WO2021197146A1 - 一种具有局部增强结构的玻璃及其加工方法 - Google Patents

一种具有局部增强结构的玻璃及其加工方法 Download PDF

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Publication number
WO2021197146A1
WO2021197146A1 PCT/CN2021/082513 CN2021082513W WO2021197146A1 WO 2021197146 A1 WO2021197146 A1 WO 2021197146A1 CN 2021082513 W CN2021082513 W CN 2021082513W WO 2021197146 A1 WO2021197146 A1 WO 2021197146A1
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Prior art keywords
glass
reinforced
structure according
area
zone
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PCT/CN2021/082513
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English (en)
French (fr)
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胡伟
黄昊
谈宝权
陈芳华
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重庆鑫景特种玻璃有限公司
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Publication of WO2021197146A1 publication Critical patent/WO2021197146A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the invention belongs to the technical field of glass products, and in particular relates to a glass with a locally reinforced structure and a processing method thereof.
  • Glass products such as cover glass and glass bottom plates, can be used in consumer and commercial electronic devices, such as LCD and LED displays, computer monitors, and automated teller machines (ATM). Some of these glass products may include a "touch" function, which makes the glass product must be in contact with various objects (including the user's finger and/or stylus device), so the glass must be strong enough to withstand normal contact without damage . In addition, such glass products can also be incorporated into portable electronic devices such as mobile phones, personal media players and tablet computers. With the rapid development of electronic products, the field of electronic equipment has put forward higher requirements for glass-made protective covers, casings, enclosures and other products. They not only require high strength and scratch resistance, but also hope to become thinner and thinner.
  • the thickness of the product is generally in the range of 0.4-2mm, and the glass substrate used is thin glass in the conventional sense.
  • the glass substrate used is thin glass in the conventional sense.
  • the brittleness of the glass itself is high, the fracture toughness is small, and the large number of cracks produced are easy to expand, which leads to a great reduction in the strength of the glass.
  • its light transmittance will inevitably be sacrificed. Therefore, how to improve the strength of the edge region of the glass is a problem that needs to be solved by those skilled in the art.
  • the invention patent CN107555804A is a method for preparing touch screen glass.
  • the edge of the glass is etched to remove the burrs on the edge of the glass, which eliminates stress concentration and makes the edge of the glass more uniform, thereby greatly increasing the strength of the glass.
  • the invention patent CN103108842A discloses a method for strengthening the edge of a glass product.
  • a protective coating or film of polymer or polymer resin is applied on at least one surface of the glass product. The surface may be melted or polished, and/or chemically strengthened or thermally strengthened.
  • CN106536439A discloses a method for strengthening the edge of a liquid crystal display (LCD) or organic light emitting diode (OLED) display glass substrate.
  • the method includes exposing the edge of the display panel to an acid solution, the duration and the temperature Effectively remove glass no more than 20 microns from the edge surface, wash away the acid solution from the edge and apply a polymer protective coating to the cleaned edge to maintain the etched strength of the edge surface.
  • the above method can increase the strength of the glass edge to a certain extent, the chemical corrosion process often causes a decrease in the optical properties of the glass surface, the strength of the glass recovery cannot be sustained, and the attenuation is very serious.
  • Another way is to coat the edge of the glass with a filling liquid to fill up the micro cracks and gaps at the edge of the glass to achieve the purpose of improving the edge strength of the glass.
  • the invention patent CN107628757A discloses a method for improving the edge strength of the flat glass of the display.
  • the environmentally friendly filling liquid is used to fill the micro cracks and gaps on the edge of the flat glass, and then the peripheral edges of the flat glass are irradiated by laser to eliminate the edge.
  • the generated micro-cracks, gaps and edge chipping, etc. will not pollute the environment and are more environmentally friendly, and the method can better maintain the strength of the edge of the plate glass.
  • the disadvantage of this method is that the filling liquid is easily oxidized and corroded, and its hardness is lower than that of glass, and it is easy to be worn. Once the filling liquid is corroded or worn, the strengthening effect will be lost, causing the glass to break.
  • Glass ceramic is a new type of ceramic material developed in the 1970s. It is a composite material with microcrystals and glass phase uniformly distributed after heat treatment at a certain temperature. It is also called glass-ceramics. It has high mechanical strength and chemical Good stability and thermal stability, high service temperature, hardness and wear resistance, and many other valuable properties. In recent years, glass ceramics have been gradually applied to electronic display devices, especially as display protection screens for electronic devices. Although the mechanical properties of glass ceramics are stronger than conventional chemically strengthened glass, it also sacrifices its optical properties while increasing its strength, destroys the visual effects presented by the display of electronic equipment, and affects consumers' visual experience. Therefore, how to balance the two is also a recent research hotspot.
  • the invention patent CN1470470A discloses a partially crystallized glass, the crystallized glass contains precipitated halide crystals containing rare earth elements, the method includes: irradiating with a laser containing one or more rare earth elements and one or more halogenated The glass substrate of the object.
  • the glass involved in the patent is used to manufacture full-color displays, infrared sensors, short-wave solid-state lasers, etc., and the method to obtain partial crystallization not only requires the addition of rare earth elements and halides in the glass substrate, but also requires the application of expensive pulsed and high-focus The laser. This not only makes the cost high, but also makes the industrial production efficiency low, because the focus of the laser must pass through the material accurately and the focus can only handle a very small volume.
  • the purpose of the present invention is to provide a glass and a glass cover plate with a partially reinforced structure to solve the defects of the existing sheet glass such as low peripheral strength and poor light transmission performance.
  • the present invention also provides a glass processing method with a locally reinforced structure, which solves the problems of low production efficiency and high production cost caused by the existing processing technology generally requiring photosensitive materials or laser heating.
  • the present invention adopts the following technical solutions: a glass with a locally reinforced structure, including a locally reinforced area and a non-reinforced area, the local reinforced area contains a gradient distribution of crystal phase; in the glass In the transverse cross-section, the crystallinity of the locally enhanced zone is in a decreasing distribution in the direction in which the non-enhanced zone extends.
  • the crystallinity of the locally enhanced zone is distributed in the range of 10-100 wt%, and the crystallinity at the center of the non-enhanced zone is 0 wt%. Further, the crystallinity of the local enhanced zone is distributed in the range of 40-100 wt%.
  • the crystal size of the local enhancement zone is 20 nm to 200 nm. Further, the crystal size of the local enhancement zone is 20 nm to 85 nm.
  • the present invention also provides a glass with a locally reinforced structure, which includes a locally reinforced area and a non-reinforced area; the locally reinforced area includes a gradient distribution of crystal phases; on the lateral section of the glass, the visible light in the locally reinforced area is transmitted The rate shows an increasing distribution in the direction in which the non-enhanced zone extends.
  • the locally enhanced area has a transmittance of at least 80% in the visible light range; the non-enhanced area has a transmittance of at least 90% in the visible light range. Further, the visible light transmittance of the local enhanced area is 85% to 91%, and the visible light transmittance of the non-enhanced area is 91% to 93%.
  • the thickness of the glass product is 0.2 mm to 1.5 mm.
  • the mol% content of Li, Na or K oxides in the glass product is 5%-30%, and Na 2 O is less than or equal to Al 2 O 3 and B 2 The total amount of O 3.
  • the glass product includes the following mol% components: Si 2 O at least 64%; Al 2 O 3 : 4-12%; B 2 O 3 : 1-3%; Li 2 O: 5-25%; P 2 O 5 :0 ⁇ 3%; ZrO 2 :0 ⁇ 3%; NaCl: 0 ⁇ 1%; Na 2 SO 4 :0 ⁇ 1%; Among them, Na 2 O: less than or equal to alumina and B 2 O 3 The total amount.
  • the local reinforced zone occupies 1/25 to 3/5 of the total area of the glass product.
  • the local reinforced area is at least one side area of the glass product.
  • the "edge" is a band formed by extending a certain width from the edge of the glass product to the inside of the glass.
  • the glass is rectangular
  • the local reinforced area is the frame area of the rectangular glass
  • the length of the frame is the length of the side where the rectangular glass is located
  • the frame width is m or n, where m is 5% to 10% of the width of the rectangular glass, n It is 5%-20% of the length of the rectangular glass; m ⁇ n.
  • the present invention also provides a glass cover plate, which is formed by chemically strengthening the above-mentioned glass with a partially reinforced structure.
  • a glass cover plate which is formed by chemically strengthening the above-mentioned glass with a partially reinforced structure.
  • the present invention also provides a glass processing method with a locally reinforced structure, which performs heat treatment on the cut and shaped precursor glass.
  • the heat treatment includes nucleation treatment and crystallization treatment, and the maximum heat treatment temperature of the heat treatment in the non-reinforced zone is controlled to be lower than that in the reinforced zone. The lowest nucleation treatment temperature. Further, the maximum heat treatment temperature of the non-reinforced zone is lower than the nucleation treatment temperature of the reinforced zone by 10-100°C.
  • the heating rate during the heat treatment is lower than 50°C/min. Further, the heating rate during the heat treatment is 10°C/min-30°C/min.
  • the temperature of the nucleation treatment is 5 to 80° C. above the DSC glass transition point (Tg), and the nucleation treatment is 2-7 hours. Further, the temperature of the nucleation treatment is 30 to 70°C above the DSC glass transition point (Tg), and the nucleation treatment is 2 to 5 hours. Further, the temperature of the nucleation treatment is 35 to 65° C. above the DSC glass transition point (Tg), and the nucleation treatment is 3 to 4 hours.
  • the crystallization temperature is 20 ⁇ 150°C below the first crystallization peak of DSC or 70 ⁇ 150°C below the second crystallization peak of DSC.
  • the crystallization treatment is 1 to 2 times, and each treatment is 2 ⁇ 6h. .
  • the first main surface and the second main surface of the reinforced area are directly heated at the same time; the heating of the non-reinforced area is the heat conduction method of the reinforced area, and the second main surface of the non-reinforced area
  • the one main surface and the second main surface correspond to the heat sink, and the maximum temperature is controlled to be lower than the minimum nucleation treatment temperature of the enhanced zone.
  • a thermal conductive silicone grease layer is arranged between the first main surface and the second main surface of the non-reinforced area and the heat dissipation device, respectively. The thickness of the thermally conductive silicone grease layer is less than 0.3 mm.
  • the present invention also provides a glass processing equipment with a local reinforcement structure, including a heating device and a heat dissipation device; the heating device has heating parts for heating two opposite surfaces of a designated local reinforcement zone of the precursor glass; the heat dissipation device It has a heat dissipation part that dissipates heat from two opposite surfaces of the non-reinforced area designated for the precursor glass.
  • the heating part has two heating surfaces, the outer contour of the heating surface is consistent with the local reinforced area of the glass, the heat dissipating part has two heat dissipating surfaces, and the outer contour of the heat dissipating surface is consistent with the glass product The non-enhanced zone is consistent.
  • the distance between the heating surface and the two opposite surfaces of the reinforced area is less than or equal to 1/2 of the thickness of the glass, including 0; the distance between the heat dissipation surface and the two opposite surfaces of the non-reinforced area is less than or equal to 1/2 of the thickness of the glass, including zero.
  • the heating device is a temperature-controlled electric heating plate, which is connected to the controller.
  • the heat dissipating device is also provided with a heat dissipating pipe, the heat dissipating pipe is located around and/or inside the heat dissipating part, and two ends of the heat dissipating pipe are provided with openings, which are respectively communicated with the inlet and the outlet of the cooling medium.
  • the heat dissipating part is made of high thermal conductivity metal with a thermal conductivity of 350-450 W/mK.
  • the high thermal conductivity metal uses silver, copper, silver alloy or copper alloy.
  • the present invention has the following beneficial effects:
  • the local reinforcement zone contains a gradient distribution of crystal phases; in the transverse section of the glass, the crystallinity of the local reinforcement zone is in the direction in which the non-reinforcement zone extends. Decreasing distribution, in the longitudinal cross-section of the glass, the crystallinity of the local reinforced zone is respectively uniformly distributed in the direction extending from the main surface of the glass to the inside. In this way, not only the local strength of the glass product is effectively improved, but also the high light transmittance in the non-reinforced area is effectively ensured.
  • the fracture toughness of the local reinforcement zone is 9%-50% higher than that of the non-local reinforcement zone, and the Vickers hardness of the local reinforcement zone is 2%-10% higher than the Vickers hardness of the non-local reinforcement zone, so that the obtained glass product It has the characteristics of high local mechanical strength, thinner, lighter, stronger, more resistant to cracking and high light transmission performance, and solves the problems of the edge strength of thin glass and the poor visual effect of the display.
  • the present invention performs differential heating treatment on the local reinforced area and non-reinforced area of the glass plate, so that the temperature of the local reinforced area presents a gradient distribution on the transverse section, so that the reinforced area is in the transverse section.
  • the crystallinity and visible light transmittance also present a gradient distribution with temperature, and the non-enhanced area cannot achieve nucleation and crystallization due to the limitation of heat treatment temperature, which ensures that the unenhanced area of the glass product also has high light transmittance and maintains a good visual effect.
  • the basic components of the glass of the present invention must control the amount of sodium oxide introduced in the glass, less than or equal to the amount of alumina and boron oxide introduced, to ensure the ratio of bridging oxygen, so that the lithium disilicate in the glass ceramic is the main crystalline phase. Based on a single "molecular weight" lithium silicate crystal without bridging oxygen, a single “molecular weight” lithium disilicate has a bridging oxygen, and the structure is relatively stable, thereby improving the crystallization efficiency of the local enhanced zone.
  • the production method is simple, does not require ultraviolet light or laser heating, the production process is easy to control, and the production cost is low, the process is unique, the operability is strong, and it is easy to popularize and apply, and can realize batch industrial production.
  • FIG. 1 is a schematic structural diagram of an embodiment of glass with a partially strengthened structure of the present invention.
  • Fig. 2 is a cross-sectional view taken along the line A-A in Fig. 1.
  • Fig. 3 is a curve of visible light transmittance at different wavelengths of a glass with a locally strengthened structure prepared by the present invention.
  • FIG. 4 is a schematic diagram of the structure of the glass processing equipment with a partially strengthened structure according to the present invention.
  • precursor glass is a glass sheet cut and shaped, and the size is suitable for products such as handheld electronic devices to be installed.
  • “chemically strengthened glass” is a chemically toughened glass that has been processed by a high-temperature ion exchange process.
  • the alkali metal ions with a large ion radius replace the alkali metal ions with a small ion radius in the glass to generate a difference in exchange ion volume, and a high-to-low compressive stress is generated in the surface layer of the precursor glass, which hinders and delays the glass.
  • the expansion of micro-cracks achieves the purpose of improving the mechanical strength of the glass.
  • the depth of the compressive stress layer refers to the depth position in the strengthened product where the compressive stress generated from the strengthening process reaches zero.
  • first and second major surface can be used interchangeably to refer to the opposite major surface of the component.
  • first main surface may refer to the front surface facing the target user, for example, emitting light to the user or displaying an image to the user.
  • second major surface can refer to a back surface that faces away from the user, such as the back plate of the device (if present).
  • the conventional method is used to measure the light transmittance
  • the transmittance of the top surface of the glass plate is used
  • the light spot of the test instrument is circular
  • the diameter of the light spot ⁇ (1/3a, 1/2a) measured every 10nm within 360-740nm
  • a glass with a locally reinforced structure includes a locally reinforced zone 1 and a non-reinforced zone 2; the local reinforced zone 1 contains a gradient distribution of crystal phases; on the lateral cross-section of the glass, locally The crystallinity of the reinforced zone 1 shows a decreasing distribution in the direction in which the non-reinforced zone 2 extends; on the longitudinal section of the glass, the crystallinity of the local reinforced zone is uniformly distributed in the direction extending from the main surface of the glass to the inside.
  • the glass has a non-isothermal temperature distribution in the direction extending to the non-reinforced zone in the transverse cross-section.
  • This temperature gradient distribution can be derived from the energy of the glass precursor in the local reinforced zone and the non-reinforced zone when the precursor glass is formed into a glass product.
  • Different temperatures are precisely set to control whether it can be nucleated and crystallized; in addition, due to the temperature difference between the contact area between the local reinforced area and the non-reinforced area of the glass product, heat can be transferred.
  • the temperature in the direction of the extension of the enhancement zone shows a decreasing distribution, so that the number of nucleation nuclei in the local enhancement zone and the crystallinity also show a decreasing distribution with the temperature. Due to the thin thickness of the glass product, the temperature difference of the local reinforced zone in the longitudinal section is not large, and the heat transfer to the external environment is negligible. Therefore, the crystallinity of the local reinforced zone is evenly distributed in the direction extending from the main surface of the glass to the inside. .
  • the thickness is preferably in the range of 0.2 mm to 1.5 mm, and more preferably in the range of 0.8 mm to 1 mm.
  • the glass article may possess a composition that is substantially transparent in the visible light range and remains substantially transparent after the development of its compressive stress zone.
  • the crystallinity of the local enhancement zone is distributed in the range of 10-100%.
  • the crystallinity of the local enhancement zone is distributed in the range of 40-100%.
  • the crystallinity at the center of the non-enhanced area is 0%, which guarantees the visual effect of the display area of the electronic device.
  • the average size of the crystals in the local enhancement zone is between 20 nm and 200 nm, preferably between 20 nm and 85 nm.
  • the crystals with an average crystal size between 20nm and 85nm do not affect the visible light transmittance of the glass.
  • the local enhancement zone contains the crystal phase and the glass phase, and the crystal phase is distributed inside the glass phase.
  • the scattering effect on the interface has a greater influence on the average visible light transmittance of the local enhancement zone.
  • the greater the scattering effect the smaller the average visible light transmittance of the local enhancement zone.
  • the size of the scattering effect mainly depends on the average size of the crystal.
  • the smaller the average size of the crystal the smaller the area of the cross section that causes the scattering effect.
  • the smaller the scattering effect of the cross section on visible light the corresponding local enhancement area The greater the average visible light transmittance.
  • the average crystal size of the crystal in the local enhancement zone of the present invention is less than or equal to 85 nm. Accordingly, the cross-sectional area of the crystal that causes light scattering is relatively small, and the light scattering effect of the crystal is relatively small.
  • the local reinforced zone of the glass product of the present invention also contains a crystal phase.
  • the average hardness, flexural strength, fracture toughness and other mechanical properties of the local reinforced zone can be improved. Thereby adjusting the anti-scratch and anti-drop properties of the local reinforced area.
  • the crystals in the local reinforced zone of the present invention can deflect the propagation path of the glass phase microcracks, making it difficult for the microcracks to propagate.
  • the average size of the crystal is, the higher the average visible light transmittance of the local enhancement zone is correspondingly.
  • the average size of the crystals in the local reinforcement zone will affect the mechanical properties of the glass-ceramics. Generally speaking, the smaller the average size of the crystals in the local reinforcement zone, the worse the mechanical properties of the corresponding glass-ceramics. Based on this, a preferred average size of the crystals in the present invention is 20 nm to 85 nm. In this way, the local reinforced area of the glass product solves the problems of micro-cracks, chipping points, and chipping caused by insufficient strength, while ensuring its high transmittance in the visible light waveband.
  • a glass with a local reinforced structure includes a local reinforced zone 1; the local reinforced zone contains a gradient distribution of crystal phases; in the transverse cross-section of the glass, The visible light transmittance of the locally enhanced zone 1 is distributed in an increasing direction in the direction in which the non-enhanced zone 2 extends.
  • the local reinforced area in the glass occupies 1/25 to 3/5 of the total area of the glass cover; preferably, the area of the local reinforced area is 1/5 of the total area of the glass cover.
  • the local reinforcement area is at least one side area of the glass product.
  • the "side area” is a band-shaped area formed by extending a certain width from the edge of the glass product to the inside of the glass.
  • the local reinforced area of the glass product is at least one frame area 1 of the rectangle, the length of the frame is the length of the side where the rectangular glass is located, and the width of the frame is m or n, and m is 5% to 10% of the width of the rectangular glass.
  • N is 5%-20% of the length of the rectangular glass; m ⁇ n.
  • the visible light transmittance of the glass with a locally strengthened structure of the present invention is tested at different wavelengths. Specifically, the visible light transmittance of the above rectangular glass product is analyzed as an example. As shown in FIG.
  • the frame 1 is a local Reinforced area
  • the middle area 2 is a non-reinforced area
  • curve A is measured by the test instrument's light spot cut on the outermost part of the local reinforced area of the glass product (that is, the outer edge of the glass product), and its average range is 87%- 89.5%, the lowest value is greater than 81%
  • curve B is measured by the test instrument's spot cut at the border between the local reinforced area and the non-reinforced area of the glass product (that is, the innermost part of the local reinforced area of the glass product), and its average range is 90.5% -91.5%, the lowest value is greater than 86%
  • curve C is measured by the test instrument's light spot cut on the center line between the outermost and innermost part of the local enhancement area of the glass product.
  • the average range is 89.5%-90.5%, and the lowest value is greater than 84%. It can be seen that, in the invention, the glass is transparent, and the local reinforced area of the glass with a thickness of 1 mm has an average light transmittance of 87% or higher, 88% or higher, 89% or higher, 90% in the visible light range. % Or higher (including surface reflection loss).
  • the usual glass-ceramics may be translucent in the wavelength range of 380nm to 780nm, and for glass-ceramic products with a thickness of 1mm, the average translucent glass-ceramics in the wavelength range of 450nm to 600nm
  • the overrate is 20% to 85% or less.
  • the local reinforced area of the glass product of the present invention extends from the edge of the glass to the inside, so that the microcrack propagation at the edge of the glass can be well controlled, and the strength of the glass, especially the edge of the glass, is improved without affecting the main display screen of the glass. Visual effect.
  • the present invention provides a glass cover plate, comprising: a first main surface and an opposite second main surface, a plurality of frames, and a glass product of a certain thickness,
  • the glass product has a plurality of ion-exchangeable alkali metal ions, which can form a compressive stress region extending from the main surface to the first selected depth in the glass product; at least one frame is a local reinforced region, and the local
  • the reinforced zone includes a crystalline phase with a gradient distribution; on the lateral cross-section of the glass product, the crystallinity of the local reinforced zone shows a decreasing distribution in the direction extending from the outer edge to the non-reinforced zone 2.
  • the frame refers to at least one side of any polygon of a glass product (or glass cover) or four perimeters of a rectangle. It may include one or any combination of straight edge portions, curved edge portions, beveled edge portions, rough edge portions, and sharp edge portions.
  • the thickness is preferably in the range of 0.2 mm to 1.5 mm, and more preferably in the range of 0.5 mm to 1 mm.
  • the glass article may possess a composition that is substantially transparent in the visible light range and remains substantially transparent after the development of its compressive stress zone.
  • the compressive stress zone may be formed by a strengthening process (e.g., by thermal tempering, chemical ion exchange, or the like).
  • the amount of compressive stress (CS) associated with the compressive stress zone and the depth of the compressive stress layer (DOL) may vary based on the specific use of the article 100.
  • the maximum compressive stress in the compressive stress region is 300-400 MPa, and the first selected depth is at least 5% of the thickness of the article.
  • the glass cover plate disclosed in the present invention can be widely used in other products, such as partial protective cover glass for handheld devices, notebook computers, desktop computers and televisions, and can also be used to form display substrates, touch sensors or integral touches. Cover at least part of the glass, or any article that requires some transparency, scratch resistance, abrasion resistance, or a combination thereof.
  • it can be applied to electronic devices, such as mobile phones, tablets, computers, virtual reality (VR) terminal devices, augmented reality (AR) terminal devices, wearables Equipment, television, etc.
  • VR virtual reality
  • AR augmented reality
  • the electronic device includes a housing having a front surface, a rear surface, and a side surface; electronic components located in the housing; a display located on the front surface of the housing or adjacent to the front surface of the housing; and
  • the covering substrate on the display is used to isolate and protect the display panel, and to prevent damage to the display panel caused by external things or forces.
  • the covering substrate or the outer shell includes any of the above-mentioned glass cover plates. As mentioned above, the glass cover has good light transmittance, so it will not affect the use of the display panel. At the same time, since the frame of the glass cover plate has better mechanical strength, the scratch resistance and drop resistance of the glass cover plate are improved, so it is not easy to be damaged.
  • the present invention also provides a glass processing method with a partially reinforced structure.
  • the precursor glass is cut and shaped, and the precursor glass is subjected to heat treatment including nucleation treatment and crystallization treatment, and the maximum temperature of heat treatment in the non-reinforced zone is controlled to be lower than The lowest nucleation temperature in the enhanced zone. Further, the maximum heat treatment temperature of the non-reinforced zone is lower than the nucleation treatment temperature of the reinforced zone by 10-100°C.
  • the non-reinforced area of the glass will not be nucleated during the heat treatment process, and during the crystallization process, since the non-reinforced area of the glass is not nucleated, it is difficult to crystallize in this temperature range and will not be due to thermal expansion. Cracked, so there is no crystal in the non-reinforced area of the glass product.
  • heat treatment is a key process for producing a crystal phase and a glass phase in the glass.
  • the crystallization of the base glass undergoes two stages of nucleation and crystallization in the heat treatment process.
  • the nucleation temperature should be slightly higher than the softening temperature of the glass.
  • the crystallization is to grow the crystal nuclei into micro/nano crystals of the target size, and the crystallization temperature is generally the exothermic temperature of crystal growth.
  • the structure and performance of the glass mainly depend on the heat treatment process.
  • a specific mold is used to perform temperature treatment with a temperature difference on a specified area of the glass.
  • the temperature is lower than the nucleation temperature of the glass, so the non-reinforced area cannot complete the crystallization; and the nucleation temperature and crystallization temperature during the heat treatment of the reinforced area can make the crystal nuclei in the glass grow.
  • the heat treatment temperature is positively correlated with the number of crystal nuclei. Due to the temperature difference between the contact area of the local reinforced zone and the non-reinforced area, there is heat transfer between the contact surfaces of the above two areas. Therefore, the local reinforced area presents a temperature gradient distribution in the direction in which the local reinforced area extends to the non-reinforced area in the transverse section.
  • the degree of crystallinity also presents a gradient distribution in the direction in which the local enhanced zone extends to the non-enhanced zone in the transverse section.
  • part of the microcracks of the glass will heal during the heat treatment process, and the fracture toughness of the precipitated crystals is relatively large, which can prevent the unhealed microcracks from further expanding. Therefore, the present invention can better control the crystallizing area through temperature control, so as to achieve the purpose of local strengthening.
  • the nucleation temperature may be 5 to 80°C above the glass transition point (Tg).
  • the nucleation temperature may be 30 to 70°C above the glass transition point (Tg).
  • the nucleation temperature may be 35 to 65°C above the glass transition point (Tg).
  • Heating to the nucleation temperature may involve a single heating rate or multiple heating rates.
  • the glass article can be heated from the initial temperature to the intermediate temperature at a higher rate (for example, 15-25°C/min), and at a lower rate (for example, 6-12°C/min) Heating from intermediate temperature to nucleation temperature.
  • the glass product After the glass product reaches the nucleation temperature, the glass product is maintained at the nucleation temperature for a period of time, during which nuclei are established in the glass product.
  • the nucleation time can be 2 to 7 hours; preferably, the nucleation time can be 2 to 5 hours, and more preferably, the nucleation time can be 3 to 4 hours.
  • the glass article After nucleation, the glass article is heated from the nucleation temperature to the crystallization temperature.
  • the crystallization temperature is 20-150°C below the first crystallization peak of DSC or 70-150°C below the second crystallization peak of DSC.
  • the glass structure is unstable during low temperature heat treatment, and the proportion of bridge oxygen formed is relatively small.
  • lithium silicate is mainly precipitated; if you want to form lithium disilicate in the glass as the main crystalline phase, you can extend the time or increase the crystallization temperature.
  • the structure gradually stabilizes, the bridge oxygen ratio increases, and lithium silicate is gradually transformed into lithium disilicate.
  • the glass product After the glass product reaches the crystallization temperature, the glass product is maintained at the crystallization temperature for a period of time; during this process, at least one crystal phase grows in the glass.
  • the crystallization temperature is such that lithium disilicate is formed as the main crystalline phase in the glass.
  • the crystallization time can be 2 to 6 hours. At the end of the crystallization period, the glass article has become a localized crystalline phase.
  • the heat treatment temperature of the reinforced zone is 10-100° C. higher than the heat treatment temperature of the non-reinforced zone. Within this temperature range, the glass in the non-reinforced zone can be controlled not to nucleate or break due to thermal expansion. In another embodiment, the temperature during the heating process is adjustable, and the heating rate is lower than 50°C/min and all ranges and sub-ranges therebetween to prevent the glass plate from bursting.
  • the heating rate is preferably 45°C/min or Smaller, 40°C/min or less, 35°C/min or less, 30°C/min or less, 25°C/min or less, 20°C/min or less, 15°C/min or less , 10°C/min or less, 5°C/min or less, more preferably 10-30°C/min.
  • a thermally conductive silicone grease layer is provided on the non-reinforced area on the first main surface and the second main surface of the precursor glass .
  • the thermally conductive silicone grease layer can be coated, printed and/or attached in other ways as a thin film on the first and second main surfaces of the non-reinforced area of the glass product. In this way, the body of the non-reinforced area can be increased. High heat dissipation efficiency, and avoid damage to the apparent quality of the non-reinforced area during the heat treatment process.
  • the thickness of the thermally conductive silicone grease layer is less than 0.3 mm, and has a thickness of 0.2 mm or less, 0.1 mm or less, 0.05 mm or less, 0.04 mm or less, 0.03 mm or less, 0.02 mm or less. , A thermal grease layer with a thickness of 0.01mm or less.
  • the raw materials are accurately weighed, and after the raw materials are fully mixed, they are heated at a high temperature for melting.
  • the melting of glass is a very complex process, which includes a series of physical, chemical, and physical and chemical phenomena and reactions. The results of these phenomena and reactions make various raw materials change from mechanical mixtures into complex melts, namely glass. liquid.
  • the melting of glass can be roughly divided into five stages: silicate formation, melting to form molten glass, clarification of molten glass, homogenization of molten glass, and cooling of molten glass.
  • the melting temperature used in the preparation of the present invention is 1610°C to 1650°C.
  • the preparation process of precursor glass is a process of transforming molten glass into products with geometric shapes.
  • the precursor glass may be a precursor glass plate or a precursor glass brick.
  • the molten glass can be made into a precursor glass plate by a calendering method, a float method, or an overflow method, or the molten glass can be made into a precursor glass brick by a casting method.
  • the calendering process, float process, overflow process, and casting process used in the present invention can all adopt existing technologies.
  • the precursor glass is mechanically cut into a precursor glass plate with a certain shape, usually a rectangular glass plate.
  • the glass product or precursor glass of the present invention mainly includes the following mol% components (the following components are referred to as glass products or precursor glass): silica: 64 to 72%; alumina: 4 to 12%; B 2 O 3 : 1 to 3%; Li 2 O: 5 to 25%; Na 2 O: less than or equal to the total amount of alumina and B 2 O 3.
  • the glass product or precursor glass also includes the following mol% components: P 2 O 5 : 0-3%; ZrO 2 : 0-3%; NaCl: 0-1%; Na 2 SO 4 : 0-1% .
  • SiO 2 is the main glass forming oxide, which is a glass network former, and can form a silicon-oxygen tetrahedron as the basic network of glass.
  • Al 2 O 3 can also provide a stable network and is a glass network intermediate, which can form a basic network of aluminum-oxygen tetrahedrons and silicon-oxygen tetrahedra to form glass; it can increase the viscosity of the glass and inhibit crystallization. If the amount of alumina is too high, the fraction of lithium silicate crystals may decrease to the point where the interlocking structure cannot be formed, and the viscosity of the melt will usually increase.
  • the glass composition may include 4-12 mol% Al 2 O 3 and all ranges and sub-ranges therebetween, such as 4-11.5 mol%, 4-11 mol%, 4-10.5 mol%, 4 ⁇ 10mol%, 4 ⁇ 9.5mol%, 4 ⁇ 9mol%, 5 ⁇ 11.5mol%, 5 ⁇ 11mol%, 5 ⁇ 8.2mol%, 8.6 ⁇ 8.8mol%, 9mol%, 9.4mol%, 9.6mol%, 9.8 mol%, 10 mol%, 10.2 mol%, 10.4 mol%, 10.6 mol%, 10.8 mol%, 11 mol%, 11.2 mol%, 11.4 mol%, 11.6 mol%, 11.8 mol%, or 12 mol%.
  • B 2 O 3 can also be used as a glass network former, which can form a basic network of glass with boron-oxygen tetrahedrons and silicon-oxygen tetrahedrons. Helps to provide a glass precursor with a low melting point.
  • adding B 2 O 3 to the original silk glass and glass-ceramics helps to realize the interlocking crystal microstructure, and can also improve the damage resistance of the glass-ceramics.
  • the glass composition may include 1 to 3 mol% Al 2 O 3 and all ranges and sub-ranges therebetween, such as 1 to 2.8 mol%, 1 to 2.5 mol%, 1 to 2.4 mol%, 1 ⁇ 2mol%, 1 ⁇ 1.5mol%, 2 ⁇ 3mol%, 2 ⁇ 2.5mol%, 2.5 ⁇ 3mol%, 1mol%, 1.4mol%, 1.6mol%, 1.8mol%, 2mol%, 2.2mol%, 2.4 mol%, 2.6 mol%, 2.8 mol%, 3 mol%.
  • Na 2 O can reduce the viscosity of the glass liquid and break the network in the glass network. Too much Na ions will reduce the proportion of bridging oxygen in the glass network. 1 mol of sodium oxide provides 1 mol of oxygen for alumina or boron oxide to form a tetrahedron. 1 mol of bridging oxygen, so the amount of sodium oxide added needs to be less than or equal to the total amount of alumina and B 2 O 3.
  • the glass composition may include Na 2 O: less than or equal to the total amount of alumina and B 2 O 3 and all ranges and sub-ranges therebetween, such as 5-15 mol%, 4-11 mol% , 4 ⁇ 10.5mol%, 4 ⁇ 10mol%, 4 ⁇ 9.5mol%, 4 ⁇ 9mol%, 5 ⁇ 11.5mol%, 5 ⁇ 11mol%, 5 ⁇ 8.2mol%, 8.6 ⁇ 8.8mol%, 5mol%, 6mol %, 7mol%, 8mol%, 9mol%, 10mol%, 11mol%, 11.4mol%, 11.6mol%, 11.8mol%, 12mol%, 13mol%, 14mol%, 14.5mol%, or 15mol%.
  • Li 2 O can significantly reduce the viscosity of the glass liquid, and too much introduction will cause the glass to crystallize at low temperature.
  • Lithium oxide is generally used for the formation of glass ceramics, while other alkali metal oxides tend to reduce the formation of glass ceramics, forming aluminosilicate residual glass in glass ceramics.
  • the glass composition may include Li 2 O 5-25% and all ranges and sub-ranges therebetween, such as 5-24 mol%, 5-22 mol%, 5-20 mol%, 5-18 mol% , 5 ⁇ 10mol%, 4 ⁇ 25mol%, 4 ⁇ 20mol%, 4 ⁇ 18mol%, 4 ⁇ 15mol%, 4 ⁇ 10mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%, 10mol%, 11mol %, 12mol%, 15mol%, 18mol%, 20mol%, 21mol%, 22mol%, 23mol%, 24mol%, or 25mol%.
  • the composition of the glass may also include P 2 O 5 , and P 2 O 5 can be used as a nucleating agent to generate a large amount of nucleation.
  • P 2 O 5 can be used as a nucleating agent to generate a large amount of nucleation.
  • a small amount of introduction will cause Li 3 PO 4 crystal nuclei to be precipitated during the heat treatment of the glass, and it will be easier to precipitate in the presence of heavy metal ions (lower temperature). If the concentration of P 2 O 5 is too high, it will be difficult to control the denitration effect of the precursor glass after forming and cooling.
  • the glass composition may include 0-3% P 2 O 5 and all ranges and sub-ranges therebetween, such as 0-2.8 mol%, 0-2.6 mol%, 0-2 mol%, 0 ⁇ 1.8mol%, 0 ⁇ 1.0mol%, 1 ⁇ 2.5mol%, 1 ⁇ 2.0mol%, 1 ⁇ 1.8mol%, 1 ⁇ 1.5mol%, 1 ⁇ 1.2mol%, 0mol%, 1.5mol%, 1.8mol %, 2mol%, 2.9mol%, 2.8mol%, 2.6mol%, 2.5mol%, 2.1mol%, 0.8mol%, 0.6mol%, 0.5mol%, 0.4mol%, 0.3mol%, 0.2mol%, or 0.1 mol%.
  • the glass composition can also include ZrO 2.
  • ZrO 2 can also be used as a nucleating agent to generate a large amount of nucleation. It can significantly reduce the denitrification effect of the glass during the formation process and lower the liquidus temperature to increase Li 2 O-Al 2 The stability of O 3 -SiO 2 -P 2 O 5 glass. The addition of ZrO 2 also helps to reduce the grain size of the crystals, thereby contributing to the formation of transparent glass ceramics.
  • the glass composition may include 0-3% ZrO 2 and all ranges and sub-ranges therebetween, such as 0-2.8 mol%, 0-2.6 mol%, 0-2 mol%, 0-1.8 mol%, 0 ⁇ 1.0mol%, 1 ⁇ 2.5mol%, 1 ⁇ 2.0mol%, 1 ⁇ 1.8mol%, 1 ⁇ 1.5mol%, 1 ⁇ 1.2mol%, 0mol%, 1.5mol%, 1.8mol%, 2mol%, 2.9mol%, 2.8mol%, 2.6mol%, 2.5mol%, 2.1mol%, 0.8mol%, 0.6mol%, 0.5mol%, 0.4mol%, 0.3mol%, 0.2mol%, or 0.1mol %.
  • the composition of the glass can also be a chemical fining agent.
  • clarifying agents include but are not limited to NaCl and Na 2 SO 4 .
  • the glass composition may include NaCl 0-1% and all ranges and sub-ranges therebetween, such as 0-0.9 mol%, 0-0.8 mol%, 0-0.7 mol%, 0-0.6 mol%, 0 ⁇ 0.5mol%, 0 ⁇ 0.4mol%, 0.5 ⁇ 1.0mol%, 0.5 ⁇ 0.8mol%, 0.5 ⁇ 0.7mol%, 0.5 ⁇ 0.6mol%, 1mol%, 0.9mol%, 0.8mol%, 0.7 mol%, 0.6 mol%, 0.5 mol%, 0.4 mol%, 0.3 mol%, 0.2 mol%, or 0.1 mol%.
  • the glass composition may include Na 2 SO 4 0-1% and all ranges and sub-ranges therebetween, such as 0-0.9 mol%, 0-0.8 mol%, 0-0.7 mol%, 0 ⁇ 0.6mol%, 0 ⁇ 0.5mol%, 0 ⁇ 0.4mol%, 0.5 ⁇ 1.0mol%, 0.5 ⁇ 0.8mol%, 0.5 ⁇ 0.7mol%, 0.5 ⁇ 0.6mol%, 1mol%, 0.9mol%, 0.8 mol%, 0.7 mol%, 0.6 mol%, 0.5 mol%, 0.4 mol%, 0.3 mol%, 0.2 mol%, or 0.1 mol%.
  • a single "molecular weight” lithium silicate crystal has no bridging oxygen
  • a single “molecular weight” lithium disilicate has a bridging oxygen
  • the structure is relatively stable.
  • the structure of the glass is rearranged during the heat treatment, and the silicon-oxygen tetrahedrons are connected by bridging oxygen.
  • the bridging oxygen is less, and lithium silicate is preferentially precipitated; at the same time, the addition of sodium oxide breaks the glass network , The number of bridge oxygen decreases and the lithium silicate crystals increase.
  • the sodium oxide content increases to a certain ratio, only lithium silicate crystals can be precipitated. Therefore, the amount of sodium oxide introduced in the glass must be controlled to be less than or equal to the amount of alumina and boron oxide introduced to ensure the ratio of bridging oxygen, so that the lithium disilicate in the glass ceramic is the main crystalline phase.
  • the partially reinforced glass product prepared by the present invention further includes contacting at least one of the first major surface and the second major surface of the glass product with a salt bath after heat treatment (nucleation and crystallization)
  • the salt bath includes a plurality of ion-exchange alkali metal ions, and each ion-exchange alkali metal ion has a size larger than that of the ion-exchangeable alkali metal ion.
  • the traditional ion exchange process usually occurs in an elevated temperature range that does not exceed the glass transition temperature. This process is performed by immersing the glass in a molten bath containing alkali metal salts (usually nitrates) whose ions are larger than the main alkali metal ions in the glass.
  • the host alkali metal ions are exchanged for larger alkali metal ions.
  • glass containing Na + can be immersed in a molten potassium nitrate (KNO 3 ) bath.
  • KNO 3 molten potassium nitrate
  • the larger K + in the molten bath will replace the smaller Na + in the glass. Due to the presence of larger alkali metal ions at the sites previously occupied by smaller alkali metal ions, compressive stress is generated at or near the surface of the glass, and tension is generated inside the glass.
  • the ion exchange depth (that is, the penetration depth of the invaded larger alkali metal ions into the glass) is usually 20-300 ⁇ m, such as 40-300 ⁇ m, and the ion exchange depth is controlled by the glass composition and the immersion time. In the present invention, the ion exchange depth Not less than 5% of the thickness of the glass.
  • the time and temperature of ion exchange have an effect on the surface compressive stress of chemically strengthened glass ceramics.
  • the surface compressive stress presents a trend of first increasing and then decreasing; based on this, the suitable ion exchange temperature of the present invention is 380°C to 450°C.
  • the surface compressive stress presents a tendency to first increase and then decrease; based on this, the suitable ion exchange time of the present invention is 2h-18h.
  • One or more ion exchange processes used to strengthen glass and/or glass ceramics may include, but are not limited to: immersing them in a single bath, or immersing them in multiple baths with the same or different compositions.
  • the composition of one or more baths may include more than one type of larger ion (e.g., Na + and K + ) or a single larger ion.
  • exemplary bath compositions may include nitrates, sulfates, and chlorides of larger alkali metal ions.
  • Typical nitrates include KNO 3 , NaNO 3 , LiNO 3 , NaSO 4 and combinations thereof.
  • the partially reinforced glass product is immersed in a molten salt bath of 100% KNO 3 or a combination of NaNO 3 , KNO 3 and LiNO 3 , and the temperature of the molten salt bath is 370°C to 480°C.
  • the salt bath components mentioned in this article are all calculated in wt%.
  • the inner glass layer may be immersed in a molten mixed salt bath that includes 1% to 99% of NaNO 3.
  • the salt bath may include NaNO 3 1 to 99%.
  • the salt bath may include KNO 3 1 to 99% and all ranges and sub-ranges therebetween, such as 1 to 90%, 1 to 80%, 1 to 70%, 1 to 60%, 1 to 50%, 1 to 40%, 10 to 90%, 20 to 80 %, 30 to 70%, 40 to 60%, 1%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99%.
  • the salt bath may include KNO 3 1 to 99% and all ranges and sub-ranges therebetween, such as 1 to 90%, 1 to 80%, 1 to 70%, 1 to 60%, 1 to 50%, 1 to 40%, 10 to 90%, 20 to 80%, 30 to 70%, 40 to 60%, 1%, 20%, 30%, 40%, 50%, 60%, 70% , 80%, 90%, or 99%.
  • 0% to 2% LiNO 3 LiNO 3 .
  • the inner glass layer after the inner glass layer is immersed in the first ion exchange solution, it may be immersed in the second ion exchange solution.
  • the first ion exchange solution and the second ion exchange solution may have different compositions and/or temperatures from each other.
  • the immersion time in the first ion exchange solution and the second ion exchange solution can be varied.
  • the immersion in the first ion exchange solution may be longer than the immersion in the second bath.
  • the process of one-step ion exchange mainly consists of immersing glass ceramics in pure KNO 3 and/or NaNO 3 and/or LiNO 3 molten salt for 2 to 18 hours.
  • the process of multi-step ion exchange mainly includes: in the first step, the ion exchange temperature is immersed in a salt bath of pure KNO 3 and/or NaNO 3 and/or LiNO 3 for T 1 h at 380°C to 450°C; The second step is to soak in pure KNO 3 and/or NaNO 3 and/or LiNO 3 salt bath for T 2 h at 380°C ⁇ 450°C; the third step is to soak in pure KNO 3 and/or NaNO 3 and/or LiNO 3 Salt bath, immersion for T 3 h at 380°C to 450°C...
  • the nth step soak in pure KNO 3 and/or NaNO 3 and/or LiNO 3 salt bath at 380°C to 450°C for T n hours.
  • the first ion exchange temperature is higher than the second ion exchange temperature, and/or the glass article is in contact with the first ion exchange medium for longer than the time in contact with the second ion exchange medium.
  • the present invention also provides an equipment for preparing partially reinforced structural glass.
  • the device includes a heating device and a heat dissipating device.
  • the heat dissipating device has a heat dissipating portion 3 for dissipating heat from two opposite surfaces of the non-reinforced area 2 designated by the glass.
  • the heating portion 6 has two heating surfaces 7, the outer contour of the heating surface 7 is consistent with the local reinforced area 1 of the glass, and the heat dissipation portion 3 has two heat dissipation surfaces 4 , The outer contour of the heat dissipation surface 4 is consistent with the non-reinforced area 2 of the glass product.
  • the size of the heating part of the device can be adjusted, and then the width of the local reinforcement zone can be adjusted to meet different requirements.
  • the middle part is the non-reinforced zone, which cannot be nucleated and crystals cannot be precipitated. In this way, the strength of the glass cover is improved without affecting the light transmittance and display effect of the main display interface.
  • the distance between the heating surface 7 and the upper and lower surfaces of the glass product is less than or equal to 1/2 of the thickness of the glass, specifically it can be 40% or less, 30% or more of the thickness of the glass product. Small, 20% or less, 10% or less, or the distance between the heating surface 7 and the upper and lower surfaces of the glass product is 0, that is, the heating surface is in close contact with the upper and lower surfaces of the glass product.
  • the distance between the heat dissipation surface 4 and the upper and lower surfaces of the glass product is less than or equal to 1/2 of the thickness of the glass product. Specifically, it can be 40% or less, 30% or less, 20% or less of the thickness of the glass product. It is smaller, 10% or less, or the distance between the heat dissipation surface 3 and the upper and lower surfaces of the glass product is 0, that is, the heating surface is in close contact with the upper and lower surfaces of the glass product.
  • the heating device is a temperature-controlled electric heating plate, which is connected to the controller to facilitate precise control of the temperature in the enhancement zone.
  • the heat dissipation portion is formed of a material with high thermal diffusivity and a material with a thermal conductivity greater than 350 W/mK.
  • the thermal conductivity of the high thermal conductivity metal is 350-450 W/mK.
  • the heat sink is formed of one or more alloys of the materials listed in Table 1 below.
  • the heat dissipation portion may be shaped or structured in one or more ways to improve the heat conduction in the non-reinforced area.
  • FIG. 4 shows that the two heat dissipation surfaces 4 in the heat dissipation portion 3 are composed of several heat dissipation plates 5 arranged side by side and perpendicular to the upper and lower surfaces of the non-reinforced area. In this way, the contact area between the heat dissipation plate and the air is increased, and the heat dissipation efficiency is increased.
  • a heat dissipation pipe may also be provided in the heat dissipation device, and the heat dissipation pipe is located around and/or inside the heat dissipation portion.
  • the radiating pipes can be arranged in the following manner, but are not limited to the following manners: for example, the radiating pipes are arranged side by side along the two upper and lower surfaces of the non-reinforced area, and are located between any two adjacent radiating plates. In practice, the two ends of the radiating pipe are provided with openings, which are respectively communicated with the inlet and the outlet of the cooling medium.
  • the cooling medium may be, but is not limited to, cooling water or oil or gas mixture. This further increases the heat dissipation effect of the non-enhanced area. In this way, the cooling rate of the non-reinforced area is increased, and the heat transfer efficiency from the non-reinforced area to the local reinforced area is also enhanced.
  • step S3 Perform heating and heat dissipation treatments on the locally reinforced and non-reinforced areas on the first main surface and the second main surface of the precursor glass obtained in step S2, respectively, and control the pairing of the first heating plate and the second heating plate of the heating device
  • a heating rate of 20°C/min to heat up the heating plate to 530°C, hold for 5 hours to nucleate the precursor glass plate
  • a heating rate of 30°C/min to heat the heating plate Raise the temperature to 600°C, keep it for 5h for the first crystallization treatment, then raise the temperature to 640°C, keep it for 2h, carry out the second crystallization treatment, and control the non-reinforcement of the glass by the first heat sink and the second heat sink of the heat sink
  • the region is clamped and kept below the lowest nucleation temperature and crystallization temperature of the glass, and a glass product with a locally strengthened structure is obtained. Decreasing distribution; no crystal nucleus is formed in the non-
  • step S4 The partially strengthened glass product obtained in step S3 is subjected to ion exchange, and first is subjected to the first step of ion exchange IOX1, and the molten salt adopts a mixed salt bath of 40wt% NaNO 3 + 59.5wt% KNO 3 + 0.5wt% LiNO 3 ,
  • the strengthening temperature is 420°C, and the strengthening time is 5h. After the strengthening is completed, take it out and wash to obtain a strengthened glass plate.
  • Example 2-7 the precursor glass plates were obtained by the same method as in Example 1, except that:
  • Embodiments 2 and 5 are also provided with a thermally conductive silicone grease layer.
  • the heat dissipation devices of Embodiments 6 and 7 are also provided with heat dissipation pipes.
  • the heat dissipation pipes of Embodiment 6 are arranged on the outer circumference of the heat dissipation plate, and the heat dissipation pipes of Embodiment 7 are evenly arranged inside the heat dissipation plate.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 SiO 2 67 68 68 69 69 70
  • Al 2 O 3 6 4.5 5.5 4.2 5 4
  • B 2 O 3 1.5 1.2 1 1 0.5 1 2 Na 2 O 1.5 2.1 6 5 6
  • the strengthened glass plates prepared in Examples 1 to 7 were analyzed for crystals, including the width and size of the crystal regions, and the visible light transmittance and mechanical properties of the crystal regions of the glass-ceramics were tested at the same time.
  • the visible light transmittance was measured at a wavelength of 550nm , The results are shown in Table 4.
  • the present invention heats the local reinforced area and the non-reinforced area of the glass plate with a temperature difference, so that the temperature of the local reinforced area presents a gradient distribution in the transverse section, so the crystallinity of the enhanced area in the transverse section
  • the transmittance of visible light and visible light also presents a gradient distribution with temperature, and the non-enhanced area cannot achieve nucleation and crystallization due to the limitation of the heat treatment temperature. This ensures that the non-enhanced area of the glass product also has a high light transmittance and maintains a good visual effect.
  • the Vickers hardness of the reinforced zone is 2%-10% higher than that of the non-reinforced zone, and the fracture toughness of the reinforced zone is 9%-50% higher than that of the non-reinforced zone, which effectively improves the fracture toughness and Vickers hardness of the reinforced zone.
  • the hardness significantly improves the fracture toughness of the glass edge, can prevent the further expansion of unhealed micro-cracks, and effectively avoid the phenomenon of a large number of micro-cracks, chipping points and chipping on the glass edge.
  • the glass product prepared by the present invention not only improves the strength of the reinforced area (edge) of the thin glass, but also maintains a good visual effect in the non-reinforced area (display screen), and is suitable for partial protection and coverage of handheld devices, notebook computers, desktop computers, and televisions. .

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Abstract

一种具有局部增强结构的玻璃及其加工方法，包括局部增强区和非增强区，局部增强区包含呈梯度分布的晶体相；在玻璃横向截面上，局部增强区的结晶度向非增强区延伸的方向上呈递减分布。这样，不仅有效地提高了玻璃制品的局部强度，还有效保证非增强区的可见光的透光率。使获得的玻璃制品具有局部机械强度高和透光性能好的特点。该生产方法简单，生产工艺容易控制，并且生产成本较低，工艺独特，可操作性强，易于推广应用。

Description

一种具有局部增强结构的玻璃及其加工方法 技术领域
本发明属于玻璃制品技术领域，尤其涉及一种具有局部增强结构的玻璃及其加工方法。
背景技术
玻璃制品，例如覆盖玻璃和玻璃底板等，可用于消费者和商用电子器件，例如LCD和LED显示器、电脑监测器以及自动取款机(ATM)等。部分此类玻璃制品可包括“触摸”功能，这使得玻璃制品必须与各种物体(包括用户的手指和/或手写笔装置)接触，这样，玻璃必须足够的牢固，以经受常规接触而不损坏。此外，此类玻璃制品还可结合到便携式电子器件中，如移动电话、个人媒体播放器和平板电脑。随着电子产品的快速发展，电子设备领域对玻璃制成的保护盖板、外壳、封罩等制品提出了更高的要求，其不仅要求高强度、耐刮擦，还希望变得更薄、更轻、更坚固、更抗破裂和更美观。制品的厚度范围一般在0.4-2mm，所用的玻璃基材是常规意义上的薄玻璃。而上述薄玻璃在生产过程中，需要切割成合适的尺寸，切割时不可避免地会导致玻璃边部区域产生大量微裂纹、崩点和崩边。并且玻璃本身的脆性高，断裂韧性小，产生的大量裂纹极易扩展，从而导致玻璃强度的极大降低。为了能够满足使用的要求，必须使玻璃在较薄厚度下仍具有高的强度。然而，提高玻璃强度的同时，必然会牺牲其透光性。因此，如何提高玻璃边部区域的强度是本领域技术人员需要解决的问题。
为了解决上述问题学者们也做了大量的研究。传统方法是将玻璃的边部区域进行腐蚀处理，进而消除微裂纹，提升玻璃边部区域的强度。如发明专利CN107555804A一种触摸屏玻璃的制备方法，蚀刻玻璃的边缘，去除玻璃的边缘的毛刺，消除了应力集中，使玻璃边缘受力更均匀，从而大幅地增加了玻璃的强度。发明专利CN103108842A公开了强化玻璃制品边缘的方法，在玻璃制品的至少一个表面上施加有聚合物或聚合物树脂的保护涂层或膜。所述表面可熔化产生或经过抛光，以及/或者经过化学强化或热强化。用蚀刻剂蚀刻边缘以减小边缘上瑕疵的尺寸并减少其数量，从而强化边缘。CN106536439A公开了一种针对液晶显示器(LCD)或者有机发光二极管(OLED)显示器玻璃基材的边缘进行强化的方法，该方法包括将显示器面板的边缘暴露于酸溶液，持续的时间和所处的温度有效地从边缘表面去除不超过20微米的玻璃，从边缘清洗掉酸溶液并对经清洗的边缘施加聚合物保护涂层，以维持边缘表面的蚀刻后强度。上述方法虽然在一定程度上可以提升玻璃边缘的强度，但化学腐蚀过程经常会引起玻璃表面光学性能的降低，玻璃恢复的强度不能持久， 衰减十分严重。另一种方式是在玻璃的边缘涂覆填充液，进而填补玻璃边缘的微裂纹和缝隙，达到提升玻璃边缘强度的目的。如发明专利CN107628757A公开了一种提高显示器平板玻璃边缘强度的方法，采用环保的填充液先对平板玻璃边缘的微裂纹和缝隙进行填充，然后再通过激光照射平板玻璃的四周边缘，进而消除该边缘产生的微裂纹、缝隙和崩边等，因而不会对环境造成污染，更加环保，而且该方法能够更好地保持平板玻璃边缘的强度。但这种方式的弊端是填充液容易被氧化腐蚀，并且其硬度低于玻璃，易被磨损，一旦填充液被腐蚀或磨损即失去强化作用，导致玻璃的破裂。
玻璃陶瓷是20世纪70年代发展起来的新型陶瓷材料，它是在一定温度下热处理后变成有微晶体和玻璃相均匀分布的复合材料，也称作微晶玻璃，具有机械强度高、化学稳定性及热稳定性好、使用温度高及坚硬耐磨等许多宝贵性能。近几年玻璃陶瓷逐步应用到电子显示设备，特别是作为电子设备显示保护屏。虽然玻璃陶瓷机械性能强于常规化学强化玻璃，但在提高强度的同时也牺牲了其光学性能，破坏电子设备显示屏呈现的视觉效果，影响了消费者的视觉体验感。因此如何平衡两者也是最近的研究热点。例如发明专利CN1470470A公开了一种局部结晶的玻璃，所述结晶玻璃包含有稀土元素的沉淀卤化物结晶，所述方法包括：用激光照射包含一种或多种稀土元素和一种或多种卤化物的玻璃基底。但该专利涉及的玻璃用作制造全色显示器、红外传感器、短波固态激光器等，且获得局部结晶的方法不仅需要在玻璃基底中加入稀土元素和卤化物，而且需要应用昂贵的脉冲式和高聚焦的激光器。这不仅使得成本高昂，也使得工业生产化的效率较低，因为激光器的焦点必须精确穿过材料并且该焦点只能够处理非常小的体积。
因此，如何提供一种具有局部增强的玻璃制品，提高薄片玻璃边缘强度、维持电子设备显示区域的视觉效果成为当前所属领域技术人员急需解决的技术难题。
发明内容
针对上述现有技术的不足，本发明的目的在于提供一种具有局部增强结构的玻璃、玻璃盖板，解决现有薄片玻璃周边强度不高和透光性能不好等缺陷。
本发明还提供一种所述具有局部增强结构的玻璃加工方法，解决现有的加工工艺一般需要光敏材料或激光加热，造成生产效率低和生产成本高等问题。
为了解决上述技术问题，本发明采用了如下的技术方案：一种具有局部增强结构的玻璃，包括局部增强区和非增强区，所述局部增强区包含呈梯度分布的晶体相；在所述玻璃横向截面上，所述局部增强区的结晶度向非增强区延伸的方向上呈递减分布。
作为进一步优化，所述局部增强区的结晶度在10～100wt％范围内分布，非增强区中心 位置的结晶度为0wt％。进一步，所述局部增强区的结晶度在40～100wt％范围内分布。
作为进一步优化，所述局部增强区的晶体尺寸为20nm～200nm。进一步，所述局部增强区的晶体尺寸为20nm～85nm。
本发明还提供一种具有局部增强结构的玻璃，包括局部增强区和非增强区；所述局部增强区包含呈梯度分布的晶体相；在所述玻璃横向截面上，局部增强区的可见光透过率向非增强区延伸的方向上呈递增分布。所述局部增强区在可见光范围内光具有至少80％的透过率；所述非增强区的可见光范围内光具有至少90％的透光率。进一步，所述局部增强区的可见光透过率85％～91％，非增强区的可见光透过率为91％～93％。
作为进一步优化，所述玻璃制品的厚度为0.2mm～1.5mm。
作为进一步优化，所述具有局部强化结构的玻璃，所述玻璃制品中Li、Na或K的氧化物的mol％含量为5％～30％，Na 2O小于或等于Al 2O 3和B 2O 3的总量。进一步，所述玻璃制品包括以下mol％的成分：Si 2O至少64％；Al 2O 3：4～12％；B 2O 3：1～3％；Li 2O：5～25％；P 2O 5：0～3％；ZrO 2：0～3％；NaCl：0～1％；Na 2SO 4：0～1％；其中，Na 2O：小于或等于氧化铝和B 2O 3的总量。
其中，所述局部增强区占玻璃制品总面积的1/25～3/5。所述局部增强区为玻璃制品的至少一边部区域。所述“边部”为玻璃制品边缘往玻璃内部延伸一定宽度所形成的带状。例如，该玻璃为矩形，所述局部增强区为矩形玻璃的边框区域，边框的长度为矩形玻璃所在边的长度，边框宽度为m或者n，m为矩形玻璃宽的5％～10％，n为矩形玻璃长的5％～20％；m≦n。
本发明还提供一种玻璃盖板，采用上述具有局部增强结构的玻璃经化学强化处理而成。在用于手持设备、笔记本电脑、桌面电脑和电视机的部分保护覆盖玻璃方面的用途，或在形成显示器基材、触摸传感器或者整体式触摸覆盖玻璃的至少部分方面的用途。
本发明还提供一种具有局部增强结构的玻璃加工方法，针对切割成型的前体玻璃进行热处理，所述热处理包括核化处理和晶化处理，控制非增强区热处理的最高热处理温度低于增强区的最低核化处理温度。进一步，所述非增强区最高热处理温度低于增强区的核化处理温度10～100℃。
作为进一步优化，所述热处理过程中加热速率低于50℃/min。进一步，所述热处理过程中加热速率为10℃/min～30℃/min。
作为进一步优化，所述核化处理的温度为DSC玻璃转变点(Tg)以上5～80℃，核化处理2-7h。进一步，所述核化处理的温度为DSC玻璃转变点(Tg)以上30～70℃，核化处 理2～5h。进一步，所述核化处理的温度为DSC玻璃转变点(Tg)以上35～65℃，核化处理3～4h。
作为进一步优化，所述晶化温度为DSC第一个析晶峰以下20～150℃或DSC第二个析晶峰以下70～150℃，晶化处理1～2次，每次处理2～6h。
作为进一步优化，对前体玻璃核化处理与晶化处理采用对增强区的第一主表面和第二主表面同时直接加热；而非增强区的加热为增强区热传导方式，非增强区的第一主表面和第二主表面对应散热装置，控制其最高温度低于增强区的最低核化处理温度。进一步，在热处理过程中所述非增强区的第一主表面和第二主表面分别与散热装置之间设置导热硅脂层。所述导热硅脂层厚度小于0.3mm。
本发明还提供一种具有局部增强结构的玻璃加工设备，包括加热装置和散热装置；所述加热装置具有对前体玻璃指定的局部增强区的两个相对表面加热的加热部；所述散热装置具有对前体玻璃指定的非增强区的两个相对表面散热的散热部。所述加热部具有两个加热表面，所述加热表面的外部轮廓与所述玻璃的局部增强区相一致，所述散热部具有两个散热表面，所述散热表面的外部轮廓与所述玻璃制品的非增强区相一致。进一步，所述加热表面分别与增强区的两个相对表面距离小于或等于所述玻璃厚度的1/2，包括0；所述散热表面分别与非增强区的两个相对表面的距离小于或等于所述玻璃厚度的1/2，包括0。
作为进一步优化，所述加热装置为温控电加热板，与控制器相连。所述散热装置内还设置了散热管，所述散热管位于散热部的四周和/或内部，所述散热管的两端设有开口，分别与冷却介质的进口和出口相连通。进一步，所述散热部采用导热系数为350～450W/mK的高导热金属。所述高导热金属采用银、铜、银的合金或铜的合金。
相比现有技术，本发明具有如下有益效果：
1、本发明所述具有局部增强结构的玻璃中，其局部增强区包含呈梯度分布的晶体相；在所述玻璃的横向截面上，局部增强区的结晶度向非增强区延伸的方向上呈递减分布，在所述玻璃的纵向截面上，局部增强区的结晶度分别由玻璃主表面向内部延伸的方向上均匀分布。这样，不仅有效的提高了玻璃制品的局部强度，还有效的保证了非增强区高透光率。其中局部增强区的断裂韧性比非局部增强区的断裂韧性提高9％～50％，局部增强区的维氏硬度比非局部增强区的维氏硬度提高2％～10％，使获得的玻璃制品具有局部机械强度高、更薄、更轻、更坚固、更抗破裂和透光性能好高的特点，解决薄玻璃边缘强度和显示屏视觉效果不佳的问题。
2、本发明在制备玻璃材料时，本发明通过对玻璃板的局部增强区和非增强区进行差 异加热处理，使局部增强区在横向截面上温度呈梯度分布，因而增强区在横向截面上的结晶度和可见光透光率也随温度呈梯度分布，而非增强区由于热处理温度限制无法实现成核和析晶，保障玻璃制品的非增强区还具有高透光率，维持良好的视觉效果。
3、本发明玻璃基础成分必须控制玻璃内氧化钠的引入量，小于等于氧化铝和氧化硼的引入量，保证桥氧的比例，使玻璃陶瓷内二硅酸锂为主晶相。基于单个“分子量”的硅酸锂晶体无桥氧，单个“分子量”的二硅酸锂有一个桥氧，结构相对稳定，从而提高了局部增强区的结晶效率。
4、该生产方法简单，无需紫外光或激光加热，生产工艺容易控制，并且生产成本较低，工艺独特，可操作性强，易于推广应用，可以实现批量化工业化生产。
附图说明
图1为本发明具有局部强化结构玻璃一实施例的结构示意图。
图2为图1的A-A剖视图。
图3为本发明制备具有局部强化结构玻璃在不同波长下的可见光透过率的曲线。
图4为本发明具有局部强化结构玻璃加工设备的结构示意图。
具体实施方式
下面结合实施例对本发明作进一步的详细说明。
以下是对本发明相关专用名称及相关测量方法的解释：
在本发明中，“前体玻璃”是切割成型的玻璃片，大小适用于待安装的手持电子设备等产品。
在本发明中，“化学强化玻璃”是经过高温离子交换工艺处理后的化学钢化玻璃。在高温熔盐中大离子半径的碱金属离子取代玻璃中的小离子半径的碱金属离子从而产生交换离子体积差，在前体玻璃的表层中产生由高到低的压应力，阻碍和延缓玻璃微裂纹的扩展，达到提高玻璃机械强度的目的。
在本发明中，“压缩应力层的深度(DOL)”是指在强化制品内从强化过程生成的压缩应力达到零的深度位置。
在本发明中，术语“第一”和“第二”主表面可以互换使用，以指代组件的相对主表面。在一些实施方式中，“第一”主表面可以指的是面朝目标用户的前表面，例如，将光发射到用户或者向用户显示图像。类似地，“第二”主表面可以指的是面朝远离用户的背表面，例如朝向装置的背板(如果存在的话)。
在本发明中采用常规方法测量透光率，采用玻璃板俯视面的透过率，测试仪器光斑为 圆形，光斑直径∈(1/3a，1/2a)，360-740nm内每隔10nm测量一次透过率，得到透过率曲线。
参见图1～2，一种具有局部增强结构的玻璃，包括局部增强区1和非增强区2；所述局部增强区1包含呈梯度分布的晶体相；在所述玻璃的横向截面上，局部增强区1的结晶度向非增强区2延伸的方向上呈递减分布；在所述玻璃的纵向截面上，局部增强区的结晶度分别由玻璃主表面向内部延伸的方向上均匀分布。所述玻璃在横向截面上向非增强区延伸方向上存在非等温的温度分布，这种温度梯度分布可来自在将前体玻璃形成为玻璃制品时玻璃前体在局部增强区和非增强区能精准的设置不同的温度，来控制其是否能核化并结晶；另外由于玻璃制品的局部增强区和非增强区的接触区域存在温差，能够进行热传递，所以局部增强区在横向截面上向非增强区延伸的方向上温度呈递减分布，进而使局部增强区成核晶核的数量和结晶度也随温度呈递减分布。由于玻璃制品厚度较薄，局部增强区在纵向截面上温度相差不大，和外界环境之间的热传递可忽略不计，因此局部增强区的结晶度由玻璃主表面向内部延伸的方向上均匀分布。
当玻璃制品以基板或板状的形式被采用时，厚度优选地在0.2mm～1.5mm的范围内，并且更优选地在0.8mm至1mm的范围内。进一步，玻璃制品可拥有在可见光范围内基本上透明并且在其压缩应力区域的发展之后保持基本上透明的成分。
在一个实施方式中，所述局部增强区的结晶度在10～100％范围内分布，作为优选的，所述局部增强区的结晶度在40～100％范围内分布。非增强区中心位置的结晶度为0％，则保障了电子设备显示区域的视觉效果。局部增强区的晶体的平均尺寸在20nm～200nm之间，优选在20nm～85nm之间。平均晶体尺寸在20nm～85nm之间的晶体不影响玻璃的可见光透过率，局部增强区包含晶体相和玻璃相，晶体相分布在玻璃相内部。当可见光射入局部增强区内部时，会在晶体相和玻璃相的分界面(所述分界面为引起散射作用的截面)发生散射和/或折射。其中，分界面上散射作用对局部增强区的平均可见光透过率影响较大。通常散射作用越大，局部增强区的平均可见光透过率越小。散射作用的大小主要取决晶体平均尺寸的大小，一般来说，晶体平均尺寸越小，引起散射作用的截面的面积就越小，相应地，截面对可见光的散射作用就越小，相应局部增强区的平均可见光透过率越大。本发明的局部增强区晶体的平均晶体尺寸小于或等于85nm，相应地晶体引起光散射作用的截面积较小，相应地晶体对光的散射作用较小。
而本发明的玻璃制品的局部增强区中除了含有玻璃相的原子外，还含有晶体相，借助晶体本身的机械性能，可以提高局部增强区的平均硬度、抗折强度、断裂韧性等机械性能， 从而调整局部增强区的抗划伤和抗跌落等性能。并且，本发明的局部增强区中的晶体可以偏转玻璃相微裂纹的扩展路径，使微裂纹难以扩展。
晶体的平均尺寸越小，相应地局部增强区的平均可见光透过率越高。但是，局部增强区内晶体平均尺寸的大小，会对微晶玻璃的机械性能产生影响。一般来说，局部增强区内晶体的平均尺寸越小，相应微晶玻璃的机械性能越差。基于此，本发明中晶体的一个较佳的平均尺寸是20nm～85nm。这样，该玻璃制品的局部增强区在解决因强度不足造成的微裂纹、崩点和崩边等问题的同时保障其在可见光波段具有较高的透过率。
在一个实施方式中，参见如图2所示，一种具有局部增强结构的玻璃，包括局部增强区1；所述局部增强区包含呈梯度分布的晶体相；在所述玻璃的横向截面上，局部增强区1的可见光透过率向非增强区2延伸的方向上呈递增分布。
本发明中，所述玻璃中局部增强区占玻璃盖板总面积的1/25～3/5；优选的，局部增强区的面积为玻璃盖板总面积的1/5。优选的，所述局部增强区为玻璃制品的至少一边部区域，文中，所述“边部区域”为玻璃制品的边缘往玻璃内部延伸一定宽度形成的带状区域。如图1所示，玻璃制品的局部增强区为矩形的至少一个边框区域1，边框的长度为矩形玻璃所在边的长度，边框宽度为m或者n，m为矩形玻璃宽的5％～10％，n为矩形玻璃长的5％～20％；m≦n。在一些实施例中，本发明具有局部强化结构玻璃在不同波长下测试可见光透过率，具体的，以上述矩形玻璃制品为例分析其可见光透光率，如图1所示，边框1为局部增强区，中间区域2为非增强区，参见图3，曲线A为测试仪器光斑切于玻璃制品局部增强区的最外侧(即玻璃制品的外边缘)所测得，其平均值范围87％-89.5％，最低值大于81％；曲线B为测试仪器光斑切于玻璃制品局部增强区与非增强区的接壤处(即玻璃制品局部增强区的最内侧)所测得，其平均值范围90.5％-91.5％，最低值大于86％；曲线C为测试仪器光斑切于玻璃制品局部增强区最外侧和最内侧之间的中心线所测得，其平均值范围89.5％-90.5％，最低值大于84％。可见，在发明中，所述玻璃是透明的，有1mm的厚度玻璃的局部增强区在可见光范围内平均透光率为87％或更高，88％或更高，89％或更高，90％或更高(包括表面反射损失)。而通常的微晶玻璃可能在380nm到780nm的波长范围内是半透明的，并且对于厚度为1mm的微晶玻璃制品，在450纳米至600纳米的波长范围内，半透明微晶玻璃的平均透过率为20％至85％以下。本发明玻璃制品的局部增强区由玻璃的边缘向内部延伸，这样能很好的控制玻璃边缘的微裂纹扩展，提高玻璃的强度，尤其是玻璃边缘的强度，同时不影响玻璃的主显示屏的视觉效果。
在另一个实施方式中，参见如图1和图2，本发明提供了一种玻璃盖板，包括：第一 主表面及其相对的第二主表面、多个边框和一定厚度的玻璃制品，所述玻璃制品具有多个可离子交换的碱金属离子，可以形成从所述主表面延伸到所述玻璃制品中的第一选择深度的压缩应力区域；至少一个边框为局部增强区，所述局部增强区包含呈梯度分布的晶体相；在所述玻璃制品的横向截面上，局部增强区的结晶度由外部边缘向非增强区2延伸的方向上呈递减分布。
作为说明，边框是指玻璃制品(或玻璃盖板)的任意多边形至少一边或矩形的四条周边。可包括直边缘部分、弯边缘部分、斜边缘部分、粗糙边缘部分和锐利边缘部分当中的一种或任意组合。当玻璃制品以基板或板状的形式被采用时，厚度优选地在0.2mm～1.5mm的范围内，并且更优选地在0.5mm至1mm的范围内。进一步，玻璃制品可拥有在可见光范围内基本上透明并且在其压缩应力区域的发展之后保持基本上透明的成分。
在一个或多个实施例中，该压缩应力区域可以由强化过程(例如，通过热回火、化学离子交换或类似过程)来形成。与压缩应力区域相关联的压缩应力(CS)的量和压缩应力层的深度(DOL)可以基于制品100的特定用途而变化。一些实施例中，在所述压缩应力区域中的最大压缩应力为300～400MPa，并且所述第一选择深度为所述制品的所述厚度的至少5％。
本发明所公开的玻璃盖板可广泛用于另一制品中，如手持设备、笔记本电脑、桌面电脑和电视机的部分保护覆盖玻璃，还可以用于形成显示器基材、触摸传感器或者整体式触摸覆盖玻璃的至少部分，或需要一些透明度、耐划伤性、耐磨性或其组合的任何制品。特别地，可以被应用在电子装置中，例如手机(mobile phone)、平板电脑(Pad)、电脑、虚拟现实(virtual reality，VR)终端设备、增强现实(Augmented Reality，AR)终端设备、可穿戴设备、电视等。该电子装置包括具有前表面、后表面和侧表面的外壳；位于所述外壳内的电子组件；位于所述外壳的前表面或者与所述外壳的前表面相邻的显示器；以及布置在所述显示器上的覆盖基材，以便隔离和保护显示面板，避免外界事物或者作用力对显示面板造成损坏。所述覆盖基材或外壳包括上述任意所述的玻璃盖板。如前所述，该玻璃盖板具有较好的光线透过率，故而不会影响在显示面板的使用。同时，由于该玻璃盖板边框具有较好的机械强度，因此，玻璃盖板抗划伤与抗跌落等性能获得提升，故而不容易损坏。
本发明还提供一种局部增强结构的玻璃加工方法，采用切割成型的前体玻璃，对所述前体玻璃进行包括核化处理与晶化处理的热处理，控制非增强区热处理的最高温度低于增强区最低的核化处理温度。进一步，所述非增强区最高热处理温度低于增强区的核化处理温度10-100℃。这样，在热处理过程中玻璃的非增强区不会发生核化，并且在晶化处理过 程中，由于玻璃的非增强区没有核化，因此在此温度范围内难以析晶，并且不会因为热膨胀破裂，所以玻璃制品的非增强区内无晶体。
作为说明，热处理是使玻璃产生晶体相和玻璃相的关键工序，使基础玻璃结晶化，在热处理工艺中先后经历核化和晶化两个阶段。其中，核化温度应稍高于玻璃的软化温度，晶化是使晶核生长成目标大小的微纳米晶体，晶化温度一般取晶体生长的放热温度。在原料确定后，玻璃的结构与性能主要取决于热处理工艺。本发明在制备的玻璃制品时，采用特定的模具对玻璃的指定区域进行具有温差的温度处理。非增强区在进行热处理时，温度低于玻璃的核化温度，所以非增强区无法完成析晶；而增强区热处理时的核化温度和晶化温度，能使玻璃中的晶核长大，以使晶核长大成目标大小的微纳米晶体，并且热处理温度与晶核数量呈正相关。由于局部增强区与非增强区的接触区域存在温度差，导致上述两个区域的接触面之间存在热传递，因此在局部增强区在横向截面上向非增强区延伸的方向上呈温度梯度分布，进而在局部增强区在横向截面上向非增强区延伸的方向上结晶度也呈梯度分布。另外，热处理过程中玻璃的部分微裂纹会因此愈合，析出的晶体的断裂韧性较大，能够阻碍未愈合的微裂纹进一步扩展。因此本发明通过温度调控可较好的控制析晶的区域，从而达到局部强化的目的。
对于上文所述的玻璃，成核温度可以是玻璃转变点(Tg)以上5～80℃。作为优选，成核温度可以是玻璃转变点(Tg)以上30～70℃。作为优选，成核温度可以是玻璃转变点(Tg)以上35～65℃。加热至成核温度可涉及单加热速率或者多加热速率。例如，在多加热速率的情况下，可以较高速率(例如，15～25℃/分钟)将玻璃制品从初始温度加热至中间温度，以及以较低速率(例如，6～12℃/分钟)从中间温度加热至成核温度。
在玻璃制品到达成核温度之后，将玻璃制品在成核温度维持一段时间，在该过程中在玻璃制品中建立起晶核。成核时长可以为2～7h；作为优选，成核时长还可以为2～5h，更为优选的，成核时长还可以为3～4h。
在成核之后，将玻璃制品从成核温度加热至结晶温度。结晶温度为DSC第一个析晶峰以下20～150℃或DSC第二个析晶峰以下70～150℃。低温热处理时玻璃结构不稳定，形成的桥氧比例相对较少，此时主要析出硅酸锂；如果希望在玻璃中形成二硅酸锂作为主晶相，则可以延长时间或者提高结晶温度，玻璃结构逐渐稳定，桥氧比例提升，硅酸锂逐渐转变为二硅酸锂。
在玻璃制品到达结晶温度之后，将玻璃制品在结晶温度维持一段时间；在该过程中，至少一个晶相在玻璃中生长。在一个实施方式中，结晶温度使得在玻璃中形成二硅酸锂作 为主晶相。结晶时长可以为2～6h。在结晶时间段结束时，玻璃制品已经变成局部的结晶相。
在一个实施例中，所述增强区的热处理温度比非增强区热处理温度高10～100℃，此温度范围内既可以控制非增强区的玻璃不会核化，也不会因为热膨胀破裂。在另一个实施例中，加热过程中的温度可调，加热升温速率低于50℃/min及其之间的所有范围和子范围，以防玻璃板炸裂，加热升温速率优先为45℃/min或更小、40℃/min或更小、35℃/min或更小、30℃/min或更小、25℃/min或更小、20℃/min或更小、15℃/min或更小、10℃/min或更小、5℃/min或更小，更优选为10～30℃/min。
在另一实施例中，对所述前体玻璃进行核化处理与晶化处理前，在所述前体玻璃的第一主表面和第二主表面上的非增强区上设置导热硅脂层。导热硅脂层可以作为薄膜被涂布、印刷和/或以其它方式附接在玻璃制品的非增强区的第一主表面和第二主表面上设置，这样，既可以增加对非增强区本体的散热效率，又避免热处理过程对非增强区表观质量的破坏。进一步，所述导热硅脂层厚度小于0.3mm，具有为0.2mm或更小、0.1mm或更小、0.05mm或更小、0.04mm或更小、0.03mm或更小、0.02mm或更小、0.01mm或更小的厚度的导热硅脂层。
在本发明中，准确称量原料，将原料充分混合之后，将其高温加热，进行熔化。玻璃的熔化是一个非常复杂的过程，它包括一系列物理的、化学的、物理化学的现象和反应，这些现象和反应的结果使各种原料由机械混合物变成了复杂的熔融物，即玻璃液。玻璃的熔化大致可以分为硅酸盐形成、熔化形成玻璃液、玻璃液澄清、玻璃液均化、玻璃液冷却5个阶段。本发明在制备时采用的熔化温度为1610℃～1650℃。
前体玻璃的制备过程是将熔融的玻璃液转变为具有几何形状制品的过程。前体玻璃可以是前体玻璃板或前体玻璃砖。本发明在前体玻璃的制备过程可以通过压延法、或浮法、或溢流法工艺将玻璃液制成前体玻璃板，或通过浇铸法工艺将玻璃液制成前体玻璃砖。具体地，本发明中采用的压延法工艺、浮法工艺、溢流法、浇铸法工艺均采用现有技术即可。具体地，本发明将前体玻璃经过机械裁切制备成具有一定形状的前体玻璃板，通常为矩形玻璃板。
本发明中玻璃制品或前体玻璃主要包括以下mol％的成分(以下涉及成分时以玻璃表示玻璃制品或前体玻璃)：二氧化硅：64～72％；氧化铝：4～12％；B 2O 3：1～3％；Li 2O：5～25％；Na 2O：小于或等于氧化铝和B 2O 3的总量。
进一步，玻璃制品或前体玻璃还包括以下mol％的成分：P 2O 5：0～3％；ZrO 2：0～3％；NaCl：0～1％；Na 2SO 4：0～1％。
在玻璃和微晶玻璃中，SiO 2作为主要玻璃形成氧化物，是玻璃网络形成体，能够形成硅-氧四面体作为玻璃的基础网络。同样，Al 2O 3也可以提供稳定的网络，是玻璃网络中间体，能够形成铝-氧四面体与硅-氧四面体形成玻璃的基础网络；可提高玻璃粘度，抑制析晶。若氧化铝的量过高，锂硅酸盐晶体的分数可能会减少，可能到无法形成连锁结构的程度，同时熔体的粘度通常也会增加。在一些实施例中，所述玻璃组合物可包括4～12mol％Al 2O 3及其之间的所有范围和子范围，例如4～11.5mol％，4～11mol％，4～10.5mol％，4～10mol％，4～9.5mol％，4～9mol％，5～11.5mol％，5～11mol％，5～8.2mol％，8.6～8.8mol％，9mol％，9.4mol％，9.6mol％，9.8mol％，10mol％，10.2mol％，10.4mol％，10.6mol％，10.8mol％，11mol％，11.2mol％，11.4mol％，11.6mol％，11.8mol％，或者12mol％。
B 2O 3也可作为玻璃网络形成体，能够形成硼-氧四面体与硅-氧四面体形成玻璃的基础网络。有助于提供低熔点的玻璃前驱体。此外，在原丝玻璃和微晶玻璃中加入B 2O 3有助于实现互锁晶体微观结构，还可以提高微晶玻璃的抗损伤能力。在一些实施例中，所述玻璃组合物可包括1～3mol％Al 2O 3及其之间的所有范围和子范围，例如1～2.8mol％，1～2.5mol％，1～2.4mol％，1～2mol％，1～1.5mol％，2～3mol％，2～2.5mol％，2.5～3mol％，1mol％，1.4mol％，1.6mol％，1.8mol％，2mol％，2.2mol％，2.4mol％，2.6mol％，2.8mol％，3mol％。
Na 2O能降低玻璃液粘度，在玻璃网络中起断网作用，Na离子过多会降低玻璃网络中的桥氧比例，1mol氧化钠提供1mol氧供氧化铝或氧化硼形成四面体，即提供1mol桥氧，所以氧化钠的加入量需要小于或等于氧化铝和B 2O 3的总量。在一些实施例中，所述玻璃组合物可包括Na 2O：小于或等于氧化铝和B 2O 3的总量及其之间的所有范围和子范围，例如5～15mol％，4～11mol％，4～10.5mol％，4～10mol％，4～9.5mol％，4～9mol％，5～11.5mol％，5～11mol％，5～8.2mol％，8.6～8.8mol％，5mol％，6mol％，7mol％，8mol％，9mol％，10mol％，11mol％，11.4mol％，11.6mol％，11.8mol％，12mol％，13mol％，14mol％，14.5mol％，或者15mol％。
Li 2O能够显著降低玻璃液粘度，引入过多会使玻璃低温析晶。氧化锂一般用于玻璃陶瓷的形成，而其他的碱金属氧化物则倾向于减少玻璃陶瓷的形成，在玻璃陶瓷中形成铝硅酸盐残留玻璃。在一些实施例中，所述玻璃组合物可包括Li 2O 5～25％及其之间的所有范围和子范围，例如5～24mol％，5～22mol％，5～20mol％，5～18mol％，5～10mol％，4～25mol％，4～20mol％，4～18mol％，4～15mol％，4～10mol％，5mol％，6mol％，7mol％，8mol％，9mol％，10mol％，11mol％，12mol％，15mol％，18mol％，20mol％，21mol％，22mol％， 23mol％，24mol％,或者25mol％。
玻璃的组合物还可以包括P 2O 5，P 2O 5可以作为成核剂产生大量成核。少量引入就会使玻璃热处理过程中可以析出Li 3PO 4晶核，重金属离子存在情况下会更易析出(较低温)。若P 2O 5的浓度过高，前驱体玻璃成型冷却后的脱硝作用就难以控制。在一些实施例中，所述玻璃组合物可包括P 2O 50～3％及其之间的所有范围和子范围，例如0～2.8mol％，0～2.6mol％，0～2mol％，0～1.8mol％，0～1.0mol％，1～2.5mol％，1～2.0mol％，1～1.8mol％，1～1.5mol％，1～1.2mol％，0mol％，1.5mol％，1.8mol％，2mol％，2.9mol％，2.8mol％，2.6mol％，2.5mol％，2.1mol％，0.8mol％，0.6mol％，0.5mol％，0.4mol％，0.3mol％，0.2mol％,或者0.1mol％。
玻璃的组合物还可以包括ZrO 2，ZrO 2也可以作为成核剂产生大量成核，可以通过显著降低玻璃在形成过程中的脱氮作用和降低液相线温度来提高Li 2O-Al 2O 3-SiO 2-P 2O 5玻璃的稳定性。ZrO 2的加入还有助于降低晶体的晶粒尺寸，从而有助于透明玻璃陶瓷的形成。在一些实施例中，所述玻璃组合物可包括ZrO 20～3％及其之间的所有范围和子范围，例如0～2.8mol％，0～2.6mol％，0～2mol％，0～1.8mol％，0～1.0mol％，1～2.5mol％，1～2.0mol％，1～1.8mol％，1～1.5mol％，1～1.2mol％，0mol％，1.5mol％，1.8mol％，2mol％，2.9mol％，2.8mol％，2.6mol％，2.5mol％，2.1mol％，0.8mol％，0.6mol％，0.5mol％，0.4mol％，0.3mol％，0.2mol％,或者0.1mol％。
玻璃的组合物还可以化学澄清剂。这种澄清剂包括但不限于NaCl和Na 2SO 4。在一些实施例中，所述玻璃组合物可包括NaCl 0～1％及其之间的所有范围和子范围，例如0～0.9mol％，0～0.8mol％，0～0.7mol％，0～0.6mol％，0～0.5mol％，0～0.4mol％，0.5～1.0mol％，0.5～0.8mol％，0.5～0.7mol％，0.5～0.6mol％，1mol％，0.9mol％，0.8mol％，0.7mol％，0.6mol％，0.5mol％，0.4mol％，0.3mol％，0.2mol％,或者0.1mol％。在一些实施例中，所述玻璃组合物可包括Na 2SO 40～1％及其之间的所有范围和子范围，例如0～0.9mol％，0～0.8mol％，0～0.7mol％，0～0.6mol％，0～0.5mol％，0～0.4mol％，0.5～1.0mol％，0.5～0.8mol％，0.5～0.7mol％，0.5～0.6mol％，1mol％，0.9mol％，0.8mol％，0.7mol％，0.6mol％，0.5mol％，0.4mol％，0.3mol％，0.2mol％，或者0.1mol％。
作为说明，单个“分子量”的硅酸锂晶体无桥氧，单个“分子量”的二硅酸锂有一个桥氧，结构相对稳定。热处理过程中玻璃的结构重排，硅氧四面体通过桥氧连接，当低温热处理时，玻璃结构不够稳定，桥氧较少，硅酸锂优先析出；同时，氧化钠的加入断开了玻璃网络，桥氧数减少，硅酸锂晶体增多当氧化钠含量增大到一定比例时，只能够析出硅酸锂晶 体。因此，必须控制玻璃内氧化钠的引入量，小于等于氧化铝和氧化硼的引入量，保证桥氧的比例，使玻璃陶瓷内二硅酸锂为主晶相。
作为又一实施例，本发明制备的局部增强型玻璃制品在热处理(核化和晶化)后还包括将所述玻璃制品的第一主表面和第二主表面中的至少一个与盐浴接触，所述盐浴包括多个离子交换碱金属离子，且每个离子交换碱金属离子具有比所述可离子交换的碱金属离子的尺寸大的尺寸。将前述的局部增强型玻璃进行离子交换之后得到化学强化微晶玻璃。离子交换之后，增强区表面的碱金属离子被半径更大的碱金属离子所替换得到化学强化微晶玻璃。
传统的离子交换过程通常发生在不超过玻璃的转变温度的升高的温度范围内。通过以下方式进行该过程：将玻璃浸没在包含碱金属盐(通常是硝酸盐)的熔浴中，所述碱金属盐的离子大于所述玻璃中的主体碱金属离子。所述主体碱金属离子被交换为较大的碱金属离子。例如，可以将含Na +的玻璃浸在硝酸钾(KNO 3)熔浴中。熔浴中的较大K +将置换玻璃中的较小Na +。由于在之前被较小的碱金属离子占据的位点存在较大的碱金属离子，在玻璃表面处或表面附近产生压缩应力，在玻璃内部产生张力。
在离子交换过程之后，将玻璃从熔浴中取出并冷却。离子交换深度(即侵入的较大碱金属离子渗入玻璃的深度)通常为20-300μm，例如40-300μm，并通过玻璃组成和浸泡时间控制所述离子交换深度，在本发明中离子交换的深度不低于玻璃厚度的5％。离子交换的时间和温度对化学强化微晶玻璃的表面压应力存在影响。随着离子交换温度的不断升高(离子交换时间相同)，表面压应力呈现先升高后降低的趋势；基于此，本发明合适的离子交换温度为380℃～450℃。另外，随着离子交换时间的延长(离子交换温度不变)，表面压应力呈现先升高后降低的趋势；基于此，本发明合适的离子交换时间为2h～18h。
用来强化玻璃和/或玻璃陶瓷的一种或更多种离子交换过程可包括，但不限于：将其浸没在单一浴中，或者将其浸没在具有相同或不同组成的多个浴中。另外，一个或多个浴的组成可以包括一种以上类型的较大离子(例如，Na +和K +)或单个较大离子。本领域技术人员将理解，离子交换工艺的参数包括但不限于：浴的组成和温度、浸入时间、内部玻璃层在一个或多个盐浴中的浸入次数、多个盐浴的使用、附加步骤(诸如退火、洗涤)，示例性熔池组成可以包括较大碱金属离子的硝酸盐、硫酸盐和氯化物。典型的硝酸盐包括KNO 3、NaNO 3、LiNO 3、NaSO 4及其组合。
作为优选的，将局部增强型玻璃制品浸入100％的KNO 3或NaNO 3、KNO 3和LiNO 3的组合的熔融盐浴中，所述熔融盐浴的温度为370℃至480℃。其中，本文提到的盐浴组 分均以wt％计。在一些实施例中，可以将内部玻璃层浸入熔融混合盐浴中，所述盐浴包括1％至99％的NaNO 3，在一些实施例中，所述盐浴中可包括NaNO 31～99％及其之间的所有范围和子范围，例如1～90％，1～80％，1～70％，1～60％，1～50％，1～40％，10～90％，20～80％，30～70％，40～60％，1％，20％，30％，40％，50％，60％，70％，80％，90％，99％。在一些实施例中，所述盐浴中可包括KNO 31～99％及其之间的所有范围和子范围，例如1～90％，1～80％，1～70％，1～60％，1～50％，1～40％，10～90％，20～80％，30～70％，40～60％，1％，20％，30％，40％，50％，60％，70％，80％，90％,或者99％。和0％至2％的LiNO 3。在一个或多个实施例中，在将内部玻璃层浸入第一离子交换溶液之后，可将其浸入第二离子交换溶液中。第一离子交换溶液和第二离子交换溶液可以具有彼此不同的组成和/或温度。在第一离子交换溶液和第二离子交换溶液中的浸入时间可以变化。例如，在第一离子交换溶液中的浸入可以比在第二浴中的浸入更长。例如，一步法离子交换的工艺主要为：将微晶玻璃在纯KNO 3和/或NaNO 3和/或LiNO 3熔盐中浸泡2h～18h。又例如，多步法离子交换的工艺主要为：第一步，离子交换温度在纯KNO 3和/或NaNO 3和/或LiNO 3盐浴，380℃～450℃条件下浸泡T 1h；第二步，在纯KNO 3和/或NaNO 3和/或LiNO 3盐浴，380℃～450℃条件下浸泡T 2h；第三步，在纯KNO 3和/或NaNO 3和/或LiNO 3盐浴，380℃～450℃条件下浸泡T 3h……第n步，在纯KNO 3和/或NaNO 3和/或LiNO 3盐浴，380℃～450℃条件下浸泡T n小时。在某些实施例中，第一离子交换温度高于第二离子交换温度下，并且/或玻璃制品与第一离子交换介质接触的时间长于与第二离子交换介质接触的时间。
参见图4，本发明还提供一种制备局部增强结构玻璃的设备，该装置包括加热装置和散热装置，所述加热装置具有对玻璃指定的局部增强区1的两个相对表面加热的加热部6；所述散热装置具有对玻璃指定的非增强区2的两个相对表面散热的散热部3。在另一个实施例中，所述加热部6具有两个加热表面7，所述加热表面7的外部轮廓与所述玻璃的局部增强区1相一致，所述散热部3具有两个散热表面4，所述散热表面4的外部轮廓与所述玻璃制品的非增强区2相一致。
作为优选，可以调整设备加热部的尺寸，进而调整局部增强区的宽度，以满足不同的需求。而中间部位为非增强区不能核化无法析出晶体。这样，既提高了玻璃盖板的强度，又不影响主显示界面的透光率和显示效果。
在一个实施例中，所述加热表面7分别与玻璃制品的上下表面距离小于或等于所述玻璃厚度的1/2，具体可以为所述玻璃制品厚度的40％或更小，30％或更小，20％或更小，10％ 或更小，或加热表面7分别与玻璃制品的上下表面距离为0，即加热表面与玻璃制品的上下表面紧贴。
所述散热表面4分别与玻璃制品的上下表面的距离小于或等于所述玻璃厚度的1/2，具体可以为所述玻璃制品厚度的40％或更小，30％或更小，20％或更小，10％或更小，或散热表面3分别与玻璃制品的上下表面距离为0，即加热表面与玻璃制品的上下表面紧贴。
在另一个实施例中，加热装置为温控电加热板，与控制器相连，可以方便对增强区的温度进行精准管控。
在一个实施例中，所述散热部由具有高热扩散率的材料形成，导热系数大于350W/mK的材料形成，作为优选的，所述高导热金属的导热系数为350～450W/mK。在另一个实施例中，所述散热器由下表1中列出的材料中的一个或多种合金形成。
表1
材料名称 导热系数(W/mK)
银 429
铜 380
代替或补充利用高导热金属材料，散热部可以以一种或多种方式成型或构造以改善非增强区的热传导。图4中显示散热部3中的两个散热表面4具有并排设置且垂直于非增强区上下表面的若干个散热板5组成。这样增加了散热板与空气的接触面积，增加了散热效率。
在另一个实施例中，为了进一步的提高非增强区的散热效果，还可以在所述散热装置内设置散热管，所述散热管位于散热部四周和/或内部。散热管可以按以下方式设置但并不限于以下方式：如散热管沿着非增强区的两个上下表面并排设置，且位于任意相邻的两个散热板之间。在可实施中，所述散热管的两端设有开口，分别与冷却介质的进口和出口相连通。所述冷却介质可以但不限于是冷却水或油或气体混合物等。这进一步的增加了非增强区的散热效果。这样，既提高了非增强区的冷却速率，也增强了非增强区向局部增强区热传递效率。
实施例1
S1：首先根据玻璃前体原材料的配比准确称量(见表2)，然后将原料充分混合之后，将其1630℃的高温下保温4h，进行熔化，得到玻璃液。
S2：将玻璃液浇铸在预热好的不锈钢模具中，再放入退火炉中，在退火点左右进行长时间梯度退火，以消除玻璃的内应力。将退火完成后的玻璃砖，六面进行余量切割，获得尺寸合适的玻璃砖，再采用线切割机、CNC精雕机、平磨抛光机进行尺寸精切割、平磨、扫边，得到尺寸为160mm*80mm*0.65mm的前体玻璃板；
S3：将步骤S2得到的前体玻璃的第一主表面和第二主表面上的局部增强区和非增强区分别进行加热和散热处理，控制加热装置的第一加热板和第二加热板对玻璃的局部增强区进行夹持，首先采用20℃/min的升温速率将加热板升温到530℃，保温5h对前体玻璃板进行核化处理；然后采用30℃/min的升温速率将加热板升温到600℃，保温5h进行第一次晶化处理，后升温至640℃，保温2h，进行第二次晶化处理，控制散热装置的第一散热板和第二散热板对玻璃的非增强区夹持其保持在低于所述玻璃最低的核化温度和晶化温度，制得具有局部强化结构的玻璃制品在横向截面上，局部增强区的结晶度向非增强区延伸的方向上呈递减分布；非增强区未形成晶核无结晶。
S4：将步骤S3制得的局部强化玻璃制品进行离子交换，首先将其进行第一步离子交换IOX1，熔盐采用40wt％NaNO 3+59.5wt％KNO 3+0.5wt％LiNO 3的混合盐浴，强化温度为420℃，强化时间为5h，强化完成后，取出洗净，得到强化玻璃板。
实施例2～7采用实施例1相同的方法获得前体玻璃板，不同的是：
1.各实施例玻璃前体原材料配方不同(表2)；
2.离子交换的盐溶及时间，以及热处理条件不同(表3)；
3.实施例2、5还设置了导热硅脂层。
4.实施例6、7的散热装置还设置了散热管，实施例6的散热管设置在散热板的外周，实施例7的散热管均匀间隔设置在散热板的内部。
表2
成份(mol％) 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7
SiO 2 67 68 68 69 69 70 70
Al 2O 3 6 4.5 5.5 4.2 5 4 5
B 2O 3 1.5 1.2 1 1 0.5 1 2
Na 2O 1.5 2.1 6 5 6 4.5 4
Li 2O 21 22 17 18 17 17 17
P 2O 5 1.2 0.6 0.5 1 1 1.4 1
ZrO 2 1.5 1.4 1.4 1.4 1.4 1.5 1
NaCl 0.3 0.3 0.4 0.5 0.5 0.3 0.3
Na 2SO 4 0.1 0.2 0.1 - - 0.2 0.2
注：“-”表示前体玻璃中不含有该成分。
表3
Figure PCTCN2021082513-appb-000001
注：“-”表示玻璃制品未进行该步骤。
将实施例1～7制备的强化玻璃板进行晶体分析，包括结晶区宽度、晶体尺寸，同时测试微晶玻璃结晶区的可见光透过率和机械性能，其中可见光透光率是在550nm波长下测定的，结果如表4所示。
表4
Figure PCTCN2021082513-appb-000002
通过表4可以看出，本发明通过对玻璃板的局部增强区和非增强区进行温度差异的热处理，使局部增强区在横向截面上温度呈梯度分布，因而增强区在横向截面上的结晶度和可见光透光率也随温度呈梯度分布，而非增强区由于热处理温度限制无法实现成核和析晶，保障玻璃制品的非增强区还具有高透光率，维持良好的视觉效果。而经过结晶处理后 增强区比非增强区的维氏硬度提高了2％～10％，增强区比非增强区的断裂韧性提高了9％～50％，有效提升增强区的断裂韧性和维氏硬度，显著提高玻璃边缘的断裂韧性，能够阻碍未愈合的微裂纹进一步扩展，有效避免玻璃边缘产生大量微裂纹、崩点和崩边的现象。可见，本发明制备的玻璃制品不仅提高薄片玻璃增强区(边部)强度还维持非增强区(显示屏)良好的视觉效果，适用于手持设备、笔记本电脑、桌面电脑和电视机的部分保护覆盖。
以上所述仅为本发明的较佳实施例而已，并不以本发明为限制，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (34)

  1. 一种具有局部增强结构的玻璃，其特征在于，包括局部增强区和非增强区，所述局部增强区包含呈梯度分布的晶体相；在所述玻璃横向截面上，所述局部增强区的结晶度向非增强区延伸的方向上呈递减分布。
  2. 根据权利要求1所述具有局部增强结构的玻璃，其特征在于，所述局部增强区的结晶度在10～100wt％范围内分布，非增强区中心位置的结晶度为0wt％。
  3. 根据权利要求2所述具有局部增强结构的玻璃，其特征在于，所述局部增强区的结晶度在40～100wt％范围内分布。
  4. 根据权利要求1所述具有局部增强结构的玻璃，其特征在于，所述局部增强区的晶体尺寸为20nm～200nm。
  5. 根据权利要求4所述具有局部增强结构的玻璃，其特征在于，所述局部增强区的晶体尺寸为20nm～85nm。
  6. 一种具有局部增强结构的玻璃，其特征在于，包括局部增强区和非增强区；所述局部增强区包含呈梯度分布的晶体相；在所述玻璃横向截面上，局部增强区的可见光透过率向非增强区延伸的方向上呈递增分布。
  7. 根据权利要求6所述具有局部增强结构的玻璃，其特征在于，所述局部增强区在可见光范围内光具有至少80％的透过率；所述非增强区的可见光范围内光具有至少90％的透光率。
  8. 根据权利要求7所述具有局部增强结构的玻璃，其特征在于，所述局部增强区的可见光透过率85％～91％，非增强区的可见光透过率为91％～93％。
  9. 根据权利要求1～8任一所述具有局部增强结构的玻璃，其特征在于，所述玻璃制品的厚度为0.2mm～1.5mm。
  10. 根据权利要求1～8任一项所述具有局部增强结构的玻璃，其特征在于，所述玻璃制品中Li、Na或K的氧化物的mol％含量为5％～30％，Na 2O小于或等于Al 2O 3和B 2O 3的总量。
  11. 根据权利要求10所述具有局部增强结构的玻璃，其特征在于，所述玻璃制品包括以下mol％的成分：Si 2O至少64％；Al 2O 3：4～12％；B 2O 3：1～3％；Li 2O：5～25％；P 2O 5：0～3％；ZrO 2：0～3％；NaCl：0～1％；Na 2SO 4：0～1％；其中，Na 2O：小于或等于Al 2O 3和B 2O 3的总量。
  12. 根据权利要求1～8任一项所述具有局部增强结构的玻璃，其特征在于，所述局部增强区占玻璃制品总面积的1/25～3/5。
  13. 根据权利要求1～8任一项所述具有局部增强结构的玻璃，其特征在于，所述局部增强区为玻璃制品的至少一边部区域。
  14. 根据权利要求1～8任一项所述具有局部增强结构的玻璃，其特征在于，该玻璃为矩形，所述局部增强区为矩形玻璃的边框区域，边框的长度为矩形玻璃所在边的长度，边框宽度为m或者n，m为矩形玻璃宽的5％～10％，n为矩形玻璃长的5％～20％；m≦n。
  15. 一种玻璃盖板，其特征在于，采用权利要求1～8任一项所述具有局部增强结构的玻璃经化学强化处理而成。
  16. 一种如权利要求15所述玻璃盖板，其特征在于，在用于手持设备、笔记本电脑、桌面电脑和电视机的部分保护覆盖玻璃方面的用途，或在形成显示器基材、触摸传感器或者整体式触摸覆盖玻璃的至少部分方面的用途。
  17. 一种具有局部增强结构的玻璃加工方法，其特征在于，针对切割成型的前体玻璃进行热处理，所述热处理包括核化处理和晶化处理，控制非增强区热处理的最高热处理温度低于增强区的最低核化处理温度。
  18. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述非增强区处理的最高热处理温度低于增强区的核化处理温度10～100℃。
  19. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述热处理过程中加热速率低于50℃/min。
  20. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述热处理过程中加热速率为10℃/min～30℃/min。
  21. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述核化处理的温度为DSC玻璃转变点(Tg)以上5～80℃，核化处理2～7h。
  22. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述核化处理的温度为DSC玻璃转变点(Tg)以上30～70℃，核化处理2～5h。
  23. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述核化处理的温度为DSC玻璃转变点(Tg)以上35～65℃，核化处理3～4h。
  24. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，所述晶化温度为DSC第一个析晶峰以下20～150℃或DSC第二个析晶峰以下70～150℃，晶化处理1～2次，每次处理2-6h。
  25. 根据权利要求17所述具有局部增强结构的玻璃加工方法，其特征在于，对前体玻璃核化处理与晶化处理采用对增强区的第一主表面和第二主表面同时直接加热；而非增 强区的加热为增强区热传导方式，非增强区的第一主表面和第二主表面对应散热装置，控制其最高温度低于增强区的最低核化处理温度。
  26. 根据权利要求25所述具有局部增强结构的玻璃加工方法，其特征在于，在热处理过程中所述非增强区的第一主表面和第二主表面分别与所述散热装置之间设置有导热硅脂层。
  27. 据权利要求26所述具有局部增强结构的玻璃加工方法，其特征在于，所述导热硅脂层厚度小于0.3mm。
  28. 一种具有局部增强结构的玻璃加工设备，其特征在于，包括加热装置和散热装置；所述加热装置具有对前体玻璃指定的局部增强区的两个相对表面加热的加热部；所述散热装置具有对前体玻璃指定的非增强区的两个相对表面散热的散热部。
  29. 根据权利要求28所述具有局部增强结构的玻璃加工设备，其特征在于，其特征在于，所述加热部具有两个加热表面，所述加热表面的外部轮廓与所述玻璃的局部增强区相一致，所述散热部具有两个散热表面，所述散热表面的外部轮廓与所述玻璃制品的非增强区相一致。
  30. 根据权利要求28所述具有局部增强结构的玻璃加工设备，其特征在于，所述加热表面分别与局部增强区的两个相对表面距离小于或等于所述玻璃厚度的1/2，包括0；所述散热表面分别与非增强区的两个相对表面的距离小于或等于所述玻璃厚度的1/2，包括0。
  31. 根据权利要求28所述具有局部增强结构的玻璃加工设备，其特征在于，所述加热装置为温控电加热板，与控制器相连。
  32. 根据权利要求28所述具有局部增强结构的玻璃加工设备，其特征在于，所述散热装置内还设置了散热管，所述散热管位于散热部的四周和/或内部，所述散热管的两端设有开口，分别与冷却介质的进口和出口相连通。
  33. 根据权利要求28所述具有局部增强结构的玻璃加工设备，其特征在于，所述散热部采用导热系数为350～450W/mK的高导热金属。
  34. 根据权利要求33所述具有局部增强结构的玻璃加工设备，其特征在于，所述高导热金属采用银、铜、银的合金或铜的合金。
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