CN117486488A - Chemically strengthened glass and glass device comprising same - Google Patents

Chemically strengthened glass and glass device comprising same Download PDF

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Publication number
CN117486488A
CN117486488A CN202210895438.5A CN202210895438A CN117486488A CN 117486488 A CN117486488 A CN 117486488A CN 202210895438 A CN202210895438 A CN 202210895438A CN 117486488 A CN117486488 A CN 117486488A
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CN
China
Prior art keywords
chemically strengthened
strengthened glass
glass
equal
tensile stress
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CN202210895438.5A
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Chinese (zh)
Inventor
覃文城
袁小彬
华文琼
黄昊
朱广祥
陈杰杰
黄义宏
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Huawei Technologies Co Ltd
Chongqing Aureavia Hi Tech Glass Co Ltd
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Huawei Technologies Co Ltd
Chongqing Aureavia Hi Tech Glass Co Ltd
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Application filed by Huawei Technologies Co Ltd, Chongqing Aureavia Hi Tech Glass Co Ltd filed Critical Huawei Technologies Co Ltd
Priority to CN202210895438.5A priority Critical patent/CN117486488A/en
Priority to PCT/CN2023/105864 priority patent/WO2024022064A1/en
Publication of CN117486488A publication Critical patent/CN117486488A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/02—Tempering or quenching glass products using liquid
    • C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
    • 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
    • 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
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)

Abstract

The application provides chemically strengthened glass and a glass device comprising the chemically strengthened glass, wherein the chemically strengthened glass meets the following conditions: the tensile stress linear density CT_LD of the chemically strengthened glass is larger than or equal to 40000MPa/mm, the ratio of CT_LD/S is larger than or equal to 7.5 and smaller than or equal to 20, so that the obtained chemically strengthened glass has excellent anti-falling performance, and in the preparation process of the chemically strengthened glass, the content of lithium ions released by the glass into a salt bath is less than that of the existing lithium aluminum silicon glass, thereby being beneficial to prolonging the service life of the salt bath, and ensuring that the chemically strengthened glass produced has stable anti-falling performance.

Description

Chemically strengthened glass and glass device comprising same
Technical Field
The present application relates to the field of glass technology, and in particular, to chemically strengthened glass and glass devices comprising chemically strengthened glass.
Background
In recent years, lithium aluminum silicon reinforced glass has been widely used for display protection covers of mobile phones and rear covers of mobile phones. Along with the updating iteration of the smart phone, the requirements of mobile phone manufacturers on the anti-falling performance of cover glass are higher and higher, and the anti-falling performance of the existing lithium aluminum silicon glass products is insufficient. In the face of the high requirements of the market on the anti-falling performance, some products realize the improvement of the anti-falling height by carrying out a large amount of ion exchange, namely, the anti-falling height is improved by increasing the ion exchange amount to obtain enough stress level. However, the ion exchange capacity is large, so that excessive volume change is easily formed on the surface layer of the substrate glass after strengthening, the dispersion of the anti-drop height distribution of samples in the same batch is large, the probability of low anti-drop height in the samples in the same batch is increased, and the anti-drop performance of the chemically strengthened glass produced in mass production is extremely unstable. Meanwhile, the large ion exchange amount means that in the process of preparing the chemically strengthened glass, the large amount of lithium ions released by the glass into the salt bath can lead to the shortened service life of the salt bath, thereby increasing the manufacturing cost of the lithium aluminum silicon reinforced glass, in particular the reinforcing cost.
Therefore, developing a chemically strengthened glass that can reduce manufacturing costs, has improved drop resistance, and ensures that mass produced chemically strengthened glass has more stable drop resistance will greatly increase the competitiveness of the product.
Disclosure of Invention
The object of the present application is to provide a chemically strengthened glass having improved drop resistance and to ensure that a mass produced chemically strengthened glass has more stable drop resistance. The specific technical scheme is as follows:
a first aspect of the present application provides a chemically strengthened glass that satisfies the following conditions: the tensile stress linear density CT_LD of the chemically strengthened glass is larger than or equal to 40000MPa/mm, and the ratio of CT_LD/S is larger than or equal to 7.5 and smaller than or equal to 20; the chemically strengthened glass comprises a compressive stress layer positioned on the surface of the chemically strengthened glass and a tensile stress layer positioned inside the chemically strengthened glass, wherein an X-ray energy spectrum analyzer is used for testing a signal intensity distribution curve corresponding to the sodium element content of the chemically strengthened glass along the thickness direction, the signal intensity distribution curve is fitted into a smooth curve, the area of a graph formed by x=x1, x=x2, y=y0 and the smooth curve is S, X1 is a test depth value corresponding to the surface of the chemically strengthened glass, X2 is a test depth value corresponding to the place where the compressive stress is zero, and y0 is an intensity value corresponding to the sodium element content in the tensile stress layer in the smooth curve.
In some embodiments of the present application, the surface CS of the chemically strengthened glass is greater than or equal to 900MPa and less than or equal to 1600MPa, preferably greater than or equal to 1000MPa and less than or equal to 1600MPa.
In some embodiments of the present application, the depth of layer of compressive stress dol—0 of the chemically strengthened glass is from 0.15t to 0.22t, where t is the thickness of the chemically strengthened glass.
In some embodiments of the present application, the Young's modulus of the chemically strengthened glass is greater than or equal to 85GPa, preferably greater than or equal to 90GPa.
In some embodiments of the present application, the chemically strengthened glass has a tensile stress linear density, CT_LD, of greater than or equal to 42000MPa/mm and less than or equal to 70000MPa/mm, preferably greater than or equal to 43000MPa/mm and less than or equal to 70000MPa/mm.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～18.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 0～10.00mol％、Na 2 O 2.00～8.00mol％、MgO 0～8.00mol％。
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, further comprises: b (B) 2 O 3 0 to 5.00mol%, preferably B 2 O 3 0～3.00mol％。
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 0～8.00mol％、La 2 O 3 0.10～3.00mol％。
In some embodiments of the present application, the composition in the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, satisfies: la (La) 2 O 3 /Y 2 O 3 0.2 to 1.0; and/or
Al 2 O 3 +Li 2 O.ltoreq.22.00 mol%, preferably Al 2 O 3 +Li 2 O≤20.00mol％。
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, further comprises: 0 to 3.00mol percent of SrO, and the SrO/(MgO+SrO) is less than or equal to 0.35; and/or K 2 O 0～3.00mol％。
In some embodiments of the present application, srO/(MgO+SrO). Ltoreq.0.35 in mole percent of oxide.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 1.00～8.00mol％、La 2 O 3 0.20～1.50mol。
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, satisfies: siO (SiO) 2 64.00 to 70.00mol% and/or Li 2 O8.00-12.00 mol% and/or Na 2 4.00 to 6.00mol percent of O and/or 2.00 to 7.50mol percent of MgO and/or La 2 O 3 0.20～1.50mol％。
In some embodiments of the present application, the composition of the substrate glass, expressed as mole percent of oxides, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 1.00～8.00mol％、La 2 O 3 0.20～3.00mol％，La 2 O 3 /Y 2 O 3 0.2 to 1.0.
In some embodiments of the present application, the composition of the substrate glass, expressed as mole percent of oxides, comprises: siO (SiO) 2 64.00～70.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 8.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 4.00～6.00mol％、MgO 2.00～7.50mol％、La 2 O 3 0.20～1.50mol％。
In some embodiments of the present application, 0.7mm thick chemically strengthened glass is tested for sag resistance using 120 mesh sandpaper, with an average sandpaper sag resistance height greater than or equal to 1.60m, preferably greater than or equal to 1.70m.
In some embodiments of the present application, the chemically strengthened glass, 0.7mm thick, is subjected to a drop test using 120 mesh sandpaper, and the sandpaper drop height has a B10 value of greater than or equal to 1.1m, preferably 1.1 to 2.0m.
In some embodiments of the present application, the B10 value of the 0.7mm thick chemically strengthened glass sandpaper drop height is no more than 25% less than the average sandpaper drop height, and the number of sandpaper used in the test is 120 mesh.
In a second aspect, the present application provides a glass device made from the chemically strengthened glass of any one of the embodiments described above.
A third aspect of the present application provides an electronic device comprising the chemically strengthened glass of any one of the embodiments described above.
In some embodiments of the present application, the electronic device comprises a cell phone, tablet, smart wearable, display, or television. Wherein, intelligent wearing includes intelligent bracelet, intelligent wrist-watch and intelligent glasses etc. and the display includes high definition display, on-vehicle display, avionics display etc..
Any one of the technical schemes has the following beneficial effects:
the application provides the chemically strengthened glass with improved anti-falling performance, and the content of lithium ions released into the salt bath during preparation of the chemically strengthened glass is less than that of the existing lithium aluminum silicon glass, so that the service life of the salt bath is prolonged, and the strengthening cost is reduced. And the reduction of the ion exchange amount is beneficial to reducing the dispersion of the drop-resistant height distribution of batch samples, and ensures that the chemically strengthened glass produced in mass has stable drop-resistant performance.
Of course, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other embodiments may be obtained according to these drawings by a person having ordinary skill in the art.
FIG. 1 is a schematic diagram of the chemically strengthened glass of example 3 as measured by a Brookfield EDS-X-ray spectroscopy analyzer;
FIG. 2 is a graph showing the signal intensity distribution curve corresponding to the sodium element content of the chemically strengthened glass of example 3;
FIG. 3 is a smoothed curve of the signal intensity distribution curve of FIG. 2, which is fitted;
FIG. 4 is a schematic diagram showing the temperature distribution of a long quartz tank in a crystallization upper limit temperature test;
FIG. 5 is a graph of a sample in a long quartz cell after crystallization upper limit temperature test.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. Based on the embodiments herein, a person of ordinary skill in the art would be able to obtain all other embodiments based on the disclosure herein, which are within the scope of the disclosure herein.
Interpretation of the terms
Chemically strengthened glass: is strengthened glass treated by a high-temperature ion exchange process. Alkali metal ions with large ion radius replace alkali metal ions with small ion radius in glass in high-temperature salt bath to generate exchange ion volume difference, and high-to-low compressive stress is generated on the surface layer of the base material glass from the surface to the inside to block and delay the expansion of glass microcracks, so that the aim of improving the mechanical strength of the glass is fulfilled.
Substrate glass: is a glass base material which is not strengthened.
Surface CS: surface compressive stress/surface compressive stress, after chemical strengthening of the glass, alkali metal ions with smaller surface radius are replaced by alkali metal ions with larger radius, and compressive stress is generated on the surface of the glass due to the crowding effect of the alkali metal ions with larger radius. Measured by a stress meter FSM-6000 of Japanese foldaway (Orihara).
Dol_0: the depth of layer of compressive stress, also referred to as the depth of layer of compressive stress, refers to the distance of any surface of the glass from a location near that surface where the compressive stress is zero. Measured by a stress meter SLP-2000 of Japanese foldaway (Orihara).
CT_LD: the tensile stress linear density is obtained by recording the ratio of the fixed integral of the tensile stress curve of the tempered glass to the thickness of the tempered glass. The substrate glass is placed in a salt bath for ion exchange to form a strengthening layer (compressive stress layer/compressive stress layer), in the ion exchange process, a tensile stress layer is formed inside the glass, the tensile stress layer is provided with an upper boundary which is separated from the upper surface of the chemically strengthened glass by a certain interval and a lower boundary which is separated from the lower surface of the chemically strengthened glass by a certain interval, a curve drawn by a certain point on a line segment which is perpendicular to the upper boundary and the lower boundary and in which the upper and lower endpoints respectively fall on the upper boundary and the lower boundary at the same time in the tensile stress layer is marked as a tensile stress curve, and a ratio of a fixed integral of the tensile stress curve to the thickness of the strengthened glass is marked as a tensile stress line density. I.e., the ratio of the sum of tensile stresses of the strengthened glass to the thickness of the glass as measured by the SLP-2000 stress meter.
CT_LD max : the substrate glass is subjected to ion exchange chemical strengthening under the specific salt bath condition, and the maximum tensile stress linear density (CT_LD) value which can be obtained is the maximum tensile stress linear density CT_LD which can be obtained under the salt bath condition of the substrate glass max . This data can characterize the strengthening/ion-exchangeable properties of the substrate glass.
In the chemical strengthening process, as the strengthening time increases, the tensile stress linear density (CT_LD) value obtained by the substrate glass tends to increase and decrease, and the maximum value CT_LD of the tensile stress linear density obtained by strengthening under the specific salt bath condition can be determined by continuously monitoring the change condition of the tensile stress linear density in the glass in the strengthening process max 。
The inventors of the present application have found that, when the conventional lithium aluminum silicon chemically strengthened glass is subjected to chemical strengthening treatment, a large amount of sodium ions and lithium ions are exchanged, and that a high stress level can be achieved by introducing a large amount of sodium ions into the base glass, or a large amount of sodium ions can be introduced into the glass due to excessive strengthening. The exchange amount of sodium ions and lithium ions is large, excessive volume change is easy to form on the surface layer of the glass, and under the condition of small volume change in the glass, the original microcracks on the surface of the glass are easy to expand, so that the dispersion of the anti-drop height distribution of the chemically strengthened glass produced in quantity is large, the probability of low anti-drop height in samples in the same batch is increased, the anti-drop performance of the chemically strengthened glass produced in quantity is extremely unstable, and the use experience of the final product is influenced. Meanwhile, a high stress level is achieved through a large amount of sodium-lithium exchange, and the amount of lithium ions precipitated into the salt bath is increased, so that the service life of the salt bath is reduced, and the production cost of mass production is increased.
In view of the above, the present application provides a chemically strengthened glass, and a glass device and an electronic apparatus including the chemically strengthened glass. In the application, the ion exchange stress effect refers to the stress effect generated by exchanging the same amount of ions when the substrate glass is subjected to ion exchange in the chemical strengthening treatment process, and the ion exchange stress effect is different when different glass structures are different. In general, the higher the ion exchange stress effect, the less ion exchange is required to achieve high levels of stress.
A first aspect of the present application provides a chemically strengthened glass that satisfies the following conditions: the tensile stress linear density CT_LD of the chemically strengthened glass is greater than or equal to 40000MPa/mm, preferably the tensile stress linear density CT_LD is greater than or equal to 42000MPa/mm and less than or equal to 70000MPa/mm, more preferably the tensile stress linear density CT_LD is greater than or equal to 43000MPa/mm and less than or equal to 70000MPa/mm; the value of CT_LD/S is greater than or equal to 7.5 and less than or equal to 20; the chemically strengthened glass comprises a compressive stress layer positioned on the surface of the chemically strengthened glass and a tensile stress layer positioned inside the chemically strengthened glass, wherein an X-ray energy spectrum analyzer is used for testing a signal intensity distribution curve corresponding to the sodium element content of the chemically strengthened glass along the thickness direction, the signal intensity distribution curve is fitted into a smooth curve, the area of a graph formed by x=x1, x=x2, y=y0 and the smooth curve is S, X1 is a test depth value corresponding to the surface of the chemically strengthened glass, X2 is a test depth value corresponding to the place where the compressive stress is zero, and y0 is an intensity value corresponding to the sodium element content in the tensile stress layer in the smooth curve.
The chemical strengthening glass meets specific stress design requirements by controlling the values of the tensile stress linear density CT_LD and CT_LD/S within the range, for example, the tensile stress linear density CT_LD can be 40000MPa/mm, 42000MPa/mm, 43000MPa/mm, 45000MPa/mm, 50000MPa/mm, 55000MPa/mm, 60000MPa/mm, 65000MPa/mm, 70000MPa/mm or values in a numerical range formed by taking any two values as the endpoints, and the ratio of the CT_LD/S can be 7.5, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or values in a numerical range formed by taking any two values as the endpoints. Wherein, the range of S can be 3000-6500.
In some embodiments of the present application, the surface CS of the chemically strengthened glass is greater than or equal to 900MPa and less than or equal to 1600MPa, preferably greater than or equal to 1000MPa and less than or equal to 1600MPa. For example, the surface CS of the chemically strengthened glass may be 900MPa, 950MPa, 1000MPa, 1050MPa, 1100MPa, 1150MPa, 1200MPa, 1250MPa, 1300MPa, 1350MPa, 1400MPa, 1450MPa, 1500MPa, 1550MPa, 1600MPa, or a value in a numerical range formed by using any two of the above values as an end point, which indicates that the chemically strengthened glass provided by the present application has excellent scratch resistance, deformation resistance, and the like.
The application meets specific stress design requirements by controlling the chemically strengthened glass, namely, the stress characteristics are controlled to meet the following conditions: the tensile stress linear density CT_LD is larger than or equal to 40000MPa/mm, CT_LD/S is larger than or equal to 7.5 and smaller than or equal to 20, so that the strengthening cost is reduced and the dispersion of the anti-drop height distribution of the chemically strengthened glass in the same batch is improved while the excellent anti-drop performance of the chemically strengthened glass is ensured.
In some embodiments of the present application, the depth of layer of compressive stress dol—0 of the chemically strengthened glass is from 0.15t to 0.22t, where t is the thickness of the chemically strengthened glass. For example, the depth of layer of compressive stress dol—0 may be 0.15t, 0.16t, 0.17t, 0.18t, 0.19t, 0.20t, 0.21t, 0.22t, or any two values therebetween. The thickness of the glass before and after chemical strengthening varies very little and is almost negligible. The depth of compressive stress layer DOL_0 was obtained using an SLP-2000 stress meter test. When the depth of the compressive stress layer dol—0 is within the above range, the compressive stress layer is deep enough to better prevent the generated crack from entering the tensile stress layer when the glass is in contact with a sharp object, thereby being beneficial to improving the drop resistance. The thickness t of the base glass may be selected according to the thickness of the chemically strengthened glass required, and is not limited in this application. Illustratively, the thickness of the substrate glass may be 0.4 to 2.0mm.
In some embodiments of the present application, the Young's modulus of the chemically strengthened glass is greater than or equal to 85GPa, preferably greater than or equal to 90GPa. For example, the Young's modulus of the chemically strengthened glass may be 85GPa, 86GPa, 87GPa, 88GPa, 89GPa, 90GPa, 95GPa, 100GPa, or a value within a numerical range constituted by taking any two of the above values as an end point. The chemically strengthened glass provided by the application has higher Young modulus.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～18.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 0～10.00mol％、Na 2 O 2.00～8.00mol％、MgO 0～8.00mol％。
During chemical strengthening, ions with large radius in the salt bath are exchanged with ions with small radius in the glass, so that a compressive stress layer is formed on the surface of the glass, and a tensile stress layer is formed inside the glass. Compared with the substrate glass before strengthening, the composition of the compressive stress layer is changed due to the occurrence of ion exchange, and the composition of the tensile stress layer in the glass is not changed because the ion exchange depth is generally smaller than or equal to the thickness of the compressive stress layer, namely, the composition of the tensile stress layer is the same as the composition of the substrate glass before strengthening.
In some embodiments of the present application, siO 2 The content of (C) may be 60.00mol%, 61.00mol%, 62.00mol%, 63.00mol%, 64.00mol%, 65.00mol%, 66.00mol%, 67.00mol%, 68.00mol%, 69.00mol%, 70.00mol%, 71.00mol%, 72.00mol%, 73.00mol%, 74.00mol%, 75.00mol% or a range of values defined by any two of the above values as the end pointsA numerical value; it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments of the present application, al 2 O 3 The content of (C) may be 8.00mol%, 9.00mol%, 10.00mol%, 11.00mol%, 12.00mol%, 13.00mol%, 14.00mol%, 15.00mol%, 16.00mol%, 17.00mol%, 18.00mol% or a value within a numerical range formed by taking any two of the above values as an end point; it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments of the present application, li 2 The content of O may be 7.00mol%, 7.50mol%, 8.00mol%, 8.50mol%, 9.00mol%, 9.50mol%, 10.00mol%, 10.50mol%, 11.00mol%, 11.50mol%, 12.00mol% or a value within a numerical range constituted by any two of the above values as an end point; it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments of the present application, Y 2 O 3 The content of (C) may be 0mol%, 1.00mol%, 2.00mol%, 3.00mol%, 4.00mol%, 5.00mol%, 6.00mol%, 7.00mol%, 8.00mol%, 9.00mol%, 10.00mol% or a value within a numerical range constituted by any two of the above values as the end points; it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments of the present application, na 2 The content of O may be 2.00mol%, 3.00mol%, 4.00mol%, 5.00mol%, 6.00mol%, 7.00mol%, 8.00mol% or a value within a numerical range constituted by taking any two of the above values as an end point; it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments of the present application, the MgO content may be 0mol%, 1.00mol%, 2.00mol%, 3.00mol%, 4.00mol%, 5.00mol%, 6.00mol%, 7.00mol%, 7.50mol%, 8.00mol%, or a value within a range of values inclusive of any two of the above; it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In preferred embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, further comprises: b (B) 2 O 3 0 to 5.00mol%, preferably B 2 O 3 0～3.00mol％。B 2 O 3 The addition of (2) is beneficial to reducing the melting temperature of the glass and improving the exchange speed of sodium ions and lithium ions in the chemical strengthening treatment process, but the intrinsic structure of the chemically strengthened glass can be influenced by the excessive content, thus controlling B 2 O 3 The content of (B) is within the above range, for example, B 2 O 3 The content of (C) is 0.00mol%, 0.50mol%, 1.00mol%, 1.50mol%, 2.00mol%, 2.50mol%, 3.00mol% or a value within a numerical range formed by taking any two values as the end points.
The substrate glass corresponding to the reinforced glass can be produced by the following preparation methods: overflow, float, and calender. The float process has the advantages of high yield, large sheet size, low cost and the like compared with other methods. However, the inventor of the present application found that the existing lithium aluminum silicon reinforced glass capable of realizing high stress level and high mechanical property is generally not suitable for mass production by a float process, because the aluminum content in the base material glass is too high, the melting temperature of the glass is increased, the material property is shortened, and the viscosity of the glass liquid is further reduced between 800 ℃ and 1200 ℃ to be increased. Meanwhile, aluminum and lithium are one of main components for separating out spodumene crystals, the upper crystallization limit temperature of glass can be increased due to the fact that the content of aluminum and/or lithium is too high, and crystallization defects and even devitrification can be generated in the float process of the glass, so that the glass cannot be produced by adopting a float process. Thus, the substrate glass produced in a typical float process is expressed as mole percent of oxides, wherein Al 2 O 3 And Li (lithium) 2 The content of O is not more than 12mol%. But Al is 2 O 3 The reduction of the content is disadvantageous for improving the stress effect generated by unit ion exchange, li 2 The reduction of the O content is not beneficial to the improvement of the exchange amount of sodium ions and lithium ionsAnd is disadvantageous in improving deep compressive stress and young's modulus. Due to the limitation of the float process, al in the substrate glass suitable for the mass production of the float process 2 O 3 And Li (lithium) 2 The limited O content results in a maximum value CT_LD of tensile stress linear density that can be obtained by chemical strengthening of the substrate glass produced by the existing float method max Maximum value CS of surface compressive stress max The substrate glass is lower than the prior art, which can produce chemically strengthened glass having high stress levels and high mechanical properties. That is, the mechanical strength of the chemically strengthened glass produced by the conventional substrate glass produced by the float process is relatively low, and thus the mechanical strength of the products (such as mobile phone cover plate, aviation glass, automobile glass, etc.) produced from the chemically strengthened glass is relatively low, which cannot meet the actual demands.
Based on the problems, the formula is optimized, so that the substrate glass corresponding to the chemically strengthened glass capable of meeting the performance requirements of the application can also be produced in a mass manner by adopting a float process.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 0～8.00mol％、La 2 O 3 0.10 to 3.00mol percent. For example, siO 2 The content of (C) may be 60.00mol%, 61.00mol%, 62.00mol%, 63.00mol%, 64.00mol%, 65.00mol%, 66.00mol%, 67.00mol%, 68.00mol%, 69.00mol%, 70.00mol%, 71.00mol%, 72.00mol%, 73.00mol%, 74.00mol%, 75.00mol% or a value within a numerical range constituted by any two of the above values as the end points; al (Al) 2 O 3 The content of (C) may be 8.00mol%, 8.50mol%, 9.00mol%, 9.50mol%, 10.00mol%, 10.50mol%, 11.00mol%, 11.50mol%, 12.00mol% or a value within a range of values defined by any two of the above values as the end points; li (Li) 2 The content of O may be 7.00mol%, 7.50mol%, 8.00mol%, 8.50mol%, 9.00mol%9.50mol%, 10.00mol%, 10.50mol%, 11.00mol%, 11.50mol%, 12.00mol% or a value within a numerical range defined by any two of the above values as endpoints; y is Y 2 O 3 The content of (C) may be 1.00mol%, 1.25mol%, 1.50mol%, 1.75mol%, 2.00mol%, 2.25mol%, 2.50mol%, 2.75mol%, 3.00mol% or a value within a range of values defined by any two of the above values as the end points; na (Na) 2 The content of O may be 2.00mol%, 3.00mol%, 4.00mol%, 5.00mol%, 6.00mol%, 7.00mol%, 8.00mol% or a value within a numerical range constituted by taking any two of the above values as an end point; the MgO content may be 0mol%, 1.00mol%, 2.00mol%, 3.00mol%, 4.00mol%, 5.00mol%, 6.00mol%, 7.00mol%, 8.00mol% or a value within a numerical range formed by taking any two of the above values as the end points; la (La) 2 O 3 The content of (C) may be 0.10mol%, 0.20mol%, 0.50mol%, 0.75mol%, 1.00mol%, 1.25mol%, 1.50mol%, 1.75mol%, 2.00mol%, 2.25mol%, 2.50mol%, 2.75mol%, 3.00mol% or a value within a numerical range constituted by taking any two of the above values as an end point.
SiO 2 And Al 2 O 3 Is a main component forming a glass network structure, and the addition of the two components is beneficial to improving the intrinsic strength of the glass. SiO (SiO) 2 The acid resistance of the glass can be improved, and the scratch of the glass can be reduced; al (Al) 2 O 3 The stress effect caused by ion exchange can also be improved. But too much Al 2 O 3 Can increase the melting difficulty and the crystallization upper limit temperature, and excessive SiO 2 The difficulty of melting is also increased.
Y 2 O 3 The glass network structure can be promoted to change in the glass, the formed Si-O-Y bond enables the isolated island network structure in the glass to be reconnected, the glass structure can be improved, the stability of the glass network is increased, and then the unit stress generated by sodium-lithium exchange can be improved, and the stress effect caused by ion exchange is improved. And because of the relatively large atomic mass of Y and relatively large radius, the high field strength of Y in the glass network can lead to the internal free alkali metal and alkaline earth The metal has aggregation effect, and has tightening trend on a network structure, so that the whole structure of the glass is compact in arrangement, the densification degree is high, and the atomic stacking density of the glass can be improved. Thus Y 2 O 3 The existence of the glass can also reduce the structure relaxation degree after the glass is annealed, and meanwhile, the Vickers hardness of the glass can also be improved, and the scratch resistance is improved. But Y is 2 O 3 Too much can lead to the increase of the upper limit of crystallization of glass, and also can affect the ion exchange process and the ion exchange rate and the ion exchange depth due to the too compact structure of the glass.
Alkali metal is the main component participating in ion exchange, na ion is a key exchange ion forming high compressive stress on the surface, and Li ion is a key exchange ion forming deep compressive stress. However, since the alkali metal oxide is in a free state in the glass, the redundant oxygen ions thereof break the bridging oxygen and destroy the network structure of the glass, thereby reducing the intrinsic strength of the glass. And due to Li 2 O is a main component of lithium aluminum silicon crystallization, and excessive O can raise the upper crystallization limit of glass, which causes production difficulty. While Na is 2 Although the increase of O can improve CS, reduce crystallization tendency of the lithium aluminum silicon glass and lower crystallization upper limit temperature, excessive O can prevent sodium-lithium exchange, thereby reducing deep stress and affecting the anti-falling performance of the glass. K (K) 2 The increase in O can lower the crystallization upper temperature, but excessive K ions can hinder the ion exchange rate, especially potassium-sodium ion exchange. Therefore, the content of each alkali metal oxide in the scheme needs to be strictly controlled.
Magnesium oxide (MgO) exists as a network intermediate that has the effect of reducing the high temperature viscosity of glass and can also increase the young's modulus of glass. Because of the small radius of magnesium ions, the filling density in the glass network structure is large, the effect of improving Young's modulus is large, and because of the small radius of magnesium ions, the magnesium ions belong to alkaline earth metal oxides with minimum effect of blocking ion exchange, but excessive magnesium oxide (MgO) can block ion exchange.
La 2 O 3 Can be added so as to contain only Y 2 O 3 Formula of lithium aluminum silicon glassLower crystallization tendency to obtain lower upper crystallization limit temperature, and La 2 O 3 Can further increase the compactness and the intrinsic strength in the glass, but La 2 O 3 If the amount is too large, the stress effect generated per unit exchange amount is affected.
Through optimizing the formula, the crystallization temperature of the substrate glass corresponding to the chemically strengthened glass is less than or equal to 1200 ℃ and the glass liquid has proper viscosity in the preparation process, so that the chemically strengthened glass can be prepared by adopting a float process. In addition, the substrate glass has higher ion exchange stress effect, and can achieve high stress effect under the condition of lower sodium-lithium exchange capacity in the process of preparing chemically strengthened glass by chemical strengthening, and the prepared chemically strengthened glass has excellent mechanical strength. Meanwhile, as the substrate glass has high ion exchange stress effect, when the salt bath is adopted for chemical strengthening, the content of lithium ions released by the glass into the salt bath is less than that of the existing lithium aluminum silicon glass, thereby being beneficial to prolonging the service life of the salt bath. And the reduction of the ion exchange amount is beneficial to reducing the dispersion of the drop-resistant height distribution of batch samples, and ensures the stable strength performance of the chemically strengthened glass produced in mass. The chemical strengthening treatment process is that the base glass is ion exchanged in a salt bath. It is understood that the substrate glass corresponding to the strengthened glass of the present application may also be prepared using other methods known in the art as described above.
In some embodiments of the present application, the composition in the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, satisfies La 2 O 3 /Y 2 O 3 0.2 to 1.0.Y is Y 2 O 3 Is beneficial to improving the stress effect generated by the ion exchange of the substrate glass, la 2 O 3 Can be added so as to contain only Y 2 O 3 The crystallization tendency of the lithium aluminum silicon glass formulation is reduced to obtain lower crystallization upper limit temperature, and La 2 O 3 Can further increase the compactness and the intrinsic strength in the glass, but La 2 O 3 If the amount is too large, the stress effect generated per unit exchange amount is affected. By controlling La 2 O 3 /Y 2 O 3 The ratio of (2) is within the above range, for example, la 2 O 3 /Y 2 O 3 The glass can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 or a numerical value in a numerical range formed by taking any two numerical values as endpoints, and the Young modulus and stress effect of the substrate glass can be ensured to meet the requirements while the crystallization upper limit temperature of the substrate glass is reduced, so that the glass is favorable for float production and the substrate glass with higher Young modulus is favorable for obtaining.
In preferred embodiments of the present application, the composition in the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, satisfies: al (Al) 2 O 3 +Li 2 O.ltoreq.22.00 mol%, preferably Al 2 O 3 +Li 2 O≤20.00mol％。Al 2 O 3 And Li (lithium) 2 O is the main component for separating out spodumene crystal, and Al is regulated and controlled 2 O 3 And Li (lithium) 2 The content of O is within the above range, for example, al 2 O 3 +Li 2 The O can be 16.00mol%, 17.00mol%, 18.00mol%, 19.00mol%, 20.00mol%, 21.00mol% and 22.00mol% or values in a numerical range formed by taking any two values as endpoints, so that crystallization phenomenon in the preparation process can be effectively improved, the influence on the mechanical strength of chemically strengthened glass is avoided, and meanwhile, the glass liquid can be ensured to have longer material property, so that the method is better suitable for a float process.
In preferred embodiments of the present application, the composition in the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, satisfies: la (La) 2 O 3 /Y 2 O 3 0.2 to 1.0, al 2 O 3 +Li 2 O.ltoreq.22.00 mol%, preferably Al 2 O 3 +Li 2 O is less than or equal to 20.00mol percent. The substrate glass corresponding to the chemically strengthened glass can be prepared through a float process, and the obtained substrate glass has good mechanical strength and good anti-drop performance.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, further comprises: 0 to 3.00mol percent of SrO. The addition of SrO is advantageous for reducing the crystallization speed during crystallization, further avoiding the occurrence of crystallization phenomenon, and by adjusting the content of SrO within the above range, for example, the content of SrO may be 0.00mol%, 0.50mol%, 1.00mol%, 1.50 mol%, 2.00mol%, 2.50mol%, 3.00mol% or a value within a value range formed by taking any two values as endpoints, further avoiding the occurrence of crystallization phenomenon.
In some embodiments of the present application, the content of MgO and SrO, expressed as mole percent of oxides, satisfies SrO/(MgO+SrO). Ltoreq.0.35, preferably 0.05. Ltoreq.SrO/(MgO+SrO). Ltoreq.0.35. By adjusting the value of SrO/(mgo+sro) within the above range, for example, the value of SrO/(mgo+sro) may be 0.05, 0.09, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.30, 0.35 or a value within a numerical range formed by taking any two values as endpoints, the ion exchange speed of the substrate glass during the chemical strengthening treatment is advantageously ensured, and the strengthening time is avoided from being too long.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, further comprises: k (K) 2 O0-3.00 mol%, preferably K 2 O1.00-3.00 mol%, more preferably K 2 O 1.00～2.00mol％。K 2 The addition of O is favorable for reducing the crystallization upper limit temperature, but the too high content can influence the ion exchange stress effect by regulating and controlling K 2 The content of O is within the above range, e.g., K 2 The content of O can be 0.00mol%, 0.50.00mol%, 1.00mol%, 1.50mol%, 2.00mol%, 2.50mol%, 3.00mol% or values in a numerical range formed by taking any two values as endpoints, which is beneficial to reducing the crystallization upper limit temperature and ensures that the ion exchange stress effect meets the requirement.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, further comprises: srO 0-3.00 mol%, K 2 O0-3.00 mol%. Corresponding substrates for chemically strengthened glass can be prepared by the float processThe material glass has good mechanical strength, and the obtained base material glass has good anti-drop performance.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, satisfies: siO (SiO) 2 64.00 to 70.00mol% and/or Li 2 O8.00-12.00 mol% and/or Na 2 4.00 to 6.00mol percent of O and/or 2.00 to 7.50mol percent of MgO and/or La 2 O 3 0.20 to 1.50mol percent. That is, the composition of the chemically strengthened glass tensile stress layer satisfies SiO 2 64.00～70.00mol％、Li 2 O 8.00～12.00mol％、Na 2 O 4.00～6.00mol％、MgO2.00～7.50mol％、La 2 O 3 0.20 to 1.50mol% of at least one of the components. By further optimizing the glass formula, the method not only can better meet the requirement of float mass production, effectively avoid crystallization phenomenon, improve the service life of salt bath, but also is beneficial to obtaining chemically strengthened glass with higher mechanical strength.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 1.00～8.00mol％、La 2 O 3 0.20～3.00mol％，La 2 O 3 /Y 2 O 3 0.2 to 1.0.
In some embodiments of the present application, the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxide, comprises: siO (SiO) 2 64.00～70.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O 8.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 4.00～6.00mol％、MgO 2.00～7.50mol％、La 2 O 3 0.20～1.50mol％。
In preferred embodiments of the present application, the chemically strengthened glass is expressed as mole percent of oxideThe composition of the glass tensile stress layer meets the following conditions: la (La) 2 O 3 /Y 2 O 3 0.2 to 1.0, al 2 O 3 +Li 2 O is less than or equal to 22.00mol percent. The substrate glass corresponding to the chemically strengthened glass can be prepared through a float process, and the obtained substrate glass has good mechanical strength and good anti-drop performance.
In some embodiments of the present application, 0.7mm thick chemically strengthened glass is tested for sag resistance using 120 mesh sandpaper, with an average sandpaper sag resistance height greater than or equal to 1.60m, preferably greater than or equal to 1.70m. For example, the average anti-sandpaper drop height may be 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 or values within a range of values defined by any two of the above values as endpoints, indicating that the chemically strengthened glass provided herein has excellent anti-drop properties.
In some embodiments of the present application, the chemically strengthened glass, 0.7mm thick, is subjected to a drop test using 120 mesh sandpaper, and the sandpaper drop height has a B10 value of greater than or equal to 1.1m, preferably 1.1 to 2.0m. For example, the B10 value of the sandpaper drop resistance height may be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 or a value within a range of values defined by any two of the above values as endpoints, indicating that the chemically strengthened glass provided herein has excellent drop resistance.
In some embodiments of the present application, the B10 value of the 0.7mm thick chemically strengthened glass sandpaper drop height is no more than 25% less than the average sandpaper drop height, and the number of sandpaper used in the test is 120 mesh. Wherein, B10 refers to the falling of the same batch of chemically strengthened glass at the height, 10% of the chemically strengthened glass is expected to fail or fail, and the method can be used for evaluating the dispersion of the falling-resistant height distribution of the chemically strengthened glass. For example, the width of the drop Y of the 0.7mm thick chemically strengthened glass drop height compared to the average drop height H0 of the sand paper can be 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or a value in a numerical range formed by taking any two values as endpoints, thereby indicating that the chemically strengthened glass provided by the application has small dispersion of drop height distribution, and ensuring that the chemically strengthened glass produced in a large amount has more stable drop resistance. Wherein y= (H0-B10)/h0×100%.
In a second aspect, the present application provides a glass device made from the chemically strengthened glass of any one of the embodiments described above. For example, the glass device may include, but is not limited to, a cell phone display cover plate, a cell phone battery back cover plate, a notebook screen cover plate, an automotive center glass cover plate, and the like. The chemically strengthened glass has good anti-falling performance, so that the glass device provided by the application also has good anti-falling performance.
A third aspect of the present application provides an electronic device comprising the chemically strengthened glass of any one of the embodiments described above. For example, the electronic device includes a cell phone, tablet, or other electronic terminal, which may include, but is not limited to, a smart wearable (e.g., electronic watch, smart bracelet, smart watch, smart glasses, etc.), a display (e.g., high definition display, in-vehicle display, avionic display, etc.), a television, and the like. Illustratively, an electronic device may include a housing including a front surface, a rear surface, and a side surface, and an electronic component partially within the housing, the electronic component including a display device at or adjacent the front surface of the housing, the chemically strengthened glass provided herein may be applied to the front surface or/and the rear surface or/and the side surface of the housing; preferably, the electronic device may further include a cover article covering the front surface of the case or on the display device, and the chemically strengthened glass provided herein may be applied to the cover article.
The testing method comprises the following steps:
1. testing of tensile stress linear density CT_LD
The tensile stress linear density CT_LD is calculated from the stress parameter measured by the SLP-2000 stress meter, and is the ratio of the sum of the tensile stresses of the chemically strengthened glass measured by the SLP-2000 stress meter to the thickness of the glass.
2.S calculation
The following description is given of example 3, and the other examples are similarly calculated.
The chemically strengthened glass of example 3 was scanned by a BrookEDS-X-ray spectrometer for a cross section, magnification of 250 times, and radiation intensity HV of 10.0KeV, scanning range of 300. Mu.m. As shown in FIG. 1, in order to reduce deviation and accurately test the surface position of the chemically strengthened glass, the initial test position is ten micrometers on the surface of the chemically strengthened glass, the direction indicated by the arrow in FIG. 1 is the test scanning direction, and the distance from the initial scanning position to the surface of the chemically strengthened glass is 14.4 micrometers. Thus, the intensity tends to decrease from low to high and then gradually decrease again in the test chart of 0 to 300. Mu.m. When processing the data, excluding the invalid data from the low to the high, a signal intensity distribution curve corresponding to the sodium element content as shown in fig. 2 is obtained. The smoothed curve shown in fig. 3 is then fitted by an allometric function in professional data mapping software (e.g., sciDAVis, etc.). As can be seen from the graph, as the depth increases, the signal intensity corresponding to the sodium element content gradually decreases, the decreasing speed gradually becomes slow, and finally the signal intensity corresponding to the sodium element content in the tensile stress layer tends to be higher, the signal intensity corresponding to the sodium element content in fig. 3 is y0, and y0=94.8 in fig. 3; in fig. 3, x1 to x2 are the thickness ranges corresponding to the compressive stress layers, x1 is the test depth corresponding to the chemically strengthened glass surface, x2 is the test depth value corresponding to the point where the compressive stress is zero, and x1=14.4 and x2=149.4 in fig. 3. In fig. 3, the area of the graph enclosed by x=x1, x=x2, y=y0 and the smooth curve is S, and the area of the graph can be calculated by professional data drawing software (such as SciDAVis, etc.).
3. Testing of stress parameters
Test conditions of surface CS, potassium sodium stress exchange depth: the test was carried out using a stress meter FSM-6000 of Japanese collagen, with a light source wavelength of 596nm. Before starting the test, the thickness, refractive index and photoelastic coefficient of the sample to be tested are filled into the parameter table, and then the test is performed to obtain the stress parameter value of the sample to be tested.
Test conditions of dol_0 and ct_ld: the test was carried out using a stress meter SLP-2000 of Japanese collagen, the light source wavelength being 518nm. Before starting the test, the thickness, refractive index and photoelastic coefficient of the sample to be tested are filled into a parameter table, the exposure time is adjusted to 5000usec, and then the test is performed to obtain the stress parameter value of the sample to be tested.
The refractive index and the photoelastic coefficient of the glass with different components are different, the refractive index is tested by an Abbe refractometer, and the photoelastic coefficient is tested by a UNIPT ABR-10A dual-frequency laser stress meter.
When the stress parameter of the chemically strengthened glass sample is tested by using the stress meter, the special refractive liquid is firstly dripped on the corresponding stress meter, then the chemically strengthened glass product is wiped clean and placed on a test path, the instrument is set according to the test condition, and then the test is carried out, so that the stress parameter value of the chemically strengthened glass is obtained. Among them, the refractive index of the refractive liquid for SLP-2000 was 1.51, and the refractive index of the refractive liquid for FSM-6000 was 1.72.
4. Young's modulus test
The base glass (25 mm. Times.85 mm. Times.2.5 mm) obtained in the preparation process of each example was placed on a test instrument (manufacturer: kagaku instrument commercial Co., ltd., model MK 7), and then vibrated with a tip portion, and an ultrasonic vibration propagation result was obtained by a receiver placed at the upper end, and then Young's modulus was obtained by the instrument. The Young's moduli of the base glass corresponding to the formulas 1 to 9 in Table 1 are 84GPa, 88GPa, 89GPa, 91GPa, 90GPa, 89GPa, 90GPa, 89GPa in this order, and after the base glass is reinforced, the Young's moduli thereof are further increased, so that the Young's moduli of the obtained chemically reinforced glass are all greater than or equal to 85GPa.
5. Testing of the amount of released lithium ions in salt baths
The mass of the substrate glass (length-width thickness: 50 mm. Times.50 mm. Times.0.7 mm) was measured by using an Shimadzu precision balance and is denoted as m 1 The precision of the balance is ten-thousandth gram, and the model of the balance is AUW120D.
100wt% NaNO at 450 DEG C 3 After ion exchange in salt bath for t hours, the substrate glass is taken out and washed by deionized waterAfter cleaning, the mass was re-tested to be m 2 . Wherein t hours is the time for obtaining the maximum value CT_LD of the tensile stress linear density max Processing time according to the maximum value of the tensile stress linear density CT_LD max Obtained by the test of (2).
The mass increment Deltaw of the base material glass before and after ion exchange is the mass increment brought by sodium ion exchange lithium ion, and Deltaw=m 2 -m 1 The unit is mg. In addition, sodium ions and lithium ions are equimolar exchanged, so Δw=m Na ×n-M Li X n, whereby n= Δw/(M) Na -M Li ) Amount of lithium ions released in salt bath = M Li X n. Wherein M is Na Relative atomic mass of sodium 23, M Li The relative atomic mass of lithium is 7, and n is the mole number of sodium ions or lithium ions exchanged. It is known through calculation that the maximum value CT_LD of the tensile stress linear density is obtained max At the time, the amount of lithium ions released into the salt bath by the 0.7mm thick substrate glass=m Li ×△w/(M Na -M Li )。
6. Testing of crystallization upper limit temperature
The substrate glass is broken into small blocks with the size of 2 mm-5 mm, and then the small blocks are placed into a long quartz groove and are fully paved.
Setting a temperature zone of a gradient furnace with the model JKZC-XJY01, such as a temperature zone of 1050-1225 ℃, wherein each temperature zone takes at least 6 temperature points from high to low.
After the gradient furnace reaches a preset temperature interval, the long quartz groove with the sample is placed in the gradient furnace, so that 6 temperature points respectively correspond to the glass sample at 6 positions in the long quartz groove, and reference is made to fig. 4. Placing the long quartz groove into a gradient furnace for constant temperature and heat preservation for 60-70 min, and taking out the long quartz groove.
And observing the conditions of glass samples at different positions in the long quartz groove, judging that the glass samples are devitrified if the glass samples are devitrified and fogged, and judging that the glass samples are not devitrified if the glass samples are completely transparent. Referring to fig. 5, in the long quartz cell of fig. 5, the upper region is a completely transparent sample, the lower region is a devitrified sample, and a portion of the hazy sample exists between the completely transparent sample and the devitrified sample. For observation, means such as a magnifying glass, a microscope, etc. may be used.
Determining the crystallization upper limit temperature: the crystallization upper limit temperature range is between the temperature point corresponding to the completely transparent sample and the temperature point corresponding to the adjacent devitrification or fogging sample, and the average value of the two temperature points is taken as the crystallization upper limit temperature.
If all glass samples in the long quartz tank are crystallized in the temperature interval set by the gradient furnace, resetting the upper limit temperature of the temperature interval of the gradient furnace, and measuring the upper limit temperature of the crystallization of the glass samples. If all glass samples in the long quartz tank are not crystallized in the temperature interval set by the gradient furnace, resetting the lower limit temperature of the temperature interval of the gradient furnace, and measuring the upper limit temperature of crystallization of the glass samples.
7. Drop height test and calculation of B10
Average sandpaper drop height: the sum of the measured sandpaper drop heights of the glass samples divided by the number of samples measured was used to characterize the glass contact surface cracking resistance.
At least 10 samples were taken per batch for testing, average sandpaper drop height
Where n is the number of glass coupons tested per lot and hi is the height of sandpaper drop resistance for a single coupon test.
The test method for the falling height of the sand paper of the sample comprises the following steps:
step 1: attaching a glass sample to be tested with the length, width and thickness of 158.8mm multiplied by 72.8mm multiplied by 0.7mm to the front surface of a 200g model machine;
step 2: the model machine is placed on a green map LT-SKDL-CD type falling machine, so that a glass sample faces to sand paper and falls down under the impact of a certain falling height, 120-mesh sand paper located right below the model machine is impacted, and the falling posture of a normal mobile phone is simulated.
If the glass sample is not broken, the falling height of the model machine is increased according to a certain rule. For example, the falling height starts from 0.4m, and the sample is subjected to one falling impact, if the sample is not broken, the sample is again fallen by increasing the height by 0.1m each time until the glass sample is broken.
Step 3: the last drop height at which the glass sample was broken was recorded as the sandpaper drop height, for example, the drop height at which the glass sample was broken was 0.5m, and the sandpaper drop height of the sample was 0.4m.
B10 for sandpaper drop height: the statistical value calculated by the weber distribution (Weibull distribution) is the statistical analysis of the anti-sand paper drop height data obtained by testing a plurality of samples, and the discreteness of the anti-sand paper drop height distribution of the samples is considered in calculation. The specific meaning of the application B10 is that the anti-sand paper falling height corresponding to the chemically strengthened glass sample with the failure proportion of 10 percent can be used for evaluating the anti-falling capability of a certain chemically strengthened glass.
Calculation of the sandpaper drop height B10:
the drop height of the sand paper measured by m pieces of chemically strengthened glass is sequentially recorded as N1-Nm. Then, the value of the parameter K of the PERCENTILE function was set to 0.1, and the result obtained by calculating the N1 to Nm data from the function was recorded as the value of B10 for the anti-sandpaper drop height.
Example 1
The glass sample brick is prepared by mixing materials according to the formula 1 formula design in Table 1, adding 0.4wt% (based on the total weight of the formula 1) of clarifying agent sodium chloride, placing the mixture into a platinum crucible, heating the mixture to 1650 ℃ in a high-temperature smelting furnace to melt for 10 hours, pouring the mixture into a forming grinding tool to cool and form, cooling the mixture to 800 ℃, placing the mixture into an annealing furnace, annealing the mixture at 560 ℃ for 2000 minutes, cooling the mixture to 500 ℃ for 300 minutes, preserving the heat for 300 minutes, sequentially cooling the mixture to 400 ℃ and 300 ℃ and 200 ℃ according to the cooling mode, realizing gradient slow cooling, and cooling the mixture to room temperature along with the furnace.
And then performing multi-line cutting, numerical control (CNC) lathe machining, thinning and polishing on the glass sample bricks to obtain substrate glass, wherein the thickness of the substrate glass is 0.7mm.
And then will beThe substrate glass was first treated with 100wt% NaNO at 420 DEG C 3 Treating in a salt bath for 3h, then at 420 ℃ 100wt% KNO 3 And (3) treating in a salt bath for 1h to obtain the chemically strengthened glass, wherein the thickness t of the chemically strengthened glass is 0.7mm.
Examples 2 to 9
The procedure of example 1 was repeated except that the formulation 1 was replaced with the formulations 2 to 9 in Table 1.
Comparative examples 1 to 6
The procedure was as in example 1, except that the strengthening process and formulation were adjusted as in table 2.
The parameters of each example and comparative example are detailed in Table 2, and the results of the performance test are detailed in Table 3.
TABLE 1
Note that: the contents of the respective substances in Table 1 are in mole percent, "/" indicates that the corresponding substances are not present.
TABLE 2
Note that: the "/" in table 2 indicates that no corresponding parameter exists. Taking example 1 as an example, "420 ℃ 100wt% NaNO 3 *3h420℃*100wt％KNO 3 *1h "means that the substrate glass is first subjected to 100wt% NaNO at 420 DEG C 3 Treating in a salt bath for 3h, then at 420 ℃ 100wt% KNO 3 Treatment in a salt bath for 1h gave a chemically strengthened glass, and other examples and comparative examples were analogized.
TABLE 3 Table 3
Referring to table 3, it can be seen from examples 1 to 9 and comparative examples 1 to 4 that the chemically strengthened glass of the present application has a higher average sandpaper drop height, a B10 value of sandpaper drop height, and a lower amplitude reduction Y than the comparative examples, so that the chemically strengthened glass of the present application has excellent drop resistance and a small dispersion of drop height distribution. As can be seen from examples 1 to 9, comparative examples 5 and 6 were subjected to excessive strengthening treatment, and although they had a higher average anti-sandpaper drop height, the drop width Y was significantly higher than in the examples of the present application, indicating that the same batch of samples had a large dispersion of the anti-drop height distribution, which resulted in extremely unstable anti-drop properties of the chemically strengthened glass produced in mass production. In addition, as can be seen from table 3, the surface CS and the depth of layer of compressive stress dol—0 of the examples are equivalent to or better than those of the comparative examples, which indicates that the chemically strengthened glass of the present application can achieve a further increase in mechanical strength or mechanical strength in the prior art, and more importantly, the dispersion of the drop-resistant height distribution of the chemically strengthened glass of the examples is small, so that the chemically strengthened glass produced in mass production can be ensured to have more stable drop-resistant performance.
The crystallization upper limit temperature of the base material glass corresponding to the chemically strengthened glass of the embodiment 3 to the embodiment 6, the embodiment 8 and the embodiment 9 is less than 1200 ℃, the chemically strengthened glass can be produced by adopting a float process, and the prepared chemically strengthened glass has excellent anti-falling performance, and meanwhile, the amount of lithium ions released in the salt bath is low, so that the service life of the salt bath is prolonged, and the production cost of mass production is reduced. Although the upper limit temperature of crystallization of the base glass corresponding to the chemically strengthened glass of comparative examples 1 to 3 and 6 is also lower than 1200 ℃, the reduction width Y is higher than that of the examples, that is, although the comparative examples can also be produced by a float process, the drop resistance and the dispersion of the drop height distribution of the chemically strengthened glass obtained by the application are obviously better than those of the comparative examples.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims (18)

1. A chemically strengthened glass, wherein the chemically strengthened glass satisfies the following conditions:
the tensile stress linear density CT_LD of the chemically strengthened glass is larger than or equal to 40000MPa/mm, and the ratio of CT_LD/S is larger than or equal to 7.5 and smaller than or equal to 20;
the chemically strengthened glass comprises a compressive stress layer positioned on the surface of the chemically strengthened glass and a tensile stress layer positioned inside the chemically strengthened glass, wherein an X-ray energy spectrum analyzer is used for testing a signal intensity distribution curve corresponding to the sodium element content of the chemically strengthened glass along the thickness direction, the signal intensity distribution curve is fitted into a smooth curve, the area of a graph formed by x=x1, x=x2, y=y0 and the smooth curve is S, X1 is a test depth value corresponding to the surface of the chemically strengthened glass, X2 is a test depth value corresponding to the place where the compressive stress is zero, and y0 is an intensity value corresponding to the sodium element content in the tensile stress layer in the smooth curve.
2. A chemically strengthened glass according to claim 1, wherein the surface CS of the chemically strengthened glass is greater than or equal to 900MPa and less than or equal to 1600MPa, preferably greater than or equal to 1000MPa and less than or equal to 1600MPa.
3. The chemically strengthened glass of claim 1, wherein the chemically strengthened glass has a depth of compressive stress layer dol_0 of 0.15t to 0.22t, t being the thickness of the strengthened glass.
4. A chemically strengthened glass according to claim 1, wherein the young's modulus of the chemically strengthened glass is greater than or equal to 85GPa, preferably greater than or equal to 90GPa.
5. A chemically strengthened glass according to claim 1, wherein the tensile stress linear density ct_ld of the chemically strengthened glass is greater than or equal to 42000MPa/mm and less than or equal to 70000MPa/mm, preferably greater than or equal to 43000MPa/mm and less than or equal to 70000MPa/mm.
6. The chemically strengthened glass of claim 1, wherein the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxides, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～18.00mol％、Li 2 O7.00～12.00mol％、Y 2 O 3 0～10.00mol％、Na 2 O 2.00～8.00mol％、MgO 0～8.00mol％。
7. The chemically strengthened glass of claim 6, wherein the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxides, further comprises: b (B) 2 O 3 0 to 5.00mol%, preferably B 2 O 3 0～3.00mol％。
8. The chemically strengthened glass of claim 1, wherein the chemistry is expressed as mole percent of oxidesThe composition of the strengthened glass tensile stress layer comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 0～8.00mol％、La 2 O 3 0.10～3.00mol％。
9. The chemically strengthened glass of claim 8, wherein the composition in the chemically strengthened glass tensile stress layer, expressed as mole percent of oxides, satisfies: la (La) 2 O 3 /Y 2 O 3 0.2 to 1.0; and/or
Al 2 O 3 +Li 2 O.ltoreq.22.00 mol%, preferably Al 2 O 3 +Li 2 O≤20.00mol％。
10. The chemically strengthened glass of claim 8, wherein the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxides, further comprises: 0 to 3.00mol percent of SrO, and the SrO/(MgO+SrO) is less than or equal to 0.35; and/or K 2 O0～3.00mol％。
11. The chemically strengthened glass of claim 1, wherein the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxides, comprises: siO (SiO) 2 60.00～75.00mol％、Al 2 O 3 8.00～12.00mol％、Li 2 O7.00～12.00mol％、Y 2 O 3 1.00～3.00mol％、Na 2 O 2.00～8.00mol％、MgO 1.00～8.00mol％、La 2 O 3 0.20～1.5mol％。
12. The chemically strengthened glass of claim 8, wherein the composition of the chemically strengthened glass tensile stress layer, expressed as mole percent of oxides, satisfies: siO (SiO) 2 64.00 to 70.00mol% and/or Li 2 O8.00-12.00 mol% and/or Na 2 4.00 to 6.00mol percent of O and/or 2.00 to 7.50mol percent of MgO and/or La 2 O 3 0.20～1.50mol％。
13. A chemically strengthened glass according to any one of claims 1 to 12, wherein the chemically strengthened glass is 0.7mm thick and is subjected to a drop resistance test using 120 mesh sandpaper, the average sandpaper drop resistance height being greater than or equal to 1.60m, preferably greater than or equal to 1.70m.
14. A chemically strengthened glass according to any one of claims 1 to 12, wherein the chemically strengthened glass is 0.7mm thick and is subjected to a drop test with 120 mesh sandpaper, the B10 value of the drop height of the sandpaper being greater than or equal to 1.1m.
15. A chemically strengthened glass according to any one of claims 1 to 12, wherein the chemically strengthened glass has a sandpaper drop height B10 value of 0.7mm thick that is no more than 25% reduced compared to the average sandpaper drop height, and the number of sandpaper used in the test is 120 mesh.
16. A glass device, wherein the glass device is made from the chemically strengthened glass of any one of claims 1-15.
17. An electronic device comprising the chemically strengthened glass of any one of claims 1-15.
18. The electronic device of claim 17, wherein the electronic device comprises a cell phone, a tablet, a smart wearable, a display, or a television.
CN202210895438.5A 2022-07-26 2022-07-26 Chemically strengthened glass and glass device comprising same Pending CN117486488A (en)

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