferred that the stress representing the deformation in the actual Stoney relation is not the same as the CS occurring after ion exchange in the CS utilized in the Stoney relation. Therefore, the effective stress can be determined by obtaining the stress at which the red area, which means the actual stress amount up to the effective diffusion length defined above in the stress distribution, becomes equal to the blue area having the same stress at the effective diffusion length. In other words, it can be defined as a single layer having the same stress from the blue area equal to the red area to the effective diffusion length.
  • the corresponding effective stress can be expressed by the following mathematical expression 13, and since it is possible to assume that the stress distribution simply follows the concentration distribution, if the concentration distribution is expressed in the form of an error function as in mathematical expression 3, it corresponds to 0.722 times the compressive stress CS mea measured by an optical method such as a surface stress meter (FSM). It is a well-known fact that the effective stress can be derived by calculating the area using a numerical analysis method even in a situation where the concentration distribution is not expressed in the form of a differential error function.
  • FSM surface stress meter
  • the range of suitable conditions in which CS can be utilized as an effective stress in the Stoney relationship based on elastic behavior is, for example, an ion exchange temperature less than 600°C and a DOL less than 15 ⁇ m, and preferably, the ion exchange temperature may be set to 500°C or less and a DOL less than 10 ⁇ m, but in other conditions, mathematical expression 8 may be utilized by substituting the effective stress derived from the measured CS value.
  • the present invention also defines plastic deformation that deviates from elastic deformation based on the Stoney relation mentioned above. It provides a mathematical expression related to additional deformation that occurs plastically in addition to the mathematical expression related to elastic deformation that is finally obtained.
  • the stress relaxation effect occurs significantly and plastic deformation occurs. This causes a difference between the mathematical expression based on the Stoney relation defined in the present invention and the actual value. It is known that ion exchange occurs elastically, but when the structural relaxation effect due to ⁇ -relaxation occurs, not only does stress decrease due to the change in elastic-plastic strain, but also shape change occurs additionally.
  • This invention utilizes a previously known stress calculation formula to calculate plastic deformation caused by chemical strengthening. Attempts to calculate stress caused by chemical strengthening have been continuously made, and thus, formulas for calculating stress caused by ⁇ -relaxation plastically already exist. However, these formulas were all designed for the purpose of comparing with actual stress and assume full ion exchange, and it has been confirmed that there is no attempt to calculate partial or full deformation due to shape change caused by actual ⁇ -relaxation.
  • Figure 4 shows various strain distributions caused by stress after ion exchange.
  • Figure 4 illustrates various strain distributions that occur after ion exchange, which are known to exist.
  • the chemical strengthening method by ion exchange can cause various strain distributions depending on the assumption (Varshneya, International Journal of Applied Glass Science 1 (2010) 131).
  • the strain distribution when the stress occurring only in the ion exchange depth layer after ion exchange is perfectly elastic can be defined as ⁇ C and can be expressed by mathematical equation 14.
  • the calculation is performed by integrating up to d, which is the glass thickness, and dividing by d, so that the stress in the ion exchange depth layer has the opposite sign to the stress occurring in the non-ion exchange layer.
  • B, V 0 , and ⁇ represent the linear network dilation coefficient (LNDC), constant part of Varshneya factor, and relative concentration, respectively.
  • ⁇ is a constant term for ⁇ -relaxation.
  • the strain after actual ion exchange assumes elastic deformation, so plastic deformation must be additionally calculated as plastic changes such as ⁇ -relaxation occur during the stress generation process.
  • the true strain was calculated to obtain the strain value at which ⁇ -relaxation occurred, which is a simple difference between two extreme cases and can be expressed by the following mathematical equations 18 and 19.
  • the above plastic strain change refers to the change in strain that occurs plastically by ⁇ -relaxation.
  • the final plastic strain change can be expressed as Equation 21.
  • the width change was calculated.
  • the width length change that occurs at this time corresponds to the plastic strain value that varies with depth in the ion exchange depth layer, but the average width change up to the ion exchange depth layer was defined for the purpose of simplifying the equation. Therefore, the strain expressed in mathematical expression 21 was multiplied by the width of the glass to obtain the strain, and the final width change was obtained by utilizing the integration up to the ion exchange depth layer, which can be expressed as mathematical expression 22.
  • the relative concentration ⁇ utilized in mathematical expressions 14 to 17 and 21 to 22 can be expressed by the following mathematical expression 23.
  • C s, C i and C 0 represent the concentration of exchanged alkali at the polar surface, the concentration of the corresponding alkali existing inside the glass before ion exchange and the concentration of the alkali to be ion exchanged existing inside the glass before ion exchange, respectively.
  • Figure 5 is a schematic diagram of the change in curvature caused by a change in width.
  • Equation 25 A schematic diagram of the width change that occurs when curvature occurs is illustrated in Fig. 5.
  • the curvature change that occurs due to plastic width change can be calculated by a simple geometric method, and can be expressed as Equation 25 by substituting Equation 24.
  • Equation 24 it is assumed that the width change as in Equation 24 occurs between the half position in the ion exchange depth layer and the half position in the non-ion exchange layer.
  • the above mathematical expression 25 is a calculation expression for the curvature that occurs plastically due to ⁇ -relaxation.
  • the width change is calculated by utilizing the plastic strain, and the mathematical expression for the plastic bending deformation is established in a simple geometrical manner through the above assumption, and it is confirmed that the calculation is possible by utilizing the concentration distribution of the glass after ion exchange, the ⁇ -relaxation coefficient, and the glass thickness.
  • the viscoelastic curvature can be expressed by simply adding the plastic curvature to the elastic curvature when mathematical expression 8 is re-expanded as an expression for the curvature. Therefore, the final expression that simultaneously reflects the plastic bending deformation can be expressed as mathematical expression 26.
  • Mathematical expression 26 can also be used for each curvature in Mathematical expression 9, and it simultaneously explains the plastic curvature change due to ⁇ -relaxation, which means that plastic deformation can also be intentionally induced along with stress on the glass surface.
  • mathematical expressions 25 to 26 can be utilized to calculate additional plastic curvature that cannot be explained by elastic curvature based on Stoney's relation.
  • the expression for plastic curvature can occur under suitable conditions, such as, for example, an ion exchange temperature that is excessively high or an ion exchange time that is excessively long, and the range of the suitable conditions is, for example, an ion exchange temperature of 600°C or higher, a DOL of 5 ⁇ m or higher, and preferably, an ion exchange temperature of 580°C or higher, a DOL of 10 ⁇ m or higher.
  • plastic curvature can occur under conditions of lower or higher temperature and shorter or longer ion exchange time, and can be derived through mathematical expressions 25 to 26.
  • the type of alkali used in the exchange may be Li, not K. Since the mathematical formula provided herein can calculate the diffusion depth of alkali moving from the outside to the inside of the glass through diffusion and the surface stress, the type of alkali penetrating into the glass may be replaced depending on whether the composition of the glass is lithium aluminosilicate (LAS) or sodium aluminosilicate (NAS), and the corresponding alkalis include Li, Na, K, Rb, Cs, etc.
  • LAS lithium aluminosilicate
  • NAS sodium aluminosilicate
  • the stress CS can be expressed as a negative tensile stress or a positive compressive stress, and when the stress is a negative value, the curvature can have a negative value, and when the stress is a positive value, the curvature can have a positive value.
  • the elastic curvature can be calculated using mathematical equations 7 and 9 that utilize the final diffusion depth, surface stress, and diffusion coefficient, and the plastic curvature can be calculated using mathematical equation 25 that utilizes glass-related constants and concentration distribution terms. Therefore, it is a matter of course that the mathematical equations provided in this application are not limited to the type of alkali and the composition of glass.
  • the plate glass used is sodium alumino-silicate glass having a composition of 61.22SiO 2 - 17.02Al 2 O 3 - 11.94Na 2 O - 4.22K 2 O - 4.29MgO - 1.01ZrO 2 - 0.3SnO 3 (wt%), a thickness of 100 ⁇ m, and a size of 40 ⁇ 10 mm 2 .
  • CS and DOL measured in one or more embodiments were measured via FSM, and CS or DOL obtained using optical or chemical measuring devices that measure other surface compressive stress and diffusion depth, including FSM, can also be utilized herein.
  • a slurry prepared by adding TiO 2 : KNO 3 in a molar ratio of approximately 34:66 to 100 ml of water solvent was sprayed at a pressure of 8 bar from a distance of 1 m using a general gravity spray gun to form a coating film on the cross-section of the glass.
  • the average thickness was 60 ⁇ m, and the error range by location was ⁇ 10 ⁇ m.
  • ion exchange heat treatment was performed at 350 ° C. for 90 minutes and then at 425, 440, 460, and 500 ° C. for 15 minutes in a furnace with a transparent quartz window, and this was filmed in real time using a camera with 8K quality to measure the amount of warpage deformation caused at 30-second intervals.
  • Figure 6 is a photograph of glass that has undergone deformation after ion exchange at different temperatures.
  • Figure 6 is a photograph of glass that underwent warpage deformation after ion exchange heat treatment at 425°C, 440°C, 460°C, and 500°C for 15 minutes each. It can be seen that the final warpage deformation amount varies depending on the temperature even though the slurry composition, coating thickness, and ion exchange time are the same. It was also confirmed that a large deformation occurred along one axis by using glass with a large aspect ratio.
  • Figure 7 is a graph showing real-time temperature measurement and glass deformation during heat treatment at 440°C for 15 minutes.
  • Figure 7 shows the change in bending deformation that occurred during ion exchange at 440°C for 15 minutes, measured at 30-second intervals for the part where the greatest phase change occurred at the exact center of the specimen, and the specimen temperature measured in real time while the ion exchange was in progress.
  • the tip of the temperature-measuring thermocouple was placed next to the glass to record the temperature in real time, and it was confirmed that the temperature set in the furnace and the actual recorded temperature were within the error range of ⁇ 5°C.
  • the amount of bending deformation gradually increased over time, but the amount of increase gradually decreased.
  • Figure 8 is a graph of the amount of glass deformation measured in real time according to ion exchange temperature
  • Figure 9 is a graph of the strain rate of glass measured in real time according to ion exchange temperature.
  • Fig. 8 shows the bending deformation measured at 30-second intervals in real time during cross-sectional ion exchange at 350°C, 425°C, 440°C, 460°C, and 500°C
  • Fig. 9 shows the strain rate measured at 30-second intervals at various ion exchange temperatures. The measurements were performed at least three times for each temperature, and the average values are shown. It can be confirmed that the value of the bending deformation at the same time gradually increases as the ion exchange temperature increases, but it can be confirmed that the overall deformation behavior is very similar. In addition, as a result of checking the strain rate at 30-second intervals, it was confirmed that the deformation occurs very quickly at the beginning regardless of the temperature, and then the strain rate gradually decreases over time.
  • Example 1 The results obtained in Example 1 were used to compare the results of real-time bending deformation with the results of calculation using the relational formula.
  • Figure 10 is a graph of glass curvature measured in real time according to ion exchange temperature.
  • Figure 10 shows the result of converting the bending deformation measured in Figure 8 into curvature.
  • D 0 is a constant
  • E a activation energy
  • R is the gas constant
  • T is the absolute temperature.
  • the diffusion coefficient according to the temperature can be obtained through the mathematical expression 13
  • the diffusion depth obtained through the diffusion coefficient can be obtained through the simplified mathematical expression 4 using the diffusion coefficient D as mentioned above. If the diffusion coefficient is known through mathematical expression 4, the DOL can be obtained, and the effective diffusion length can be calculated through the DOL.
  • Figure 11 shows the temperature-dependent diffusion coefficient of sodium alumino-silicate glass.
  • Figure 11 shows the temperature-dependent diffusion coefficient obtained by fitting the diffusion coefficient D obtained when the slurry composition of Example 1 is used in the sodium alumino-silicate glass used in this experiment to the mathematical expression 27.
  • Figure 12 shows the calculation of the effective diffusion length according to the virtual ion exchange time.
  • Figure 12 is a graph showing the effective diffusion length calculated at each ion exchange temperature using the data obtained in Figure 11 and plotted against an arbitrary time.
  • Figure 13 shows the relevant indicators of glass used in the calculation of the relational expression
  • Figure 14 shows the ⁇ 0 value used in the calculation by ion exchange temperature
  • Figure 15 (a) shows the change in curvature over time when CS by ion exchange temperature is a constant ⁇ 0
  • Figure 15 (b) shows the change in curvature over time by actual ion exchange temperature.
  • Fig. 13 shows the constant values utilized in using Equations 7 to 8.
  • Fig. 14 shows the CS values measured by FSM according to the ion exchange conditions at each temperature.
  • Fig. 15 (a) shows the change in curvature over time calculated when CS for each ion exchange temperature is defined as a constant of ⁇ 0 when calculating the final curvature by inputting the CS value based on Fig. 12.
  • Fig. 15 (b) shows the change in actual curvature over time for comparison. Three data were measured for each specimen on the surface where ion exchange was performed, and the average was plotted. As a result, it was confirmed that the curvature value obtained by calculating with ⁇ 0 showed a value very similar to the actually measured curvature value.
  • the experimentally obtained curvature was converted into a curvature strain that reflects the change in curvature over time, and the differential equation obtained by differentiating Equation 8 with respect to time was fitted to verify the applicability of the calculated CS, and a comparison was made with the actual measured CS value.
  • the equation obtained by differentiating Equation 8 with respect to time can be expressed as follows.
  • Figure 16 shows the time-dependent curvature strain of a cross-sectional ion-exchange glass at 425°C for 15 minutes, the behavior of the curvature strain calculated by the measured CS, and the behavior of the fitting equation.
  • Fig. 16 shows the curvature strain measured at 30-second intervals during cross-sectional ion exchange at 425°C for 15 minutes, considering the change in curvature at 30-second intervals, and comparing it with the obtained deformation obtained by fitting it to Equation 28 and the curvature strain simply calculated by inputting the measured CS into Equation 28.
  • the ⁇ value was set to 0.514.
  • the actual measured CS is 601 ⁇ 20 MPa, which is the value shown in Fig. 14, but the CS obtained by fitting Equation 28 to the measured curvature strain is 531 ⁇ 36 MPa, which is some difference, but it was confirmed that it is almost similar.
  • Figure 17 shows the change in curvature strain fitting CS according to ⁇ at different temperatures.
  • Fig. 17 shows the change in CS fitted according to various ⁇ values for the curvature strain measured in four temperature bands used in the experiment, and the average CS by DOL measured by FSM.
  • the difference between the fitting and the measured CS in the above 2-2-2 example can usually be caused by the measurement error of stress and the difference in concentration distribution, and this can be expressed by the variability of ⁇ applied to mathematical expression 7 or mathematical expression 28. Therefore, the change in CS obtained with various ranges of ⁇ values was confirmed.
  • the CS when the ⁇ value changes from 0 to 1, the CS can show a change amount of at least ⁇ 20 MPa compared to the measured value, which means that the error range by the FSM measurement can be considered.
  • Figure 18 is about the CS measurement values used for the ion exchange temperature and time-dependent calculation
  • Figure 19 (a) is about the change in curvature (line) over time when CS is ⁇ 0 for each ion exchange temperature and the curvature (symbol) calculated with the measured CS
  • (b) is about the change in curvature over time for each actual ion exchange temperature.
  • Fig. 18 shows the actual CS values according to each ion exchange condition
  • Fig. 19 (a) shows the symbols calculated by inserting the actual CS values in Fig. 15 and plotting the same actual curvature values
  • Fig. 19 (b) shows the same actual curvature values.
  • the curvature was calculated by inserting the actual CS values for all specimens on which the actual experiment was performed and this was displayed as a symbol.
  • Figure 20 shows the expected curvature change over time at different ion exchange temperatures
  • Figure 21 shows the expected curvature change over time at different CS temperatures at 425°C
  • Figure 22 shows the expected curvature change over time at different CS temperatures at 425°C.
  • Fig. 20 shows the change in curvature that occurs over time according to the ion exchange temperature, that is, the diffusion coefficient, when the properties of the glass used in the cross-sectional ion exchange are the same.
  • Figs. 21 and 22 show the expected change in curvature according to CS that occurs according to the ion exchange time and DOL, respectively, at a temperature of 425°C. As shown in Fig. 20, it can be confirmed that as the temperature increases, that is, as the diffusion coefficient increases, the curvature shows a larger deformation amount over time, assuming that the CS has a constant value of 600.8 MPa.
  • Fig. 20 shows the change in curvature that occurs over time according to the ion exchange temperature, that is, the diffusion coefficient, when the properties of the glass used in the cross-sectional ion exchange are the same.
  • Figs. 21 and 22 show the expected change in curvature according to CS that occurs according to the ion exchange time and DOL, respectively, at a temperature of 425
  • Figure 23 shows the CS, DOL, and curvature measurement values for each ion exchange condition used in calculating the effective diffusion length
  • Figure 24 shows the effective film thickness (x-axis) calculated by the Stoney relationship and the effective diffusion length (y-axis) calculated from the concentration distribution.
  • Fig. 23 shows the CS, DOL measured by FSM for the glass on which the ion-exchange condition experiment was performed, and the curvature obtained through image analysis.
  • Fig. 24 compares the effective film thickness (d cal ) calculated using the CS measured by FSM and the curvature measured after ion exchange in Equation 1, which is the existing Stoney relationship, with the effective diffusion length (d eff ) calculated from the concentration distribution equation used in Equation 7, and the value calculated using Equation 5.
  • the effective film thickness can be calculated using the data of Fig. 23, and the effective diffusion length can be calculated by integrating the concentration distribution of K ions obtained by performing component analysis by line scan on the cross-section of the glass through SEM-EDS measurement as in Fig. 2. As a result of comparing these, it was confirmed that the effective film thickness and effective diffusion length had the same values within the error range, and it was confirmed that the definition of effective diffusion length can be applied to actual ion-exchanged glass.
  • Figure 25 shows the distribution of alkali ion concentration along the depth of a cross-section of a cross-section of an ion-exchange glass at 425°C for 7 minutes as measured by SEM-EDS
  • Figure 26 shows a comparison of the optical DOL measured by FSM and the chemical DOL measured by SEM-EDS.
  • Fig. 25 is an example of the concentration distribution of K obtained by performing SEM-EDS analysis on a cross-section of a specimen that underwent cross-sectional ion exchange heat treatment at 425°C for 7 minutes.
  • Fig. 26 is a graph comparing the optical DOL measured by FSM and the chemical DOL, which is the depth at which the K concentration converges to 0 through cross-sectional line scan for a SEM-EDS cross-sectional ion exchange specimen.
  • the optical DOL and the chemical DOL must be the same. Therefore, the optical DOL measured by FSM and the chemical DOL obtained through SEM-EDS cross-sectional measurement were compared.
  • the distribution of alkali ions according to the depth measured through SEM-EDS is representatively shown in Fig. 25.
  • the specimen was subjected to cross-sectional ion exchange heat treatment at 425°C for 7 minutes through the same slurry and coating process as Example 1. Thereafter, the coating film was lightly washed with water, dried, fractured, and a line scan was performed on the cross-section. Thereafter, the obtained K concentration according to depth was fitted to mathematical equation 3, and the depth where it converges to 0 was defined to obtain the chemical DOL. Thereafter, the measured optical DOL and chemical DOL were compared, and this is shown in Fig. 26. For the 14 ion exchange conditions shown in Fig. 23, the optical DOL and chemical DOL were confirmed to be the same within the error range, and this confirmed that the optical DOL can be expressed as an effective diffusion length in terms of the concept of chemical DOL.
  • Figure 27 shows a comparison of the effective diffusion length obtained from the concentration distribution area and the effective diffusion length calculated as a constant multiple of the optically measured DOL.
  • the effective diffusion length calculated by SEM-EDS measurement and the effective diffusion length calculated as a constant multiple of the optical DOL measured by FSM are compared.
  • the same slurry/coating method as in Example 1 was applied, and glasses for a total of 14 ion-exchange temperature and time conditions were manufactured, and component analysis was performed on the K concentration in the depth direction through a cross-sectional line scan for the SEM-EDS cross-sectional ion-exchange specimen, and the effective diffusion length was calculated through the integrated area.
  • the effective diffusion length of the concentration distribution having the aforementioned error function form by the mathematical method is 0.514 times the optical DOL
  • the effective diffusion length was calculated simply through a constant multiple of the optical DOL.
  • the two effective diffusion lengths calculated in this way were compared, and as a result, it was confirmed that most of the values were within the error range. This confirms that the effective diffusion length can be calculated by multiplying only the optical DOL measured by FSM without actual concentration analysis.
  • Figure 28 shows the CS, DOL, and curvature measurement values for each ion exchange condition used in calculating the effective stress
  • Figure 29 shows the effective stress (x-axis) calculated from the stress distribution obtained from the concentration distribution and the stress (y-axis) calculated using the Stoney relationship of mathematical expression 7.
  • Fig. 28 shows the CS measured by FSM, the effective diffusion length, and the curvature obtained through image analysis for the glass on which the ion-exchange experiment was performed.
  • Fig. 29 compares the effective stress (CS eff ) calculated from the stress distribution assumed to be the same as the concentration distribution used in Equation 27, and the stress calculated by substituting the effective diffusion length calculated from the DOL measured by FSM and the curvature measured after ion exchange into Equation 7, which is the Stoney relationship provided in this application.
  • the stress can be calculated through Equation 7 using the data of Fig. 28, and assuming that the stress distribution is the same as the concentration distribution of K ions obtained by performing component analysis by line scan on the cross-section of the glass through SEM-EDS measurement as in Fig.
  • the effective stress can be calculated through integration as in Equation 13. As a result of comparing these, it was confirmed that the stress calculated by the Stoney relation and the effective stress had the same value within the error range, and it was confirmed that the definition of the effective stress could be applied to actual ion-exchanged glass.
  • Figure 30 shows a comparison of the effective stress obtained from the area and the effective stress calculated as a constant multiple of the optically measured stress, assuming that the concentration distribution is identical to the stress distribution.
  • the effective stress calculated by SEM-EDS measurement is compared with the effective stress calculated as a constant multiple of the optical CS measured by FSM.
  • the same slurry/coating method as in Example 1 was applied, and glasses for a total of 14 ion-exchange temperature and time conditions were manufactured, and component analysis was performed on the K concentration in the depth direction through a cross-sectional line scan for the SEM-EDS cross-sectional ion-exchange specimen, and then the effective stress was calculated through the integrated area under the assumption that the result is the same as the stress distribution.
  • the effective stress of the stress distribution having the above-mentioned error function form by the mathematical method is 0.722 times the optically measured CS mea .
  • the effective stress was calculated simply by a constant multiple of the CS mea .
  • the two effective stresses calculated in this way were compared, and as a result, it was confirmed that most of the values were within the error range. This confirmed that the effective stress can be calculated by only using a constant multiple of CS mea measured by FSM, without actual concentration analysis and stress analysis.
  • Example 3-1 Example of curvature occurrence due to different diffusion coefficients
  • Figure 31 shows the heat treatment conditions and CS/DOL of the air/tin side of general float glass. Journal of the Australian Ceramic Society 57 (2021) 1331), and Fig. 32 is about the bending deformation according to the glass length, and Fig. 33 is about the diffusion coefficient of the air and tin side of the general float glass ( Journal of the Australian Ceramic Society 57(2021) 1331), Fig. 34 shows the change in curvature over time obtained under heat treatment conditions at 425°C for 8 hours, and Fig. 35 shows the control of the amount of deformation under ion exchange conditions at 435°C for 12 hours of general float glass.
  • Figure 31 shows the CS and DOL according to the heat treatment conditions of the air and tin sides of the glass produced by the aforementioned float method
  • Figure 33 shows the diffusion coefficient obtained from Figure 31 ( Journal of the Australian Ceramic Society 57 (2021) 1331).
  • the composition of the glass is 72.33 SiO 2 - 13.45 Na 2 O - 0.06 K 2 O - 8.43 CaO - 4.4 MgO - 0.2 SO 3 and the glasses used are 60 ⁇ 60 mm 2 in size and 1.1, 1.8, and 4 mm thick.
  • the glass produced by the float method has a different glass composition on the tin side in contact with the tin bath and the air side exposed to the air due to tin, which directly leads to a difference in the diffusion coefficient.
  • Fig. 34 is the result calculated with a specimen size of 60 ⁇ 60 mm 2 .
  • the warpage deformation caused by the inherent diffusion coefficient difference becomes a big problem, and this is shown in Fig. 32. It can be confirmed that the amount of warpage deformation gradually increases as the glass length becomes longer, and as a result, the float glass has warpage that cannot be ignored when the existing immersion ion exchange is performed due to the difference in diffusion coefficient.
  • Figure 36 shows the conditions for non-deformation and the difference in curvature radius on the air/tin side in general float glass.
  • the unit cm of 1/R before and 1/R after in Fig. 36 means the unit of R before and R after , respectively, and the actual unit of 1/R before and 1/R after is 1/cm.
  • FIG. 36 illustrates the expected CS and DOL in which no deformation occurs by controlling ⁇ 0 or DOL of the air side when ⁇ 0 and DOL of the tin side are maintained using the diffusion coefficient and ⁇ 0 obtained in FIG. 23.
  • FIG. 35 illustrates the change in curvature over time for one of the data of FIG. 36. It can be seen through the above-described examples that the CS or DOL formed on the glass surface can be controlled by controlling the composition, thickness, etc. of the slurry, and thus the CS or DOL as in FIG. 36 can be formed. Accordingly, when the curvature is 0, the bending deformation according to the glass length is also fixed to 0, so that a specific condition in which no deformation occurs regardless of the glass length can be established.
  • FIG. 35 illustrates the change in curvature over time when the bending deformation becomes 0 under ion exchange conditions at 435°C for 12 hours. It can be confirmed that the bending deformation continuously converges to 0 regardless of time.
  • Figure 37 is about the relevant parameters of soda-lime silicate glass utilized in stress calculation (Macrelli, International Journal of Applied Glass Science 11 (2020) 730).
  • Fig. 37 is a table showing the parameters for calculating the stress distribution and CS obtained from the concentration distribution of ion-exchanged alkali ions using mathematical equation 12.
  • the composition of the glass from which the parameters were derived is 70.98 SiO 2 - 0.57 Al 2 O 3 - 0.03 Fe 2 O -3 - 0.04 TiO 2 - 12.85 Na 2 O - 0.04 K 2 O - 8.87 CaO - 6.44 MgO - 0.15 SO 3 (mol%) (Macrelli, International Journal of Applied Glass Science 11 (2020) 730).
  • the thickness direction concentration distribution of the ion-exchanged alkali ions was assumed to follow a typical error function modification as in mathematical equation 3, and the surface relative concentration of the ion-exchanged alkali ions was assumed to be 0.9.
  • Figure 38 shows the calculated values of CS according to changes in thickness and DOL
  • Figure 39 shows the changes in CS according to changes in DOL and thickness.
  • Fig. 38 shows the CS calculation results when DOL is 10, 30, 50, and 100 ⁇ m in glasses having a soda-lime silicate composition with thicknesses of 1.0, 2.0, and 3.0 mm, respectively
  • Fig. 39 is a drawing showing the CS results of Fig. 38 with respect to DOL.
  • the CS calculation results described in Figs. 38 and 39 it was confirmed that the calculated CS decreases as the thickness of the glass and DOL increase.
  • the CS decreases because the total average concentration of ion exchange, C * (t), in Equations 10 and 12 increases.
  • the change in the CS value calculated from the data in Figs. 38 and 39 was confirmed to have a difference of up to ⁇ 15 MPa in the thickness range of 1.0-3.0 mm and the DOL range of 10-100 ⁇ m, and it can be confirmed that the difference is within about 4% compared to the average CS.
  • Figure 40 is a graph of the amount of glass deformation measured in real time according to ion exchange temperature
  • Figure 41 is a graph of the strain rate of glass measured in real time according to ion exchange temperature.
  • Fig. 40 shows the bending deformation measured at 30-second intervals in real time during cross-sectional ion exchange at 580°C and 600°C
  • Fig. 41 shows the strain rate measured at 30-second intervals at various ion exchange temperatures. The measurements were performed at least three times for each temperature, and the average values are shown. It can be confirmed that the value of the bending deformation at the same time gradually increases as the ion exchange temperature increases, but it can be confirmed that the overall strain behavior is very similar. In addition, as a result of checking the strain rate at 30-second intervals, it was confirmed that the deformation occurs very quickly at the beginning regardless of the temperature, and then the strain rate gradually decreases over time.
  • Figure 42 relates to the relevant indices of glass used in the calculation of the relational formula
  • Figure 43 relates to the CS, DOL, and curvature measurement values used in the calculation according to the conditions for each ion exchange temperature.
  • Example 4 The results obtained in Example 4 were used to compare the results of real-time bending deformation with the results of calculation using the relational formula.
  • Figure 44 is a graph of glass curvature measured in real time according to ion exchange temperature.
  • Figure 44 shows the result of converting the bending deformation measured in Figure 40 into curvature.
  • the material properties such as CS and DOL can be determined by the bending deformation over time without measuring with a measuring device such as an actual FSM.
  • the diffusion coefficient can be utilized in the calculation.
  • the measured width change can be utilized through the optimized plastic deformation relation of Equation 25 to determine the concentration distribution, ⁇ -relaxation-related coefficients, etc.
  • Figure 45 is a graph of the glass sintering curvature measured in real time according to ion exchange temperature.
  • Fig. 45 the elastic curvature is calculated using Equation 8 and Figs. 42 to 43, and the plastic curvature measured through the difference of the elastic curvature calculated from the measured curvature value using Equation 26 is shown.
  • the results including the conditions of Example 1 as well as Example 4 are shown. It was confirmed that the plastic shape change occurred due to the excessively high ion exchange temperature, and that the difference in curvature occurred at a level exceeding the error range only at 580°C and 600°C as follows. In particular, it was confirmed that the plastic curvature occurred gradually over time at 580°C, and that the plastic curvature occurred from the beginning of the ion exchange at 600°C.
  • Figure 46 is a graph comparing the calculated plastic curvature and the actual curvature according to ion exchange conditions.
  • Fig. 46 the measured plastic curvature values over time at 580°C and 600°C among the data shown in Fig. 45 are compared with the calculated plastic curvature values calculated using the mathematical expression 25.
  • the plastic curvature values were calculated using the concentration distribution measured by Fig. 42 and SEM-EDS, and the results compared with the data shown in Fig. 45 show very good matching behavior.
  • the plastic bending strain obtained through mathematical expression 25 can define a plastic strain that deviates from the Stoney relation that explains the elastic bending strain.
  • the final bending strain can be accurately calculated even under conditions where plastic deformation occurs by utilizing mathematical expression 26.
  • the same parameter values as in Fig. 42 were utilized in the glass composition and size utilized in this example, it is a natural fact that the values of the corresponding parameters may be different if the glass composition or size is different.
  • a slurry was prepared by adding TiO 2 : LiNO 3 in a molar ratio of approximately 63:37 to 100 ml of water solvent, and sprayed at a pressure of 8 bar and a distance of 1 m using a general gravity spray gun to form a coating film on the cross-section of the glass.
  • the average thickness was 60 ⁇ m, and the error range by location was ⁇ 10 ⁇ m.
  • ion exchange heat treatment was performed in a furnace with a transparent quartz window at 200°C for 15 minutes, 250°C for 12 minutes, 280°C for 5.3 minutes, 300°C for 3.2 minutes, 320°C for 2 minutes, and 350°C for 0.8 minute. This was filmed in real time using an 8K resolution camera to measure the amount of bending deformation that occurred at 30-second intervals.
  • Figure 47 shows photographs of glass that was deformed after ion exchange at different temperatures using LiNO 3 slurry.
  • Figure 47 is a photograph of glass that underwent warpage deformation after ion exchange heat treatment at 200°C for 15 minutes. As in Example 1, a coating film was formed on the upper side of the glass, but the amount of warpage deformation occurred with a negative value, and it was confirmed that deformation occurred along one axis by using glass with a large aspect ratio.
  • Figure 48 is a graph of the curvature of glass measured in real time according to ion exchange temperature.
  • Fig. 48 is the curvature calculated through the bending deformation measured at real-time 30-second intervals during cross-sectional ion exchange at 200, 250, 280, 300, 320, and 350°C. The measurements were performed at least three times for each temperature, and the average values are shown. It can be seen that tensile stress, not compressive stress, occurs on the surface as alkali with a smaller ionic radius than alkali inside the glass diffuses into the glass, which causes negative stress and obtains a negative curvature value. In addition, it can be confirmed that the absolute value of the curvature gradually increases at the same time as the ion exchange temperature increases, but the overall deformation behavior is similar and can be confirmed to exhibit a behavior similar to Example 1.

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Abstract

La présente demande concerne un procédé de détermination de la déformation par bombage d'un verre à glace. Dans le procédé, le rayon de courbure du verre à glace correspondant à la déformation par bombage du verre est déterminé en fonction d'une expression relationnelle de Stoney et/ou d'une expression relationnelle de déformation élastique-plastique qui reflète une configuration pour des changements de largeur, une première couche et une deuxième couche incluses dans l'expression relationnelle de Stoney pouvant être définies de sorte que, en fonction d'une valeur obtenue par intégration d'une distribution de concentration jusqu'à une couche de profondeur d'échange d'ions après échange d'ions de verre comprenant un alcali, et d'une longueur de diffusion efficace, qui est la profondeur calculée pour avoir la même zone dans l'hypothèse où la concentration de surface reste la même en fonction de la profondeur, l'épaisseur correspondant à la longueur de diffusion efficace dans l'épaisseur du verre à glace est considérée comme étant la première couche, et l'épaisseur excluant la longueur de diffusion efficace de l'épaisseur du verre à glace est considérée comme étant la deuxième couche, et la contrainte plastique incluse dans l'expression relationnelle de déformation plastique-plastique peut être définie de sorte que, en fonction de changements de largeur se produisant après l'échange d'ions dans le verre à glace par l'intermédiaire d'un changement de forme provoqué par un effet de relaxation structurelle dû à une relaxation α, des changements de largeur se produisant progressivement en fonction de la concentration au niveau de la couche de profondeur d'échange d'ions sont moyennés pour fournir une valeur unique, les changements de largeur étant supposés se produire à partir de la demi-profondeur de la couche de profondeur d'échange d'ions jusqu'à la demi-profondeur d'une couche de profondeur sans échange d'ions, par l'intermédiaire d'un procédé géométrique simple, et la courbure plastique se produisant en fonction des changements de largeur.
PCT/KR2024/016123 2023-10-23 2024-10-23 Procédé de détermination de déformation par bombage de verre à glace, procédé de fabrication de verre le mettant en œuvre, et verre fabriqué au moyen dudit procédé de fabrication Pending WO2025089764A1 (fr)

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KR10-2023-0142371 2023-10-23
KR20230142371 2023-10-23
KR10-2024-0144869 2024-10-22
KR1020240144869A KR20250058695A (ko) 2023-10-23 2024-10-22 판 유리의 휨 변형량 결정 방법, 이를 이용한 유리의 제조 방법, 및 유리의 제조 방법에 의해 제조된 유리

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014182641A1 (fr) * 2013-05-07 2014-11-13 Corning Incorporated Moules compensés permettant de fabriquer des couvercles de verre tridimensionnels à renforcement d'échange d'ions
JP2016169143A (ja) * 2015-03-10 2016-09-23 旭硝子株式会社 化学強化ガラス
WO2016204087A1 (fr) * 2015-06-15 2016-12-22 旭硝子株式会社 Verre chimiquement renforcé
KR20190124278A (ko) * 2017-03-02 2019-11-04 코닝 인코포레이티드 낮은 휨 및 높은 내손상성 유리 물품을 위한 비대칭 응력 프로파일
KR20210037021A (ko) * 2013-10-14 2021-04-05 코닝 인코포레이티드 이온 교환 공정 및 이로부터 결과하는 화학적으로 강화된 유리 기판

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014182641A1 (fr) * 2013-05-07 2014-11-13 Corning Incorporated Moules compensés permettant de fabriquer des couvercles de verre tridimensionnels à renforcement d'échange d'ions
KR20210037021A (ko) * 2013-10-14 2021-04-05 코닝 인코포레이티드 이온 교환 공정 및 이로부터 결과하는 화학적으로 강화된 유리 기판
JP2016169143A (ja) * 2015-03-10 2016-09-23 旭硝子株式会社 化学強化ガラス
WO2016204087A1 (fr) * 2015-06-15 2016-12-22 旭硝子株式会社 Verre chimiquement renforcé
KR20190124278A (ko) * 2017-03-02 2019-11-04 코닝 인코포레이티드 낮은 휨 및 높은 내손상성 유리 물품을 위한 비대칭 응력 프로파일

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