WO2022037333A1 - 一种具有安全应力状态的强化玻璃及其加工方法 - Google Patents

一种具有安全应力状态的强化玻璃及其加工方法 Download PDF

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WO2022037333A1
WO2022037333A1 PCT/CN2021/106369 CN2021106369W WO2022037333A1 WO 2022037333 A1 WO2022037333 A1 WO 2022037333A1 CN 2021106369 W CN2021106369 W CN 2021106369W WO 2022037333 A1 WO2022037333 A1 WO 2022037333A1
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Prior art keywords
tempered glass
glass
stress state
state according
safe
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PCT/CN2021/106369
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English (en)
French (fr)
Inventor
黄义宏
谈宝权
陈石峰
姜宏
覃文城
张延起
白一波
胡伟
Original Assignee
重庆鑫景特种玻璃有限公司
华为技术有限公司
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Publication of WO2022037333A1 publication Critical patent/WO2022037333A1/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
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

Definitions

  • the invention relates to the technical field of tempered glass, in particular to a tempered glass with a safe stress state and a processing method thereof.
  • the glass used in such electronic products is mainly chemically strengthened glass after chemical strengthening.
  • Chemically strengthened glass is a kind of ion exchange process. In the salt bath, alkali metal ions with larger ionic radius replace alkali metal ions with smaller ionic radius in the glass to generate exchange ion volume difference. Low tensile stress hinders and delays the expansion of glass micro-cracks, and achieves the purpose of improving the mechanical strength of glass.
  • the tempered glass treated by the ion exchange process produces compressive stress on the surface and corresponding tensile stress on the inside.
  • Chemically strengthened glass is a stress balancer.
  • the compressive stress is low, the strength of the obtained strengthened glass is not high, which cannot meet the customer's requirements for high drop resistance when the product is dropped; if the compressive stress is too high, although it can be obtained.
  • Tempered glass but at the same time will lead to the formation of high tensile stress inside the tempered glass, such tempered glass will have potential safety hazards, explosive cracking or even self-explosion will occur under slight impact, which seriously affects the reliability of the product. It even has a serious impact on the personal safety of customers.
  • the common high-alumina-silicon and lithium-alumino-silicate glass commonly used in the existing cover glass industry can be strengthened and toughened by chemical ion exchange, but they are limited to insufficient intrinsic structural strength of the glass network, and their bifurcation threshold is limited, which cannot support high Tensile stress line density, when the tensile stress line density greatly exceeds the bifurcation threshold, the glass will bifurcate to form fragments smaller than 1mm, which will splash around when broken, causing safety hazards, and if the display screen of electronic products is broken, it will form fragments smaller than 1mm. Fragments, it is difficult to continue to use.
  • the purpose of the present invention is to provide a tempered glass with a safe stress state, so as to solve the problem that the tempered glass in the prior art is difficult to obtain sufficient compressive stress on its surface at the same time, so that it has a high resistance to drop performance while maintaining its internal tensile stress within a safe range.
  • the present invention also provides a method for processing the tempered glass with a safe stress state, so as to solve the problem that the existing processing methods cannot take both high pressure stress and high intrinsic strength into consideration.
  • the present invention adopts the following technical solutions:
  • a tempered glass with a safe stress state, the surface compressive stress and the thickness of the tempered glass satisfy the following conditions:
  • CS 50 is the compressive stress at 50 microns below the glass surface, the unit is MPa; a is -486.23; b is 0.449; 217-20T ⁇ c ⁇ 217+20/T; T is the thickness of the strengthened glass, the unit is mm.
  • the present invention also provides a method for processing the strengthened glass with a safe stress state, comprising the following steps:
  • step S2 put the precursor glass preheated in step S1 into a salt bath, and heat to carry out an ion exchange reaction to obtain the above tempered glass;
  • the salt bath is a mixed salt bath of potassium nitrate and sodium nitrate, and the mass fraction of sodium nitrate is less than the mole of Na 2 O/(Li 2 O+Na 2 O+K 2 O) in the precursor glass component
  • the ratio is greater than the molar percentage of Na 2 O in the precursor glass component, and the scaling ratio of the tempered glass is controlled at 1.5 ⁇ ⁇ 2 ⁇ .
  • the present invention has the following beneficial effects:
  • the present invention studies the stress state of the tempered glass, it is found that the tempered glass obtained by the preparation method of the present invention can make the surface of the tempered glass have a sufficiently high compressive stress, thereby making it have excellent anti-drop performance.
  • the mathematical relationship of the present invention can be used to accurately characterize and judge whether the tempered glass after tempering is in a safe stress state, that is, when the tempered glass satisfies the mathematical relationship of the present invention, it shows that The tensile stress of the processed tempered glass is controlled within a safe range, and there will be no explosive cracking or self-explosion due to slight impact.
  • the present invention explores the ion exchange reaction, it is found that in the ion exchange process, by controlling the concentration of sodium nitrate in the salt bath and the scaling ratio of the tempered glass, the degree of the ion exchange reaction can be controlled, so as to obtain a safe Tempered glass in a state of stress.
  • this kind of tempered glass has high compressive stress on the surface, which ensures the impact resistance of the tempered glass; at the same time, when the compressive stress of the tempered glass is increased, the The tensile stress is controlled within a safe range, so that the tempered glass can reach the best stress state, so that the characteristics of the tempered glass can be better exerted.
  • the present invention controls the time of the ion exchange reaction by real-time detection of the scaling ratio of the tempered glass obtained after the reaction when the precursor glass is subjected to the ion exchange reaction, so that the tempered glass obtained after the reaction reaches the optimum level.
  • the degree of ion exchange reaction is controlled by the scaling ratio.
  • the degree of ion exchange reaction is controlled by a series of parameters such as temperature, immersion time, and the number of times the glass is immersed in one or more salt baths. control, so that the obtained tempered glass can reach the best stress state.
  • Fig. 1 is a schematic diagram of the fragmented particles produced by the broken glass after being dropped from a height of 1.7 m in Example 1.
  • FIG. 2 is a schematic diagram of the front surface of a consumer electronic device according to the present invention.
  • FIG. 3 is a schematic diagram of a rear surface of a consumer electronic device according to the present invention.
  • Precursor glass It is a glass matrix material that has not been strengthened and does not contain crystals.
  • Tempered glass It is chemically strengthened glass treated by high temperature ion exchange process.
  • the alkali metal ions with large ionic radius replace the alkali metal ions with small ionic radius in the glass, resulting in the exchange ion volume difference, which produces a high-to-low compressive stress in the surface layer of the precursor glass, which hinders and retards the glass.
  • the expansion of microcracks achieves the purpose of improving the mechanical strength of the glass.
  • Depth of compressive stress layer DOL 0 refers to the depth position within the strengthened glass at which the compressive stress generated from the strengthening process reaches zero.
  • Bifurcation threshold When the glass is impacted by the tensile stress release test method, the crack is just split by its own stress when the glass is cracked, and the tensile stress linear density value at this time is the bifurcation threshold of the glass.
  • Threshold of trace band When the glass is impacted by the method of tensile stress release test, when the glass is cracked, it is caused by its own stress to produce trace band, and the linear density value of tensile stress at this time is the threshold value of trace band of glass.
  • Tensile stress release test Vickers diamond drills are used for the strengthened glass and fixed with guide rails to ensure that the drills impact the glass surface vertically. Control the penetration depth of the drill bit so that the failure point extends only two cracks instead of starbursts, so as to avoid the influence of external force on the failure state to the greatest extent. Finally, the tensile stress safety of the glass is judged by observing the failure state of the glass.
  • Tensile stress linear density CT-LD According to the SLP stress instrument test, the ratio of the integral of the tensile stress to the thickness of the glass under its thickness section is obtained. In chemically strengthened glass, the compressive stress and tensile stress are in a balanced relationship, and the SLP-1000 stress meter is more accurate in testing the tensile stress area of the glass. Therefore, the tensile stress integral and the thickness ratio are used to characterize the stress contained in the unit thickness of the glass. Used to characterize the degree of stress in chemically strengthened glass.
  • Drop test of the whole machine a method of testing the strength of tempered glass, attaching tempered glass sheets to samples of electronic devices such as mobile phones, and falling from a high place freely, recording the height at which the glass is broken, this height value can reflect the glass
  • the strength of this test method is called the drop test of the whole machine.
  • Single rod static pressure strength refers to the force of the round head rod on the glass when the glass is broken in the single rod static pressure test, also known as the breaking pressure.
  • the single rod static pressure test here refers to: the glass to be tested is made into a diameter of It is a circle of 40mm, placed on a ring with an inner diameter of 30mm, an outer diameter of 50mm and a semicircular cross-section, and then pressed down on the circle with a round head rod with a diameter of 10mm at a constant speed of 1mm/s the glass in the ring until the glass shatters.
  • This strength characterizes the deformation resistance of the cover glass, which is very effective for the bending resistance and blunt impact resistance of the glass.
  • FSM6000 and SLP1000 produced by Orihara Company can measure the surface high pressure stress area and deep low pressure stress area respectively, and use PMC software to fit the stress curve to obtain the corresponding test results.
  • PMC software can fit the stress curve to obtain the corresponding test results.
  • other stress testers that can measure the surface high pressure stress region and the deep low pressure stress region can also be used.
  • the present invention provides a tempered glass with a safe stress state, and the surface compressive stress of the tempered glass satisfies the following relationship:
  • CS 50 is the compressive stress at a depth of 50 mm from the surface of the tempered glass, in MPa; a is -486.23; b is 0.449; 217-20T ⁇ c ⁇ 217+20/T; T is the thickness of the tempered glass, in mm .
  • the strengthened glass is obtained after the precursor glass undergoes ion exchange reaction.
  • the strengthened glass is obtained through chemical strengthening, and its surface compressive stress CS is 500 MPa or greater, 600 MPa or greater, 700 MPa or greater, 800 MPa or greater, 900 MPa or greater, 1000MPa or more, the maximum is 1200MPa, so as to ensure the impact resistance of the tempered glass.
  • the depth DOL 0 of the compressive stress layer of the strengthened glass is more than 16% of the thickness of the strengthened glass, which can also be described as DOL 0 being a fraction of the thickness T of the glass.
  • the strengthened glass compressive stress layer depth DOL 0 may be equal to or greater than 0.16T, equal to or greater than 0.17T, equal to or greater than 0.18T, equal to or greater than 0.19T, equal to or greater than 0.20T, Equal to or greater than 0.21T, up to 0.22T.
  • the strengthened glass compressive stress layer depth DOL 0 may be 0.16T ⁇ 0.18T, 0.18T ⁇ 0.19T, 0.19T ⁇ 0.20T, 0.20T ⁇ 0.21T, 0.16T ⁇ 0.20T, 0.16T ⁇ 0.21T, 0.17T ⁇ 0.22T, 0.19T ⁇ 0.21T, 0.16T ⁇ 0.22T, 0.16T ⁇ 0.19T, 0.17T ⁇ 0.21T, 0.18T ⁇ 0.21T, 0.17T ⁇ 0.18T, or 0.18T ⁇ 0.22T to ensure the drop resistance of tempered glass.
  • the tempered glass has a safe compressive stress state
  • the safe compressive stress state is that the compressive stress of the tempered glass is high enough so that the drop resistance height of the tempered glass is at least 1.5m or more , and the average size of the vertical projection on the two-dimensional drawing of more than 70% of the fragment particles generated when the strengthened glass is dropped and broken is greater than 15 mm.
  • the stress state of the tempered glass of the present invention is safer, especially in the application of electronic products, it can not only meet the requirements of such users for the product's anti-drop performance, but also ensure the safety of the product.
  • the height of the tempered glass of the present invention is above 1.5m, which shows that the tempered glass of the present invention has excellent anti-drop performance.
  • the safe range of the tensile stress of the tempered glass is judged by the tensile stress release test.
  • the stress state of the tempered glass provided by the present invention can be characterized by the relationship between its CS 50 and its material thickness, and the production personnel test the prepared tempered glass, through the difference between its CS 50 and T Whether the stress of the obtained tempered glass is in a safe state is judged whether or not the above-mentioned relational expression is satisfied.
  • the compressive stress state of tempered glass that meets the above formula conditions is the best, and its stress state is characterized by the relationship between the CS 50 of the tempered glass and its thickness. It can be used as a cover plate protection material for electronic products such as mobile phones. Tempered glass, the tempered glass of the present invention has excellent anti-drop performance and safety, and its internal stress state is optimized, so that it has a wide range of applications, and can be used in the field of electronic product display protection cover plates, and has great development and application prospects.
  • the present invention also provides the processing method of the strengthened glass with a safe compressive stress state, comprising the following steps:
  • step S2 putting the precursor glass preheated in step S1 into a salt bath, heating for ion exchange reaction, and obtaining the tempered glass;
  • the salt bath is a mixed salt bath of potassium nitrate and sodium nitrate, and the mass fraction of sodium nitrate is less than the mole of Na 2 O/(Li 2 O+Na 2 O+K 2 O) in the precursor glass component
  • the ratio is greater than the molar percentage of Na 2 O in the precursor glass component, and the scaling ratio of the tempered glass is controlled at 1.5-2 ⁇ .
  • the salt bath includes at least one or more sodium-containing salts and one or more potassium-containing salts.
  • the salt bath includes KNO 3 and NaNO 3 , and the contents of KNO 3 and NaNO 3 are related to the number of ion exchange reactions, and the compressive stress state of the tempered glass can be adjusted by adjusting the concentration of the salt bath, to the optimum range.
  • the one or more ion exchange processes used to strengthen the precursor glass may include, but are not limited to, immersing it in a single salt bath, or immersing it in multiple salt baths of the same or different compositions. Additionally, the composition of one or more salt baths may include more than one larger radius ion (eg, Na + and K + ) or a single larger radius ion.
  • the composition of one or more salt baths may include more than one larger radius ion (eg, Na + and K + ) or a single larger radius ion.
  • the parameters of the ion exchange process include, but are not limited to, the composition and temperature of the salt bath, the immersion time, the number of times the inner glass layer is immersed in one or more salt baths, the use of multiple salt baths, additional Steps (such as annealing, washing), the composition of the salt bath in the embodiment can also use nitrates, sulfates and/or chlorides of alkali metal ions with larger ionic radii.
  • potassium-sodium and/or sodium-lithium ion exchange is performed on the precursor glass in a mixed salt bath of potassium salt and sodium salt, and potassium-sodium ion exchange is performed on the surface layer of the precursor glass, so that the strengthened glass can obtain sufficient surface compressive stress; at the same time, sodium ions with a smaller ionic radius in the mixed salt bath will ion-exchange with lithium ions in the depth of the precursor glass, further deepening the ion-exchange depth, thereby forming a deeper compressive stress layer depth and further improving the strength of the tempered glass. strength.
  • the precursor glass to be treated is subjected to a preheating process at 300° C. ⁇ 400° C., and the preheating time is 10 min ⁇ 30 min. Then, the precursor glass was put into a salt bath containing KNO 3 and NaNO 3 for reaction, and the temperature of the ion exchange reaction was controlled between 390°C and 460°C.
  • the salt bath components mentioned in the present invention are all in wt%.
  • the concentration of NaNO 3 in the salt bath has a certain relationship with the concentration of alkali metals in the precursor glass component, and the mass fraction of NaNO 3 in the salt bath is smaller than that of Na 2 O/(Li 2 O+Na 2 in the precursor glass component
  • the molar ratio of O+K 2 O) is greater than the molar ratio of Na 2 O to the total composition in the precursor glass composition.
  • the molar ratio of Na 2 O in the precursor glass component to the total composition is 1% to 6%
  • the mole ratio of Na 2 O/(Li 2 O+Na 2 O+K 2 O) in the precursor glass component The ratio is 4.76% ⁇ 74.07%.
  • the salt bath includes 6 %-74.07% NaNO3 and all ranges and sub-ranges therebetween, such as 6.8%-10%, 9.8%-10%, 15%-20%, 9.4%-25%, 8.5% ⁇ 35%, 9% ⁇ 44%, 10% ⁇ 59%, 25% ⁇ 68%, 13% ⁇ 37%, 24% ⁇ 46%, 6%, 10%, 15%, 25%, 36%, 47 %, 57%, or 68%.
  • the volume of the precursor glass will change after the ion exchange reaction, and the ratio of the change in size of the final tempered glass to the original size is the scaling. Compare.
  • the original size of the tempered glass is recorded before the reaction period, and the size of the tempered glass is detected in real time during the ion exchange.
  • multiple batches of precursor glass are chemically strengthened, ie, multiple batches of precursor glass are batches in the same salt bath environment.
  • Strengthen processing During the ion exchange reaction, a small amount of impurity ions will be generated in the ion exchange salt bath after chemical strengthening of each batch of precursor glass, mainly lithium ions exchanged from the precursor glass. After the chemical strengthening of the precursor glass, the concentration of lithium ions in the ion-exchange salt bath will increase.
  • the concentration of lithium ions must be controlled, because the lithium ions in the ion-exchange salt bath will become K + -Na + , Na + -Li + ion exchange hindering ions, the presence of a small amount of lithium ions will greatly reduce the degree of ion exchange and weaken the strengthening state of the strengthened glass.
  • the molar ratio of the lithium ion concentration in the salt bath to the total alkali metal ions in the salt bath is less than 0.25% and all ranges and sub-ranges therebetween, such as 0.02% to 0.2%, 0.1% to 0.16%, 0.03% to 0.2% , 0.04% ⁇ 0.18%, 0.05% ⁇ 0.1%, 0.01% ⁇ 0.24%, 0.1% ⁇ 0.25%, 0.1% ⁇ 0.18%, 0.1% ⁇ 0.15%, 0.1% ⁇ 0.12%, 0%, 0.15%, 0.18 %, 0.2%, 0.19%, 0.14%, 0.16%, 0.05%, 0.21%, 0.08%, 0.06%, 0.04%, 0.03%, 0.02%, or 0.01%.
  • the ion exchange is stopped, and lithium ions are added to the ion-exchange salt bath for purification
  • the material can be heated and reacted for a period of time.
  • 0.1%-2% of the lithium ion purified product is put into the ion-exchange salt bath, the purification temperature is controlled at 360°C to 450°C, and the reaction time is consistent with the strengthening time of the tempered glass.
  • the ion exchange is stopped and the precursor glass is removed from the ion exchange salt bath when the compressive stress on the surface of the non-first-strengthened glass drops to 10%-20% of the compressive stress on the surface of the first-strengthened glass , and then put into the ion-exchange salt bath with a mass of 1% to 5% of the lithium ion purified product of the ion-exchange salt bath.
  • the addition of lithium ion purifier is not required.
  • the lithium ion purified product is an ion sieve material, and the ion sieve material is based on the wt% of the oxide, and contains: 15% to 55% of SiO 2 , 5% to 50% of auxiliary materials, and 15% to 48% of at least one of A functional metal oxide, the metal in the functional metal oxide is a monovalent and/or divalent metal, the monovalent metal is at least one of lithium, sodium, potassium, and rubidium, and the divalent metal is The metal is at least one of magnesium, calcium, strontium and barium, and the auxiliary material forms polar covalent bonds and ionic bonds with SiO 2 , and the auxiliary material is selected from phosphorus oxide, boron oxide, aluminum oxide, zirconium oxide, chromium oxide, At least one of iron oxide, zinc oxide, bismuth oxide, and cobalt oxide.
  • the lithium ion purified product is mainly used to remove Li + in the ion exchange salt bath, control the concentration of Li + in the ion exchange salt bath, and reduce its influence on the degree of ion exchange of the strengthened glass; Other impurity ions are introduced into the bath, and the used ion sieve will not pollute the environment.
  • the use of the lithium ion purified product can effectively avoid the deactivation of the ion exchange salt bath, the weakening of its strengthening effect, and restore the activity of the ion exchange salt bath.
  • the present invention also discloses a consumer electronic terminal, comprising: a casing including a front surface, a rear surface and a side surface; and an electronic assembly partially located in the casing, the electronic assembly including a display, the display being located in the casing At or adjacent to the front surface of the housing; the front surface or/and the rear surface or/and the side surfaces comprise the strengthened glass with a safe stress state according to the present invention.
  • the consumer electronic terminals include mobile phones, tablet computers or other electronic terminals.
  • the tempered glass of the present invention may be included in other articles, such as articles with displays (or display articles) (eg, consumer electronics including mobile phones, tablets, computers, navigation systems, etc.), building products, transportation Articles (eg, automobiles, trains, airplanes, marine vehicles, etc.), appliance articles, or any article that requires a certain degree of clarity, scratch resistance, abrasion resistance, or a combination thereof.
  • displays or display articles
  • FIG. 2 shows a front surface of a consumer electronic device
  • FIG. 1 shows a front surface of a consumer electronic device
  • FIG 3 shows a rear surface of the consumer electronic device, which includes a housing including a front surface 1, a rear surface 2 and a side surface; and part of the Electronic components located within or entirely within a housing, and including not only displays but also controllers, memory, and other electronic components, wherein the displays are located at or adjacent to the front surface of the housing.
  • the front surface or/and the rear surface or/and the side surface of the housing comprise the tempered glass according to the present invention.
  • a cover article 3 covering the front surface of the casing or on the display may also be included, the cover article 3 and/or a portion of the casing comprising the tempered glass of the present invention.
  • the glass in order to obtain a strengthened glass with a safe compressive stress state, certain requirements are also imposed on the material of the glass.
  • the glass mainly includes the following components:
  • SiO 2 65mol% to 75mol%, preferably 70mol% to 75mol%;
  • the content of SiO 2 accounts for at least 78 mol % of the total amount of SiO 2 and Al 2 O 3 , preferably more than 80 mol %.
  • the glass network components are mainly SiO 2 and Al 2 O 3 , both of which can improve the strength of the glass network structure, and the high network structure composition can increase the amount of oxygen in the glass bridges, especially It is to increase the content of silicon components, which can improve the strength of the network structure of the glass.
  • Al 2 O 3 helps to increase the rigidity of the glass network
  • Al 2 O 3 can exist in the glass in a tetra- or penta-coordination, which increases the bulk density of the glass network and thus increases the compressive stress formed by chemical strengthening .
  • High network structure strength plays an important role in the ion exchange of glass, because during the ion exchange process, the glass will undergo K + -Na + , Na + -Li + binary ion exchange step by step or simultaneously to form a composite compressive stress Floor.
  • the glass will have a stress relaxation effect due to the exchange of ions of different radii, and the high temperature and long reaction time in the ion exchange reaction will weaken the composite compressive stress layer, especially the middle and deep layers. Therefore, improving the network structure strength of the glass can effectively overcome the influence of the above reasons on the composite compressive stress layer.
  • the glass may comprise 8-15 mol% Al2O3 and all ranges and subranges therebetween, eg, 8-14.5 mol%, 8-14 mol%, 8-13.5 mol% , 8mol% ⁇ 13mol%, 10mol% ⁇ 13mol%, 8mol% ⁇ 12mol%, 9mol% ⁇ 14.5mol%, 9mol% ⁇ 14mol%, 9mol% ⁇ 11.5mol%, 10mol% ⁇ 13mol%, 9mol%, 9.5mol% %, 10mol%, 10.5mol%, 11mol%, 11.2mol%, 12.4mol%, 12.6mol%, 12.8mol%, 13mol%, 13.2mol%, 13.4mol%, 13.6mol%, 13.8mol%, or 15mol% .
  • the components of the glass also include B 2 O 3 and B 2 O 3 as the secondary network structure of the glass.
  • An appropriate amount of B 2 O 3 can promote the melting of the glass at high temperature, reduce the difficulty of melting, and can effectively improve the ion exchange in the glass.
  • the rate of increase, especially the exchange capacity of K + -Na + is very significant, but excessive B 2 O 3 will lead to the weakening of the glass network structure, so it is necessary to control the amount of B 2 O 3 added, and the moles of B 2 O 3 account for The ratio is controlled within a range of not more than 3 mol%.
  • the glass may include no more than 3 mol% B2O3 and all ranges and subranges therebetween, eg, 0-2.9 mol%, 0-2.7 mol%, 0-2.1 mol%, 0 ⁇ 1.7mol%, 0 ⁇ 1.2mol%, 1mol% ⁇ 2.6mol%, 1mol% ⁇ 2.0mol%, 1mol% ⁇ 1.5mol%, 1mol% ⁇ 1.3mol%, 1mol% ⁇ 1.9mol%, 0mol%, 1.4 mol%, 1.6mol%, 2.3mol%, 2.5mol%, 2.9mol%, 2.7mol%, 2.4mol%, 2.1mol%, 0.4mol%, 0.7mol%, 0.6mol%, 0.5mol%, 0.3mol% , 0.2 mol%, or 3.0 mol%.
  • the components of the glass also include Na 2 O and Li 2 O.
  • the molar proportion of Na 2 O is in the range of 1 mol % to 6 mol %.
  • Na 2 O is the main component of ion exchange and is the key exchange ion to form surface high pressure stress.
  • the glass may include 1-6 mol% Na2O and all ranges and subranges therebetween, eg, 1-4 mol%, 1 mol%-4.6 mol%, 1 mol%-4 mol% , 1mol% ⁇ 4.7mol%, 1mol% ⁇ 3mol%, 1mol% ⁇ 3.5mol%, 2mol% ⁇ 5.9mol%, 2mol% ⁇ 4.7mol%, 2mol% ⁇ 3.8mol%, 1.5mol% ⁇ 5.6mol%, 2.6mol% ⁇ 4.9mol%, 1.5mol% ⁇ 4mol%, 3.7mol% ⁇ 5.8mol%, 1mol%, 1.5mol%, 2mol%, 2.8mol%, 2.6mol%, 2.5mol%, 2.1mol%, 3.8 mol %, 3.6 mol %, 4 mol %, 4.4 mol %, 4.3 mol %, 3.2 mol %, or 5.1
  • Li 2 O is also the main component of ion exchange.
  • the molar proportion of Li 2 O is in the range of 7 mol% to 12 mol%.
  • the radius of Na + in the ion exchange salt bath is smaller than that of K + , which enables it to penetrate deeper into the glass and interact with Li +
  • Li + in the glass is the key exchange ion to form deep compressive stress
  • Na + -Li + exchange with Na + in the ion-exchange salt bath enables the glass to form a high-depth compressive stress layer.
  • the glass may include 7-12 mol% Li2O and all ranges and subranges therebetween, eg, 7-11 mol%, 7.8-10.7 mol%, 7.5-10 mol% %, 8.6mol% ⁇ 11.7mol%, 8.2mol% ⁇ 11.4mol%, 9.1mol% ⁇ 10.8mol%, 9.2mol% ⁇ 11.5mol%, 10.2mol% ⁇ 11.9mol%, 8.5mol% ⁇ 11.5mol%, 9.5mol% ⁇ 10mol%, 10.6mol% ⁇ 11.9mol%, 7.7mol% ⁇ 9.8mol%, 7.5mol%, 8mol%, 9mol%, 7.8mol%, 8.6mol%, 9.5mol%, 10.1mol%, 11.8 mol %, 7.6 mol %, 10 mol %, 10.4 mol %, 11.3 mol %, 9.2 mol %, or 10.1 mol %.
  • the glass may include 7mol% to 13mol% Na2O + Li2O and all ranges and subranges therebetween, eg, 8mol% to 13mol%, 7mol% % ⁇ 12mol%, 8mol% ⁇ 10.5mol%, 7mol% ⁇ 10.6mol%, 8mol% ⁇ 11mol%, 7mol% ⁇ 10.5mol%, 7mol% ⁇ 11.5mol%, 9mol% ⁇ 11mol%, 7mol% ⁇ 8.9mol% %, 8.6mol% ⁇ 12.8mol%, 9mol% ⁇ 12.4mol%, 7mol% ⁇ 9.8mol%, 7mol% ⁇ 10.4mol%, 7mol% ⁇ 10.8mol%, 9mol%, 10mol%, 11.2mol%, 11.4mol% %, 11.6
  • the components of the glass further include K 2 O, and the molar proportion of K 2 O is controlled between 0 mol % and 3 mol %, and K 2 O is the main component of ion exchange.
  • the glass may include 0-3 mol% K2O and all ranges and subranges therebetween, eg, 0.1-3 mol%, 0.2-2.8 mol%, 0.1 mol%- 2.6mol%, 0.3mol% ⁇ 2mol%, 0.4mol% ⁇ 1.8mol%, 0.5mol% ⁇ 1.0mol%, 1mol% ⁇ 2.5mol%, 1mol% ⁇ 2.0mol%, 1mol% ⁇ 1.8mol%, 1mol% ⁇ 1.5mol%, 1mol% ⁇ 1.2mol%, 0mol%, 1.5mol%, 1.8mol%, 2mol%, 2.9mol%, 2.8mol%, 2.6mol%, 2.5mol%, 2.1mol%, 0.8mol%, 0.6 mol%, 0.5 mol%, 0.4 mol%, 0.3 mol%, 0.2 mol%, 0.8mol
  • the components of the glass also include MgO, and the molar proportion of MgO is controlled between 2 mol% and 7.5 mol%.
  • MgO has the effect of reducing the high temperature viscosity of the glass, thereby increasing the Young's modulus of the glass. .
  • the glass may include 2 mol% to 7.5 mol% MgO and all ranges and subranges therebetween, such as 2.5 mol% to 2.8 mol%, 2.5 mol% to 2.6 mol%, 2.6 mol% to 2.6 mol% 3.2mol%, 2.4mol% ⁇ 3.8mol%, 3.5mol% ⁇ 4.0mol%, 3mol% ⁇ 4.5mol%, 2.7mol% ⁇ 5.8mol%, 2.5mol% ⁇ 5.0mol%, 3.1mol% ⁇ 6.5mol% , 4mol% ⁇ 5mol%, 2.5mol%, 3.5mol%, 3.8mol%, 3mol%, 5mol%, 2.8mol%, 2.6mol%, 4.5mol%, 4.1mol%, 4.8mol%, 4.6mol%, 3.2 mol %, 3.4 mol %, 3.3 mol %, 3.2 mol %, or 3.1 mol %.
  • the composition of the glass also includes chemical fining agents, such fining agents including but not limited to SnO 2 and sodium chloride.
  • the glass may include no more than 1 mol% SnO and sodium chloride and all ranges and subranges therebetween, eg, 0.1 mol% to 0.9 mol%, 0.1 mol% to 0.8 mol%, 0.1 mol% mol% ⁇ 0.7mol%, 0.1mol% ⁇ 0.6mol%, 0.1mol% ⁇ 0.5mol%, 0.1mol% ⁇ 0.4mol%, 0.5mol% ⁇ 1.0mol%, 0.05mol% ⁇ 1.0mol%, 0.03mol% ⁇ 1.0mol%, 0.02mol% ⁇ 1.0mol%, 1mol%, 0.9mol%, 0.8mol%, 0.7mol%, 0.6mol%, 0.5mol%, 0.4mol%, 0.3mol%, 0.2mol%, or 0mol% %.
  • the glass does not contain phosphorus, nor does it contain other alkaline earth metal elements other than magnesium. That is, phosphorus-containing and other alkaline earth metal elements are not actively added, but may be present as impurities in very small amounts, for example, in the examples, all below 300 ppm or less. Because phosphorus pentoxide in glass can reduce the melting temperature of glass at high temperature, but because phosphorus pentoxide has a phosphorus-oxygen double bond, the structure is unstable, and its scratch resistance is poor, and the phosphorus-containing structure will lead to a decrease in the bifurcation threshold of the glass. , and in float glass, the phosphorus-containing structure will make the glass easy to phase separate and crystallize, which increases the difficulty of production.
  • Magnesium-alkaline earth metals have good high-temperature melting properties and have little effect on the ion exchange rate, but Ca, Zn, and other alkaline earth metal oxides have a larger ionic radius than magnesium, which has a greater impact on the ion exchange rate.
  • the components in the above-mentioned glass frit are smelted at a temperature between 1630°C and 1700°C, for example, 1630°C, 1640°C, 1650°C, 1680°C, 1690°C or 1700°C can be selected from tin oxide and 1700°C.
  • Sodium chloride is used as a clarifying agent, and the molar ratio of the two is not more than 1%, such as 0.1%, 0.2%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%.
  • the precursor glass can be produced by overflow down-draw method, float method and calendering method.
  • Embodiment 1 The processing method of the tempered glass with a safe compressive stress state according to the present invention takes Embodiment 1 as an example:
  • S1 First, accurately weigh the ratio of the raw materials of the glass precursor according to the raw material ratio of Example 1 in Table 1, and then fully mix the raw materials, keep them at a high temperature of 1630 ° C for 4 hours, melt them, and then shape to obtain a thickness of 0.7mm front glass plate.
  • step S2 Preheat the precursor glass plate obtained in step S1 at 350°C for 23 minutes, and put the preheated precursor glass plate into a mixed salt bath of 15wt% NaNO3 and 85wt% KNO3
  • the ion-exchange reaction was carried out in 2000, the reaction temperature was 440 °C, and the reaction time was 10 h.
  • the scaling ratio of the precursor glass plate was detected. When the scaling ratio was 2 ⁇ , after the reaction was completed, it was taken out and washed to obtain a strengthened glass plate.
  • Table 1 shows the recipes of the precursor glass and the comparative examples.
  • Table 2 shows the process parameters for preparing the tempered glass.
  • Table 3 shows the performance test parameters of the examples and the comparative examples. 4 is the test results of samples with different thicknesses in Example 1 and Example 3.
  • Example 1 the relationship between the thickness of the samples in Example 1 and Example 3 and the CS 50 was further verified. It can be seen from Table 4 that under different thicknesses, the CS 50 and the thickness of the strengthened glass after ion exchange meet the requirements of this The relation described in the invention.
  • the tempered glass of this embodiment is subjected to K + -Na + ion exchange and Na + -Li + ion exchange in a mixed salt bath of potassium and sodium to form compressive stress, and the tempered glass is subjected to compressive stress.
  • the compressive stress on the surface of the strengthened glass is more than 500MPa, which ensures the impact resistance of the glass.
  • the strengthening time is adjusted by controlling the scaling ratio, so that the CS 50 of the obtained strengthened glass and its thickness satisfy the relational expression described in the present invention, and finally the strengthened glass has high anti-drop performance.
  • the comparison example 1 does not control the scaling ratio, which also makes its anti-drop performance far inferior to that of the embodiment of the present invention.
  • Example 1 The whole machine drop test was carried out on the tempered glass obtained by the preparation method of Example 1.
  • the mobile phone mold was firmly attached to the sample made of tempered glass in Example 1, and the tempered glass sample was dropped horizontally on the marble plate with sandpaper on the surface.
  • the highest point at which the tempered glass sample is not broken is taken as the anti-drop height.
  • the anti-drop height of the tempered glass of Example 1 is 1.5m, which is much higher than that of Comparative Example 1, indicating that Example 1 has high anti-drop performance.
  • the tempered glass has a high network structure strength, and obtains a high surface compressive stress, which effectively improves the The anti-drop height of the tempered glass, and at the same time, the tensile stress of the tempered glass is controlled within a safe range to further increase the limit of the anti-drop strength, thereby ensuring the safety of the tensile stress of the tempered glass.

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Abstract

本发明公开了一种具有安全应力状态的强化玻璃及其加工方法，该强化玻璃其表面压应力与厚度的数值满足所述数学关系式，通过对应力状态进行表征直观了解经过化学强化后获得的强化玻璃的应力状态。进一步，在离子交换过程中，通过对盐浴里硝酸钠浓度以及强化玻璃的缩放比进行控制，从而对离子交换反应程度进行控制，使获得的强化玻璃与普通玻璃相比，其表面具有高的压应力，保证了强化玻璃的抗冲击性能；同时，在提升强化玻璃压应力的时候，也将强化玻璃内的张应力控制在安全范围内，使强化玻璃到达最佳的应力状态，进而能更好的发挥强化玻璃的特性。

Description

一种具有安全应力状态的强化玻璃及其加工方法 技术领域
本发明涉及强化玻璃技术领域，具体涉及一种具有安全应力状态的强化玻璃及其加工方法。
背景技术
随着科学技术的进步以及人们生活水平的提高，小型机电产品特别是便携式电子产品在日常住活中得到极大的应用，包括手机、数码相机、笔记本电脑等。由于产品的便携性使得消费者在携带或使用过程中将其失手跌落的意外时有发生，从而导致产品的破损。由于跌落冲击中物体动量的传递是在极短的间内进行的，因而与其他形式的冲击相比，产品跌落冲击力最为强烈，是导致小型电子产品外表丧失美观、内部工作性能下降甚至使用功能丧失的主要原因。而且，作为精密的高价值产品，这类电子产品往往价格不菲，其损坏带来的隐形损失甚至超出产品本身价値，如重要数据的丟失，甚至错失商业机会，还有可能造成人身安全问题等。因此，消费者购买此类产品时，在满足基本功能的条件下会更加青睐有着良好耐撞性能的产品，产品在跌落时的耐撞性能已成为产品质量的重要特性和产品的核心竞争能力。
目前，这类电子产品所使用的玻璃主要为经过化学强化后的化学强化玻璃。化学强化玻璃是一种利用离子交换工艺，在盐浴中离子半径较大的碱金属离子取代玻璃中离子半径较小的碱金属离子从而产生交换离子体积差，在玻璃一定的表层产生由高到低的张应力，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。通过离子交换工艺处理后的强化玻璃在表面产生压应力的同时，其内部也产生了相应的张应力。化学强化玻璃是一个应力平衡体，如果压应力较低，获得的强化玻璃强度不高，无法满足客户对产品跌落时高抗跌落性能的要求；如果压应力太高，虽然可以获得强度很高的强化玻璃，但同时会导致强化玻璃内部形成很高的张应力，这样的强化玻璃会存在安全隐患，在轻微的冲击下发生爆炸性开裂，甚至会产生自爆现象，这严重影响了产品的可靠性，甚至还对客户的人身安全造成严重影响。
而现有盖板玻璃行业常用的普通高铝硅及锂铝硅玻璃，虽然可以进行化学离子交换增强增韧，但是局限于玻璃网络本征结构强度不足，其分叉阈值具有极限，不能支撑高张应力线密度，当张应力线密度大幅超过分叉阈值时，玻璃会分叉形成小于1mm的碎片，在破碎时会四处飞溅，造成安全隐患，并且电子产品的显示屏幕若破碎形成小于1mm的碎片，则很难继续使用。
因此，如何使强化玻璃的压应力既能满足高抗跌落性能的要求，又使其内部的张应力维持在安全的范围内，以及如何获得这样的强化玻璃，是当前所属技术领域技术人员急需解决的技术问题。
发明内容
针对现有技术存在的上述不足，本发明的目的在于提供一种具有安全应力状态的强化玻璃，以解决现有技术中强化玻璃难以同时兼具其表面获得足够的压应力，使其具有高抗跌落性能，同时其内部的张应力维持在一个安全的范围内的问题。
本发明还提供所述具有安全应力状态的强化玻璃的加工方法，以解决现有加工方法无法兼顾高压应力与高本征强度的问题。
为了解决上述技术问题，本发明采用如下技术方案：
一种具有安全应力状态的强化玻璃，该强化玻璃其表面压应力与厚度的数值满足以下条件：
Figure PCTCN2021106369-appb-000001
其中，CS 50为距离玻璃表面以下50微米处的压应力，单位为MPa；a为－486.23；b为0.449；217－20T≦c≦217+20/T；T为强化玻璃的厚度，单位为mm。
本发明还提供一种具有安全应力状态的强化玻璃的加工方法，包括如下步骤：
S1：对前体玻璃进行预热处理；
S2：将经过步骤S1预热处理的前体玻璃放入盐浴中，加热进行离子交换反应，获得上述强化玻璃；
其中，所述盐浴为硝酸钾、硝酸钠混合盐浴，所述硝酸钠质量分数小于所述前体玻璃组分中Na 2O/(Li 2O+Na 2O+K 2O)的摩尔比值，并大于所述前体玻璃组分中Na 2O的摩尔百分比，所述强化玻璃的缩放比控制在1.5‰～2‰。
相比现有技术，本发明具有如下有益效果：
1、本发明在对强化玻璃的应力状态进行研究时，发现通过本发明所述制备方法获得的强化玻璃，可使得强化玻璃表面都具有足够高的压应力，进而使其具有优异的抗跌落性能，并且能够采用本发明所述数学关系式来准确表征和判断强化处理后的强化玻璃是否处于安全应力状态，也就是说，当所述强化玻璃满足本发明所述数学关系式时，则表明了处理得到的强化玻璃的张应力被控制在安全的范围内，不会因轻微的冲击发生爆炸性开裂，也不会产生自爆现象。
2、本发明对离子交换反应进行探究时发现，在离子交换过程中，通过对盐浴里硝酸钠浓度以及强化玻璃的缩放比进行控制，可以实现对离子交换反应程度进行控制，从而获得具有安全应力状态的强化玻璃，这种强化玻璃与普通玻璃相比，其表面具有高的压应力，保证了强化玻璃的抗冲击性能；同时，在提升强化玻璃压应力的时候，也将强化玻璃内的张应力控制在安全范围内，使强化玻璃到达最佳的应力状态，进而能更好的发挥强化玻璃的特性。
3、本发明在对前体玻璃进行离子交换反应时，通过对反应后获得强化玻璃的缩放比进行实时检测，以此来对离子交换反应的时间进行控制，使反应后获得的强化玻璃达到最佳的应力状态；同时，通过缩放比来控制离子交换反应进行的程度。与现有技术通过温度、浸渍时间、将玻璃浸入一种或多种盐浴中的次数这一系列参数来控制离子交换反应的程度相比，本发明能够对离子交换反应进行更加精准、高效的控制，从而使获得的强化玻璃达到最佳的应力状态。
附图说明
图1为实施例1强化玻璃从1.7m高度跌落后破碎产生的碎片颗粒示意图。
图2为本发明所述一种消费电子装置的前表面示意图。
图3为本发明所述一种消费电子装置的后表面示意图。
具体实施方式
下面将结合说明书附图和实施例对本发明作进一步说明。
以下是对本发明涉及的相关专用名称及相关测量方法的解释：
前体玻璃：是未被强化处理的玻璃基体材料，不含有晶体。
强化玻璃：是经过高温离子交换工艺处理后的化学强化玻璃。在高温盐浴中离子半径大的碱金属离子取代玻璃中的离子半径小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。
表面压应力CS：玻璃经过化学强化后，表面半径较小的碱金属离子被替换为半径较大的碱金属离子，由于半径较大的碱金属离子的挤塞效应，玻璃表面因此产生压应力。
表面压应力CS 50：玻璃表面以下50微米处的压应力。
压应力层深度DOL 0：是指在强化玻璃内从强化过程生成的压缩应力达到零的深度位置。
分叉阈值：当采用张应力释放试验的方法冲击玻璃时，玻璃开裂时恰好由自身的应力 使其裂纹分叉，此时的张应力线密度值即为玻璃的分叉阈值。
痕带阈值：当采用张应力释放实验的方法冲击玻璃时，玻璃开裂时恰好由自身的应力使其产生痕带，此时的张应力线密度值即为玻璃的痕带阈值。
张应力释放试验：强化后的玻璃采用维氏金刚石钻头并采用导轨固定确保钻头垂直冲击玻璃表面，冲击采用气压传导，调节气压并结合压力传感器控制冲击力大小，并且根据玻璃的厚度调节高度导轨从而控制钻头侵入深度，使得破坏点仅延伸两条裂纹而非产生星爆，最大程度避免外力对破坏状态的影响，最后通过观察玻璃破坏状态，来判断玻璃的张应力安全性。
张应力线密度CT-LD：根据SLP应力仪器测试获得玻璃在其厚度截面下，其张应力积分与厚度的比值。化学强化玻璃中压应力与张应力为平衡相等的关系，而SLP-1000应力仪对玻璃的张应力区域测试更为精准，故采用张应力积分与厚度比值表征玻璃单位厚度下容纳的应力大小，用来表征化学强化玻璃的应力程度。
整机跌落测试：一种强化玻璃强度测试的方法，将强化玻璃片与手机等电子设备样品贴附在一起，由高处自由落体跌下，记录玻璃破碎的高度，这一高度值可以反应玻璃的强度，将此测试方法称为整机跌落测试。
单杆静压强度：指在单杆静压测试中，玻璃破碎时圆头杆对玻璃的作用力，也称为破碎压力，这里的单杆静压测试是指：将待测玻璃制成直径为40mm的圆形，放置在内径为30mm、外径为50mm且横断面为半圆形的圆环上，然后用直径为10mm的圆头杆以1mm/s的恒定速度往下压置于圆环中的玻璃，直至玻璃破碎。该强度表征了盖板玻璃抗变形能力，其对于玻璃的抗弯曲，抗钝器冲击能力十分有效。
本发明中，应力测量可由Orihara公司生产的FSM6000及SLP1000分别对表层高压应力区和深层低压应力区进行测量，并采用PMC软件将应力曲线进行拟合，得到相应的测试结果。当然也可采用其他可对表层高压应力区和深层低压应力区进行测量的应力测试仪。
本发明提供一种具有安全应力状态的强化玻璃，该强化玻璃其表面压应力满足以下关系：
Figure PCTCN2021106369-appb-000002
其中，CS 50为距离强化玻璃表面50mm深度的压应力，单位为MPa；a为－486.23；b为0.449；217－20T≦c≦217+20/T；T为强化玻璃的厚度，单位为mm。
所述强化玻璃是前体玻璃进行离子交换反应后获得的。在一个或多个实施例中，经过化学强化得到所述的强化玻璃，其表面压应力CS为500MPa或更大、600MPa或更大、700MPa或更大、800MPa或更大、900MPa或更大、1000MPa或更大，最大为1200MPa，以此保证所述强化玻璃的抗冲击性能。
在一个或多个实施例中，所述强化玻璃压应力层深度DOL 0达到该强化玻璃厚度的16％以上，也可以被描述为DOL 0为玻璃厚度T的分数。在一个或多个实施例中，所述强化玻璃压应力层深度DOL 0可以等于或大于0.16T、等于或大于0.17T、等于或大于0.18T、等于或大于0.19T、等于或大于0.20T、等于或大于0.21T，最大为0.22T。在一些实施例中，所述强化玻璃压应力层深度DOL 0可以为0.16T～0.18T、0.18T～0.19T、0.19T～0.20T、0.20T～0.21T、0.16T～0.20T、0.16T～0.21T、0.17T～0.22T、0.19T～0.21T、0.16T～0.22T、0.16T～0.19T、0.17T～0.21T、0.18T～0.21T、0.17T～0.18T、或0.18T～0.22T，以保证强化玻璃的抗跌落性能。
在一个或多个实施例中，所述强化玻璃具有安全压应力状态，所述安全压应力状态为所述强化玻璃的压应力足够高，使所述强化玻璃的抗跌落高度至少在1.5m以上，且所述强化玻璃跌落破碎时产生的碎片颗粒中70％以上的碎片颗粒在二维图纸上的垂直投影平均大小大于15mm。相对于普通强化玻璃，本发明强化玻璃的应力状态更加安全，尤其是在电子产品应用方面，既能满足这类用户对产品抗跌落性能的要求，也保证了产品的安全性。在整机跌落试验中，本发明所述的强化玻璃抗跌落高度在1.5m以上，这显示本发明所述的强化玻璃具有优异的抗跌落性能。通过张应力释放实验来判断所述强化玻璃张应力的安全范围。在商业生产中，本发明提供的强化玻璃的应力状态可通过其CS 50与其材料厚度之间的关系式来进行表征，生产人员对制备得到的强化玻璃进行检测，通过其CS 50与T之间是否满足上述关系式来判断获得的强化玻璃的应力是否处于安全状态。
符合上述公式条件的强化玻璃其压应力状态为最佳状态，并通过强化玻璃CS 50与其厚度之间的关系对其应力状态进行表征，可以作为手机等电子产品的盖板保护材料，相对于普通强化玻璃，本发明强化玻璃具有优异的抗跌落性能和安全性，对其内部应力状态进行了优化，使其应用范围广泛，能够应用电子产品显示保护盖板领域，极具开发和应用前景。
本发明还提供所述具有安全压应力状态强化玻璃的加工方法，包括以下步骤：
S1：对前体玻璃进行预热处理；
S2：将经过步骤S1预热处理的前体玻璃放入盐浴中，加热进行离子交换反应，获得所述强化玻璃；
其中，所述盐浴为硝酸钾、硝酸钠混合盐浴，所述硝酸钠质量分数小于所述前体玻璃组分中Na 2O/(Li 2O+Na 2O+K 2O)的摩尔比值，并大于所述前体玻璃组分中Na 2O的摩尔百分比，所述强化玻璃的缩放比控制在1.5～2‰。
其中，所述盐浴至少包括一种或多种的含钠盐，以及一种或多种的含钾盐。优选的，所述盐浴中包括KNO 3和NaNO 3，并且KNO 3和NaNO 3的含量与离子交换反应的次数有关，通过对盐浴浓度的调整达到对所述强化玻璃压应力状态的调整，使其达到最佳范围。
用来强化前体玻璃的一种或更多种离子交换过程可包括，但不限于：将其浸没在单一盐浴中，或者将其浸没在具有相同或不同组成的多个盐浴中。另外，一个或多个盐浴的组成可以包括一种以上半径较大的离子(例如，Na +和K +)或单个半径较大的离子。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：盐浴的组成和温度、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)，实施例中盐浴的组成还可以采用离子半径较大碱金属离子的硝酸盐、硫酸盐和/或氯化物。
根据进行离子交换反应的次数不同，对反应条件的控制也有所不同。本发明通过将前体玻璃在钾盐和钠盐的混合盐浴中进行钾-钠和/或钠-锂离子交换，在前体玻璃表层进行钾-钠离子交换，使强化玻璃获得足够的表面压应力；同时，混合盐浴中离子半径更小的钠离子会与前体玻璃深处的锂离子进行离子交换，进一步加深离子交换深度，从而形成更深的压应力层深度，进一步提升强化玻璃的强度。
在一些实施例中，当所述离子交换反应的次数为单次时，将待处理的前体玻璃进行300℃～400℃预热工序，预热时间为10min～30min。然后，将前体玻璃放入含有KNO 3和NaNO 3盐浴中进行反应，离子交换反应的温度控制在390℃～460℃之间。其中，本发明中提到的盐浴组分均以wt％计。所述盐浴中NaNO 3的浓度与前体玻璃组分中碱金属的浓度存在一定关系，盐浴中NaNO 3的质量分数小于前体玻璃组分中Na 2O/(Li 2O+Na 2O+K 2O)的摩尔比值，同时大于前体玻璃组分中Na 2O占总组分的摩尔比值。其中，前体玻璃组分中Na 2O占总组分的摩尔比值为1％～6％，前体玻璃组分中Na 2O/(Li 2O+Na 2O+K 2O)的摩尔比值为4.76％～74.07％。所述盐浴包括6％～74.07％的NaNO 3及其之间的所有范围和子范围，例如6.8％～10％，9.8％～10％，15％～20％，9.4％～25％，8.5％～35％，9％～44％，10％～59％，25％～68％，13％～37％，24％～46％，6％，10％，15％，25％，36％，47％，57％，或68％。
进一步，还需要对前体玻璃进行离子交换反应后的缩放比进行控制，前体玻璃在进行离子交换反应后其体积会发生变化，最终得到的强化玻璃尺寸的变化量与原尺寸的比值为缩放比。在反应期前记录强化玻璃的原尺寸，离子交换期间对强化玻璃的尺寸进行实时检 测，通过对强化玻璃的缩放比进行控制来调整离子交换反应时间，使强化玻璃的缩放比控制在1.5‰～2‰之间，优选的1.6‰～2‰、1.7‰～2‰、1.8‰～2‰、1.9‰～2‰、1.5‰～1.6‰、1.5‰～1.7‰、1.5‰～1.8‰、1.5‰～1.9‰、1.6‰～1.7‰、1.6‰～1.8‰、1.6‰～1.9‰、1.6‰～2.0‰、1.7‰～1.8‰、1.7‰～1.9‰、1.7‰～2.0‰、1.8‰～1.9‰、1.8‰～2.0‰，或1.9‰～2.0‰等，以此对最终获得的强化玻璃的应力状态进行控制。
在一个或多个实施例中，不论是单步法还是多步法，都会对多批次的前体玻璃进行化学强化，即多批次前体玻璃在同一个盐浴环境中分批次进行强化处理。在进行离子交换反应时，完成每一批次前体玻璃化学强化后的离子交换盐浴中，会产生微量的杂质离子，主要为从前体玻璃中交换出来的锂离子，在对多批次的前体玻璃进行化学强化后，离子交换盐浴中锂离子的浓度会有所上升，此时必须对锂离子的浓度进行控制，因为离子交换盐浴中锂离子会成为K +-Na +、Na +-Li +离子交换的阻碍离子，少量锂离子的存在会大幅度降低离子交换程度，削弱强化玻璃强化状态。所述盐浴中锂离子浓度占盐浴中总碱金属离子的摩尔比少于0.25％及其之间所有范围和子范围，例如0.02％～0.2％，0.1％～0.16％，0.03％～0.2％，0.04％～0.18％，0.05％～0.1％，0.01％～0.24％，0.1％～0.25％，0.1％～0.18％，0.1％～0.15％，0.1％～0.12％，0％，0.15％，0.18％，0.2％，0.19％，0.14％，0.16％，0.05％，0.21％，0.08％，0.06％，0.04％，0.03％，0.02％，或者0.01％。
在一些实施例中，当非首批次强化玻璃表面的压应力下降至首批次强化玻璃表面压应力的5％～20％时，停止离子交换，并向离子交换盐浴中投入锂离子提纯物加热反应一段时间即可。优选的，向离子交换盐浴中投入质量为离子交换盐浴质量的0.1％～2％锂离子提纯物，提纯温度控制在360℃～450℃，反应时间与强化玻璃强化时间一致。
在一些实施例中，当非首批次强化玻璃表面的压应力下降至首批次强化玻璃表面压应力的10％～20％时，停止离子交换并将前体玻璃从离子交换盐浴中取出，然后向离子交换盐浴中投入质量为离子交换盐浴质量的1％～5％锂离子提纯物，提纯温度控制在360～450℃，反应时间与强化玻璃强化时间一致。但是，如果是多批次前体玻璃分别放入独立的盐浴中进行强化处理则不用加入锂离子提纯物。
所述锂离子提纯物为离子筛材料，所述离子筛材料基于氧化物wt％计，含有：15％～55％的SiO 2、5％～50％的辅料、15％～48％的至少一种功能性金属氧化物，所述功能性金属氧化物中的金属为一价和/或二价金属，所述一价金属为锂、钠、钾、铷中的至少一种，所述二价金属为镁、钙、锶、钡中的至少一种，所述辅料与SiO 2形成极性共价键和离子键，该辅料选自氧化磷、氧化硼、氧化铝、氧化锆、氧化铬、氧化铁、氧化锌、氧化铋、氧化 钴中的至少一种。所述锂离子提纯物主要用于除去离子交换盐浴中的Li +，控制离子交换盐浴中的Li +的浓度，减少其对强化玻璃离子交换程度的影响；同时，不会在离子交换盐浴中引入其它杂质离子，使用过后的离子筛不会对环境产生污染。锂离子提纯物的使用可以有效避免离子交换盐浴失活、其强化效果的减弱，恢复离子交换盐浴的活性。
本发明还公开一种消费电子终端，包括：外壳，所述外壳包括前表面、后表面和侧表面；以及部分位于所述外壳内的电子组件，所述电子组件包括显示器，该显示器位于所述外壳的前表面处或者毗邻所述前表面；所述前表面或/和后表面或/和侧表面包括本发明所述具有安全应力状态的强化玻璃。所述消费电子终端包括手机、平板电脑或其他电子终端。
本发明所述的强化玻璃可被包含在其他制品中，例如具有显示器的制品(或显示制品)(如，消费电子产品，包括移动电话、平板电脑、计算机、导航系统等)、建筑制品、运输制品(如，汽车、火车、飞机、海上航行器等)、器具制品、或需要一定透明度、抗划伤性、耐磨性或其组合的任何制品。包含本发明公开的任何玻璃制品的示例性制品参见附图2和附图3。具体的，附图2显示了一种消费电子装置的前表面，附图3显示了该消费电子装置的后表面，其包括外壳，该外壳包括前表面1、后表面2和侧表面；以及部分位于外壳内或者全部位于外壳内的电子组件，并且电子组件不仅包括显示器，还可包括控制器、存储器以及其他电子组件，其中，显示器位于外壳前表面处或毗邻外壳前表面。所述外壳前表面或/和后表面或/和侧表面包括如本发明所述的强化玻璃。
在一些实施方式中，还可以包括覆盖于外壳的前表面处或位于所述显示器上的覆盖制品3，所述覆盖制品3和/或外壳的一部分包括本发明所述的强化玻璃。
本发明中，为获得具有安全压应力状态的强化玻璃，对所述玻璃的料方也有一定的要求，具体地，基于氧化物的摩尔％计，所述玻璃主要包含以下组分：
SiO 2：65mol％～75mol％，优选为70mol％～75mol％；
Al 2O 3：8mol％～15mol％；
其中，SiO 2的含量占SiO 2和Al 2O 3总量的至少78mol％，优选80mol％以上。
在本发明所述玻璃的料方中，玻璃网络组成体主要为SiO 2和Al 2O 3，两者可以提高玻璃网络结构的的强度，通过高网络架构组成可以使玻璃桥氧数量增加，尤其是提高硅成分的含量，可以提高玻璃的网络结构强度。而Al 2O 3有助于增加玻璃网络的刚性，Al 2O 3可以四配位或五配位存在于玻璃中，这增加了玻璃网络的堆积密度并因此增加了化学强化所形成的压应力。高网络结构强度对玻璃进行离子交换时具有重要作用，因为玻璃在进行离子交换过程中，会分步或同时进行K +-Na +、Na +-Li +二元离子交换，以形成复合压应力层。但 在这一过程中，玻璃会因为不同半径离子进行交换而产生应力松弛效应，并且离子交换反应中的高温、较长的反应时间等因素都会对复合压应力层，尤其是中深层产生削弱作用，因此，提高所述玻璃的网络结构强度可以有效的克服上述原因对于复合压应力层的影响。在一些实施例中，所述玻璃可包括8mol％～15mol％Al 2O 3及其之间的所有范围和子范围，例如8mol％～14.5mol％，8mol％～14mol％，8mol％～13.5mol％，8mol％～13mol％，10mol％～13mol％，8mol％～12mol％，9mol％～14.5mol％，9mol％～14mol％，9mol％～11.5mol％，10mol％～13mol％，9mol％，9.5mol％，10mol％，10.5mol％，11mol％，11.2mol％，12.4mol％，12.6mol％，12.8mol％，13mol％，13.2mol％，13.4mol％，13.6mol％，13.8mol％，或者15mol％。
在所述玻璃的组分还包括B 2O 3，B 2O 3的作为玻璃的次网络架构，适量的B 2O 3可以促进玻璃高温熔化，降低融化难度，并且可以有效提高玻璃中离子交换的速率，特别是对K +-Na +的交换能力提升非常显著，但过量B 2O 3会导致玻璃网络结构的减弱，因此需要控制B 2O 3的加入量，B 2O 3的摩尔占比控制在不大于3mol％的范围内。在一些实施例中，所述玻璃可包括不大于3mol％的B 2O 3及其之间的所有范围和子范围，例如0～2.9mol％，0～2.7mol％，0～2.1mol％，0～1.7mol％，0～1.2mol％，1mol％～2.6mol％，1mol％～2.0mol％，1mol％～1.5mol％，1mol％～1.3mol％，1mol％～1.9mol％，0mol％，1.4mol％，1.6mol％，2.3mol％，2.5mol％，2.9mol％，2.7mol％，2.4mol％，2.1mol％，0.4mol％，0.7mol％，0.6mol％，0.5mol％，0.3mol％，0.2mol％，或者3.0mol％。
所述玻璃的组分还包括Na 2O和Li 2O。其中，Na 2O的摩尔占比在1mol％～6mol％的范围内。Na 2O是离子交换的主要成分，是形成表面高压应力的关键交换离子，与离子交换盐浴中的K +进行K +-Na +交换，能够使玻璃通过离子交换得到足够高的压应力，因此，在一些实施例中，所述玻璃可包括1mol％～6mol％的Na 2O及其之间的所有范围和子范围，例如1～4mol％，1mol％～4.6mol％，1mol％～4mol％，1mol％～4.7mol％，1mol％～3mol％，1mol％～3.5mol％，2mol％～5.9mol％，2mol％～4.7mol％，2mol％～3.8mol％，1.5mol％～5.6mol％，2.6mol％～4.9mol％，1.5mol％～4mol％，3.7mol％～5.8mol％，1mol％，1.5mol％，2mol％，2.8mol％，2.6mol％，2.5mol％，2.1mol％，3.8mol％，3.6mol％，4mol％，4.4mol％，4.3mol％，3.2mol％，或者5.1mol％。
Li 2O也是离子交换的主要成分，Li 2O的摩尔占比在7mol％～12mol％的范围内，离子交换盐浴中Na +半径比K +小，使其能够更加深入玻璃内部与Li +进行离子交换，玻璃中的Li +是形成深层压应力的关键交换离子，与离子交换盐浴中的Na +进行Na +-Li +交换，使玻璃 能够形成高深度的压应力层。在一些实施例中，所述玻璃可包括7mol％～12mol％的Li 2O及其之间的所有范围和子范围，例如7mol％～11mol％，7.8mol％～10.7mol％，7.5mol％～10mol％，8.6mol％～11.7mol％，8.2mol％～11.4mol％，9.1mol％～10.8mol％，9.2mol％～11.5mol％，10.2mol％～11.9mol％，8.5mol％～11.5mol％，9.5mol％～10mol％，10.6mol％～11.9mol％，7.7mol％～9.8mol％，7.5mol％，8mol％，9mol％，7.8mol％，8.6mol％，9.5mol％，10.1mol％，11.8mol％，7.6mol％，10mol％，10.4mol％，11.3mol％，9.2mol％，或者10.1mol％。
由于Na 2O和Li 2O属于碱金属氧化物，两者在玻璃内部为游离状态，其多余的氧离子会断开桥氧，因此需要将Na 2O和Li 2O的摩尔占比控制在7mol％～13mol％的范围内，在一些实施例中，所述玻璃可包括7mol％～13mol％Na 2O+Li 2O及其之间的所有范围和子范围，例如8mol％～13mol％，7mol％～12mol％，8mol％～10.5mol％，7mol％～10.6mol％，8mol％～11mol％，7mol％～10.5mol％，7mol％～11.5mol％，9mol％～11mol％，7mol％～8.9mol％，8.6mol％～12.8mol％，9mol％～12.4mol％，7mol％～9.8mol％，7mol％～10.4mol％，7mol％～10.8mol％，9mol％，10mol％，11.2mol％，11.4mol％，11.6mol％，11.8mol％，12mol％，12.1mol％，12.3mol％，12.5mol％，或者13mol％。
所述玻璃的组分还包括K 2O，K 2O的摩尔占比控制在0mol％～3mol％之间，K 2O是离子交换的主要成分。在一些实施例中，所述玻璃可包括0mol％～3mol％的K 2O及其之间的所有范围和子范围，例如0.1mol％～3mol％，0.2mol％～2.8mol％，0.1mol％～2.6mol％，0.3mol％～2mol％，0.4mol％～1.8mol％，0.5mol％～1.0mol％，1mol％～2.5mol％，1mol％～2.0mol％，1mol％～1.8mol％，1mol％～1.5mol％，1mol％～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％，0.1mol％，或者0mol％。
所述玻璃的组分还包括MgO，MgO的摩尔占比控制在2mol％～7.5mol％之间，MgO作为玻璃网络结构中间体，具有降低玻璃高温粘度，从而达到增加玻璃杨氏模量的作用。在一些实施例中，所述玻璃可包括2mol％～7.5mol％的MgO及其之间的所有范围和子范围，例如2.5mol％～2.8mol％，2.5mol％～2.6mol％，2.6mol％～3.2mol％，2.4mol％～3.8mol％，3.5mol％～4.0mol％，3mol％～4.5mol％，2.7mol％～5.8mol％，2.5mol％～5.0mol％，3.1mol％～6.5mol％，4mol％～5mol％，2.5mol％，3.5mol％，3.8mol％，3mol％，5mol％，2.8mol％，2.6mol％，4.5mol％，4.1mol％，4.8mol％，4.6mol％，3.2mol％，3.4mol％，3.3mol％，3.2mol％，或者3.1mol％。
所述玻璃的组分中还包括化学澄清剂，这种澄清剂包括但不限于SnO 2和氯化钠。在 一些实施例中，所述玻璃可包括不大于1mol％的SnO 2和氯化钠及其之间的所有范围和子范围，例如0.1mol％～0.9mol％，0.1mol％～0.8mol％，0.1mol％～0.7mol％，0.1mol％～0.6mol％，0.1mol％～0.5mol％，0.1mol％～0.4mol％，0.5mol％～1.0mol％，0.05mol％～1.0mol％，0.03mol％～1.0mol％，0.02mol％～1.0mol％，1mol％，0.9mol％，0.8mol％，0.7mol％，0.6mol％，0.5mol％，0.4mol％，0.3mol％，0.2mol％，或者0mol％。
特别说明，所述玻璃不含磷，也不含镁以外的其他碱土金属元素。即不主动添加含磷和其他碱土金属元素，但是有可能以非常少量作为杂质存在，例如在实施例中，均低于300ppm或更少。因为玻璃中五氧化二磷可以降低玻璃高温的融化温度，但是由于五氧化二磷具有磷氧双键，结构不稳定，其抗划伤能力差，且含磷结构会导致玻璃的分叉阈值下降，并且在浮法玻璃中，含磷结构会使玻璃容易分相析晶，提高生产难度。镁碱土金属具有较好的高温促熔性，且对离子交换速率影响较少，但Ca、Zn等及其他碱土金属氧化物，其离子半径比镁大，其对离子交换速率影响更大。
在本实施例中，将上述玻璃料方中的组分在熔炼温度为1630℃～1700℃之间，例如1630℃、1640℃、1650℃、1680℃、1690℃或1700℃可选用氧化锡和氯化钠作为澄清剂，两者摩尔占比不超过1％，例如0.1％、0.2％、0.5％、0.6％、0.7％、0.8％或0.9％。并根据其高温粘度及料性，可采用溢流下拉法、浮法、压延法生产得到前体玻璃。
本发明所述具有安全压应力状态的强化玻璃的加工方法，以实施例1为例：
S1：首先根据表1中实施例1的原材料比例对玻璃前体原材料的配比准确称量，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，然后成型得到厚度为0.7mm的前体玻璃板。
S2：对步骤S1得到的前体玻璃板进行350℃的预热处理，时间为23min，将预热处理后的前体玻璃板放入15wt％的NaNO 3和85wt％的KNO 3的混合盐浴中进行离子交换反应，反应温度为440℃，反应时间为10h，对前体玻璃板的缩放比进行检测，当其缩放比为2‰时，反应完成后，取出洗净，得到强化玻璃板。
下面通过具体实施例和对比例对本发明加以说明，表1为前体玻璃和对比例的料方，表2为制备强化玻璃的工艺参数，表3为实施例与对比例的性能测试参数，表4为实施例1和实施例3不同厚度样品的测试结果。
表1
Figure PCTCN2021106369-appb-000003
注：“-”表示前体玻璃中不含有该成分。
表2
性能指标 实施例1 实施例2 实施例3 实施例4 对比例1
分叉阈值(MPa/mm) 45000 48000 50000 45000 33200
痕带阈值(MPa/mm) 38000 39800 42100 38000 28000
厚度(mm) 0.7 0.7 0.7 0.8 0.7
Na 2O(摩尔百分数) 4 3 3 4 --
Na 2O/(Li 2O+Na 2O+K 2O) 29.63 25 20 29.63 --
表3
Figure PCTCN2021106369-appb-000004
注：“-”表示未对强化玻璃的该项参数进行检测。
表4
Figure PCTCN2021106369-appb-000005
其中，对实施例1和实施例3样品厚度与CS 50之间的关系做了进一步验证，从表4中可以看出，在不同厚度下，经过离子交换后强化玻璃的CS 50与其厚度满足本发明所述的关系式。
结合表2和表3，本实施例的强化玻璃在钾、钠的混合盐浴中进行K +-Na +离子交换，同时也进行Na +-Li +离子交换，形成压应力，对强化玻璃进行化学强化，提升强化玻璃的强度。强化后强化玻璃表面压应力为500MPa以上，保证玻璃的抗冲击性能。同时，通过对缩放比的控制来对强化时间进行调整，使得到的强化玻璃的CS 50与其厚度满足本发明所述 的关系式，最终使强化玻璃具有高的抗跌落性能。而对比例1没有对缩放比进行控制，这也使得其抗跌落性能远不及本发明的实施例。
对实施例1制备方法获强化玻璃进行整机跌落实验，将手机模具与实施例1强化玻璃制成的样品贴合牢固，将强化玻璃样品朝下水平跌落至表面附有砂纸的大理石板上，取所述强化玻璃样品不破碎的最高点为抗跌落高度。通过整机跌落实验测试后，实施例1强化玻璃抗跌落高度为1.5m，远高于对比例1的抗跌落高度，说明实施例1具有高的抗跌落性能。
在张应力释放实验中，实施例1强化玻璃从1.7m的高度跌落后破碎情参见附图1，破碎的颗粒中70％以上的碎片颗粒在二维图纸上的垂直投影平均大小在15mm以上，不会产生颗粒过小的碎片，表明实施例1强化玻璃的张应力在安全范围内，不会造成安全隐患。
通过表3可以看出，本发明所述的强化玻璃的压应力与张应力处于最佳的状态，所述强化玻璃具有很高的网络结构强度，并获得了高的表面压应力，有效提升了强化玻璃的抗跌落高度，同时将强化玻璃的张应力控制在安全的范围内来进一步提升抗跌落强度的极限，从而保证了强化玻璃张应力的安全性。并且，不会因轻微的冲击发生爆炸性开裂，也不会产生自爆现象。
最后需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制技术方案，本领域的普通技术人员应当理解，那些对本发明的技术方案进行修改或者等同替换，而不脱离本技术方案的宗旨和范围，均应涵盖在本发明的权利要求范围当中。

Claims (23)

  1. 一种具有安全应力状态的强化玻璃，其特征在于，该强化玻璃其表面压应力与厚度的数值满足以下条件：
    Figure PCTCN2021106369-appb-100001
    其中，CS 50为距离玻璃表面以下50微米处的压应力，单位MPa；a为－486.23；b为0.449；217－20T≦c≦217+20/T；T为强化玻璃的厚度，单位为mm。
  2. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述强化玻璃表面压应力CS为500MPa以上。
  3. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述强化玻璃压应力层深度DOL 0达到该强化玻璃厚度的16％以上。
  4. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述强化玻璃的厚度T为0.4mm～2mm。
  5. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述安全应力状态为所述强化玻璃的压应力足够高，使所述强化玻璃的抗跌落高度至少在1.5m以上，且所述强化玻璃跌落破碎时产生的碎片颗粒中70％以上的碎片颗粒在二维图纸上的垂直投影平均大小大于15mm。
  6. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述强化玻璃组分中包含Na 2O、Li 2O或K 2O。
  7. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述强化玻璃不含磷。
  8. 根据权利要求1所述具有安全应力状态的强化玻璃，其特征在于，所述强化玻璃不含镁以外的其他碱土金属元素。
  9. 一种具有安全应力状态的强化玻璃的加工方法，其特征在于，包括如下步骤：
    S1：对前体玻璃进行预热处理；
    S2：将经过步骤S1预热处理的前体玻璃放入盐浴中，加热进行离子交换反应，获得如权利要求1～8任一所述的强化玻璃；
    其中，所述盐浴为硝酸钾、硝酸钠混合盐浴，所述硝酸钠质量分数小于所述前体玻璃组分中Na 2O/(Li 2O+Na 2O+K 2O)的摩尔比值，并大于所述前体玻璃组分中Na 2O的摩尔百分比，所述强化玻璃的缩放比控制在1.5‰～2‰。
  10. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，所 述前体玻璃组分中包含Na 2O、Li 2O或K 2O。
  11. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，步骤S2中所述盐浴中锂离子浓度占盐浴中总碱金属离子的摩尔比少于0.25％。
  12. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，步骤S1中对前体玻璃进行300℃～400℃预热处理，时间为10min～30min。
  13. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，步骤S2中离子交换反应温度为350～500℃。
  14. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，步骤S2中离子交换反应温度为390～460℃。
  15. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，所述前体玻璃采用浮法、溢流法、压延法及浇铸成型法中的任一种方法成型而成。
  16. 根据权利要求9所述具有安全应力状态的强化玻璃的加工方法，其特征在于，在对多批次所述前体玻璃进行离子交换时，检测到非首批次强化玻璃表面的压应力CS下降至首批次强化玻璃表面的压应力的10％～20％时，停止离子交换反应，在盐浴中投入锂离子提纯物后，加热提纯，继续进行离子交换。
  17. 根据权利要求16所述具有安全应力状态的强化玻璃的加工方法，其特征在于，所述锂离子提纯物为离子筛材料，所述离子筛材料基于氧化物的wt％计，含有：SiO 2为15％～55％、辅料5％～50％、至少一种功能性金属氧化物为15％～48％；所述功能性金属氧化物中的金属为一价和/或二价金属。
  18. 根据权利要求16所述具有安全应力状态的强化玻璃的加工方法，其特征在于，所述锂离子提纯物为离子筛材料，所述一价金属为锂、钠、钾、铷中的至少一种，所述二价金属为镁、钙、锶、钡中的至少一种；所述辅料与SiO 2形成极性共价键和离子键，该辅料选自氧化磷、氧化硼、氧化铝、氧化锆、氧化铬、氧化铁、氧化锌、氧化铋、氧化钴中的至少一种。
  19. 根据权利要求16所述具有安全应力状态的强化玻璃的加工方法，其特征在于，所述加热提纯温度为300～500℃，反应时间与强化玻璃强化时间一致。
  20. 根据权利要求16所述具有安全应力状态的强化玻璃的加工方法，其特征在于，所述锂离子提纯物的投入量为离子交换盐浴质量的1％～5％。
  21. 一种消费电子终端，其特征在于，包括：
    外壳，所述外壳包括前表面、后表面和侧表面；
    以及部分位于所述外壳内的电子组件，所述电子组件包括显示器，该显示器位于所述外壳的前表面处或者毗邻所述前表面；
    所述前表面或/和后表面或/和侧表面包括如权利要求1～20任一所述具有安全应力状态的强化玻璃。
  22. 根据权利要求21所述消费电子终端，其特征在于，还包括覆盖于外壳的前表面处或位于所述显示器上的覆盖制品，所述覆盖制品包括如权利要求1～20任一所述具有安全应力状态的强化玻璃。
  23. 根据权利要求21或22所述消费电子终端，其特征在于，所述消费电子终端包括手机、平板电脑、或其他电子终端。
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