Glass composition, crystallized glass, and its manufacturing method and use

Abstract

This application discloses a glass composition, a crystallized glass, and its manufacturing method and use, the glass composition comprising, by mass%, 71.5-74.5% SiO2, 6.2-8.7% Al2O3, 1.7-3% P2O5, 10-12.5% ​​Li2O, 0.1-2% Na2O, and 3-5% ZrO2. In the technical solution of this application, the components SiO2, Al2O3, P2O5, Li2O, Na2O, and ZrO2 in the glass composition are combined with a specific specific gravity and combined with a crystallized glass crystallization process and a strengthening process, thereby significantly reducing the b value and haze and obtaining a crystallized glass with excellent strengthening performance.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Chinese patent application bearing application number 202111682724.5, filed on December 31, 2021, Chinese patent application bearing application number 202111681556.8, filed on December 31, 2021, and Chinese patent application bearing application number 202111682722.6, filed on December 31, 2021, the entire contents of which are incorporated herein by reference.

[0002] Technical Field This application relates to the field of glassmaking technology, and in particular to glass compositions, crystallized glasses, and methods for making and using the same. [Background technology]

[0003] With the development of display technology, glass has become a common material for protecting display devices. Commercially available protective cover glass for electronic products generally consists of high-alumina silicate glass. While high alumina is advantageous for improving stress strength and stress layer depth after ion exchange, it also has poor drop resistance. Research has shown that 70% of electronic product breakages are due to accidental drops.

[0004] By introducing a nucleating agent into the glass recipe or adjusting the oxide composition ratio in the recipe, one or more crystalline phases called glass-ceramics are formed in the subsequent heat treatment process. Glass-ceramics not only have the high transparency of glass but also the high strength of ceramics, which can improve the average hardness, fracture toughness, and other properties of glass. The microcrystalline phase in glass-ceramics can block the propagation path of microcracks, which is beneficial for overall improvement of the glass's scratch resistance, impact resistance, drop resistance, and other properties.

[0005] The performance of glass-ceramics is determined by the ratio of the crystalline phase to the glass phase, the size of the crystal grains, etc. During the manufacturing process of glass-ceramics, factors such as the aggregation of the glass composition, the interface morphology of the crystalline phase, and the external morphology of the crystal grains cause currently manufactured transparent glass-ceramics to have a large b value, high haze, and macroscopically, transmitted light to appear yellowish, which affects the transmittance and usability of the glass-ceramics. Summary of the Invention [Problem to be solved by the invention]

[0006] The main object of the present application is to provide a glass composition, a glass-ceramic, and a method for producing and using the same, in order to solve the problems of high b-value and high haze of conventional glass-ceramics. [Means for solving the problem]

[0007] In order to achieve the above object, the present invention provides a composition comprising, in mass %, 71.5-74.5% SiO2, 6.2-8.7% Al2O3, 1.7-3% P2O5, 10-12.5% ​​Li2O, 0.1-2% Na2O, and A glass composition containing 3 to 5% ZrO2 is provided.

[0008] In one embodiment, it further contains 0.1 to 1.7% B2O3 and / or 0.1 to 1.5% CaO.

[0009] In one embodiment, −1.1≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦6.7.

[0010] In one embodiment, 0.19≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.98.

[0011] In one embodiment, 0.06≦[W(ZrO2)−3×W(B2O3)] / W(P2O5)≦1.57.

[0012] In one embodiment, in weight percent: 72-74% SiO2, 7.5-8.4% Al2O3, 2-2.8% P2O5, 0.3-0.8% B2O3, 10.5-11.8% Li2O, 0.5-1.3% Na2O, and Contains 3.4-4.7% ZrO2.

[0013] In one embodiment, 0.6≦W(SiO)−6×W(AlO)−2×W(LiO)≦5.4; 0.28≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.8, 0.5≦[W(ZrO2)−3×W(B2O3)] / W(P2O5)≦1.36.

[0014] In one embodiment, in weight percent: 72.5-73.5% SiO2, 7.7-8% Al2O3, 2.1-2.5% P2O5, 0.5-0.7% B2O3, 11-11.5% Li2O, 0.7-1.1% Na2O, and Contains 3.8-4.4% ZrO2.

[0015] In one embodiment, 2.5≦W(SiO)−6×W(AlO)−2×W(LiO)≦4.3; 0.43≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.64, 0.81≦[W(ZrO2)−3×W(B2O3)] / W(P2O5)≦1.16.

[0016] The present application provides a glass composition comprising, in mass %, 72 to 74.3% SiO2, 7 to 8.5% Al2O3, 1.8 to 3% P2O5, 10.2 to 12.5% ​​Li2O, 0.5 to 2% Na2O, and 3.5 to 4.7% ZrO2.

[0017] In one embodiment, 2.9≦W(SiO)−6×W(AlO)−2×W(LiO)≦5.2; 0.26≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.85, 1.17≦W(ZrO2) / W(P2O5)≦2.61, 2.5≦[W(SiO2)−6×W(Al2O3)−2×W(Li2O)] / W(Na2O)≦5.8.

[0018] In one embodiment, in weight percent: It contains 72.8-73.9% SiO2, 7.4-8% Al2O3, 2.1-2.6% P2O5, 10.7-11.7% Li2O, 0.9-1.4% Na2O, and 3.9-4.4% ZrO2.

[0019] In one embodiment, 4.5≦W(SiO)−6×W(AlO)−2×W(LiO)≦5.2; 0.42≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.66, 1.5≦W(ZrO2) / W(P2O5)≦2.1, 3.57≦[W(SiO2)−6×W(Al2O3)−2×W(Li2O)] / W(Na2O)≦5.

[0020] The present application provides, in mass %, A glass composition is provided that includes 71.5-74% SiO2, 6.2-8.5% Al2O3, 1.7-2.6% P2O5, 0.1-1.7% B2O3, 10-12% Li2O, 0.1-2% Na2O, 0.1-1.5% CaO, and 3-5% ZrO2.

[0021] In one embodiment, in mass % based on the oxide, It contains 72-73.5% SiO2, 6.8-8.2% Al2O3, 2-2.4% P2O5, 0.4-1.1% B2O3, 10.8-11.7% Li2O, 0.4-1.7% Na2O, 0.3-1% CaO and 3.3-4.4% ZrO2.

[0022] In one embodiment, 2≦[W(ZrO2)−W(CaO)] / [W(P2O5)−W(B2O3)]≦3.22.

[0023] In one embodiment, 2.06≦[W(ZrO2)−W(CaO)] / [W(P2O5)−W(B2O3)]≦2.31.

[0024] In one embodiment, 2.3≦W(SiO)−6×W(AlO)−2×W(LiO)≦10.3; 0.27≦[W(Li2O)−W(Al2O3)] / [W(P2O5)+W(ZrO2)]≦0.87.

[0025] In one embodiment, 2.7≦W(SiO)−6×W(AlO)−2×W(LiO)≦7.8; 0.46≦[W(Li2O)−W(Al2O3)] / [W(P2O5)+W(ZrO2)]≦0.77.

[0026] The present application further provides a glass-ceramic comprising the glass composition as described above.

[0027] In one embodiment, the thickness of the crystallized glass is 0.3 to 1.5 mm.

[0028] The present application further provides a glass-ceramic comprising the above glass composition, wherein the glass-ceramic comprises a crystalline phase Li2Si2O5 and a crystalline phase LiAlSi4O 10 Contains:

[0029] In one embodiment, 0.91≦W(LiSiO) / W(LiAlSiO 10 )≦1.06.

[0030] In one embodiment, 0.97≦W(LiSiO) / W(LiAlSiO 10 )≦1.03.

[0031] In one embodiment, 10.44≦M≦12.54; Here, M = 1.3 × [W(Li2Si2O5) / W(LiAlSi4O 10 )]×{0.86×[W(SiO2)-6×W(Al2O3)-2×W(Li2O)]+1.83×[(W(Li2O)-W(Al2O3)) / (W(P2O5)+W(Zr O2))]+1.67×[W(ZrO2) / W(P2O5)]+0.25×[(W(SiO2)-6×W(Al2O3)-2×W(Li2O)) / W(Na2O)]}.

[0032] In one embodiment, 11.85≦M≦12.54.

[0033] The present application provides a glass-ceramic comprising the glass composition described above.

[0034] In one embodiment, the crystalline phase of the crystallized glass is mainly lithium disilicate and petalite, the total content of the crystalline phase of the crystallized glass is 60% to 90%, the content of the lithium disilicate is > 30%, and the content of the petalite is > 30%. The present application further provides a method for producing crystallized glass, the method comprising: Step S10 of weighing the glass composition as described above; Step S20: mixing and melting the glass composition, then fining, homogenizing, forming, annealing, and finally cutting to obtain a base glass; and step S30 of heat-treating the base glass to obtain crystallized glass.

[0035] In one embodiment, step S30 includes: The base glass is heated from room temperature to 510 to 540°C in 20 to 60 minutes, and a first nucleation treatment is carried out for 3 to 8 hours. The temperature is raised to 580-610°C in 5-30 minutes, and a second nucleation treatment is carried out for 3-8 hours. The temperature is raised to 650 to 680 ° C in 5 to 30 minutes, and crystallization treatment is carried out for 3 to 8 hours. and cooling to room temperature to obtain glass-ceramics.

[0036] In one embodiment, the step of heat-treating the base glass to obtain glass-ceramics comprises: The base glass is heated from room temperature to 530 to 570°C in 20 to 60 minutes, and a nucleation treatment is carried out for 3 hours or more. The temperature is raised to 680 to 720 ° C in 5 to 30 minutes, and the crystallization treatment is carried out for 3 hours or more. and cooling to room temperature to obtain the crystallized glass.

[0037] In one embodiment, after step S30, and a step S40 of pretreating the glass-ceramics and then placing it in an ion exchange bath to perform a salt bath to obtain chemically strengthened glass-ceramics. wherein the ion exchange bath contains, in mass %, 20 to 40% NaNO3 and 60 to 80% KNO3, and / or The salt bath strengthening temperature is 420 to 500°C, and / or The salt bath strengthening time is 3 to 8 hours.

[0038] In one embodiment, in step S20, the forming method includes float forming, overflow forming, calendar forming, or slot downdraw forming.

[0039] The present application further provides an electronic display terminal including the above-described glass-ceramics. [Effects of the Invention]

[0040] In the technical solution of this application, the components SiO2, Al2O3, P2O5, Li2O, Na2O and ZrO2 in the glass composition are combined with a specific specific gravity, and combined with the crystallization process and tempering process of the crystallized glass, thereby significantly reducing the b value and haze and obtaining a crystallized glass with excellent tempering performance. [Brief explanation of the drawings]

[0041] In order to more clearly explain the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present application, and those skilled in the art can obtain other relevant drawings based on these drawings without any creative work.

[0042] [Figure 1] 1 is a schematic flowchart of one embodiment of a method for producing crystallized glass provided in the present application. [Figure 2] 1 is a schematic flow chart of another embodiment of a method for producing crystallized glass provided herein. [Figure 3] FIG. 1 is a linear relationship diagram between M and the fracture toughness KIC of glass-ceramics in the present application.

[0043] The realization of the object, features and advantages of the function of the present application will be further explained in conjunction with the embodiments with reference to the drawings. DETAILED DESCRIPTION OF THE INVENTION

[0044] In order to clarify the objectives, technical solutions and advantages of the embodiments of the present application, the technical solutions in the embodiments of the present application will be described below clearly and completely. Obviously, the described embodiments are only some of the embodiments of the present application, but not all of the embodiments.

[0045] Unless specific conditions are specified in the examples, the procedures are performed according to standard conditions or manufacturer's recommendations. Reagents and instruments used without a manufacturer's name are all commercially available and standard. Throughout this specification, the term "and / or" refers to three parallel solutions. For example, "A and / or B" includes technical solution A, technical solution B, or a solution that simultaneously satisfies both A and B. The technical solutions in each example may be combined with each other, but only on the basis that they can be realized by a person skilled in the art. If a combination of technical solutions contradicts or is impossible to realize, such a combination of technical solutions should be considered nonexistent and not included in the scope of protection claimed by this application. All other examples obtained based on the examples of this application without the need for creative labor by a person skilled in the art are also within the scope of protection of this application.

[0046] With the development of display technology, glass has become a common material for protecting display devices. Commercially available protective cover glass for electronic products generally consists of high-alumina silicate glass. While high alumina is advantageous for improving stress strength and stress layer depth after ion exchange, the glass's drop resistance is poor. Research has shown that 70% of electronic product breakages are due to accidental drops.

[0047] Glasses that incorporate nucleating agents into their recipes or adjust the oxide composition ratios in the recipes to form one or more crystalline phases during subsequent heat treatment are called glass-ceramics. Glass-ceramics not only possess the high transparency of glass but also the high strength of ceramics, improving the average hardness, fracture toughness, and other properties of glass. The microcrystalline phase in glass-ceramics can block the propagation paths of microcracks, which is beneficial for overall improvement of the glass's scratch resistance, impact resistance, drop resistance, and other properties.

[0048] The performance of glass-ceramics is determined by the ratio of crystalline to glass phase, the size of the crystal grains, etc. During the manufacturing process of glass-ceramics, factors such as the aggregation of the glass composition, the interface morphology of the crystalline phase, and the external morphology of the crystal grains cause currently manufactured transparent glass-ceramics to have a large b value, high haze, and macroscopically, transmitted light to appear yellowish, which affects the transmittance and usability of the glass-ceramics.

[0049] In view of this, the present application provides a glass composition, and the glass-ceramics produced from this glass composition can effectively solve the problems of current transparent glass-ceramics having a large b value and high haze.

[0050] In an embodiment of the present application, a glass composition is provided that contains, by mass%, 71.5 to 74.5% SiO2, 6.2 to 8.7% Al2O3, 1.7 to 3% P2O5, 10 to 12.5% ​​Li2O, 0.1 to 2% Na2O, and 3 to 5% ZrO2.

[0051] In another embodiment, the glass composition further comprises, in mass %, 0.1 to 1.7% B2O3 and / or 0.1 to 1.5% CaO.

[0052] In the examples of the present application, the composition is, in mass%, 71.5 to 74.5% SiO2, 7.3 to 8.7% Al2O3, 1.7 to 3% P2O5, 0.1 to 1% B2O3, 10.2 to 12% Li2O, A glass composition is provided that contains 0.4 to 1.5% Na2O and 3.1 to 5% ZrO2.

[0053] In an embodiment of the present application, there is provided a glass composition containing, in mass % based on oxides, 71.5 to 74% SiO2, 6.2 to 8.5% Al2O3, 1.7 to 2.6% P2O5, 0.1 to 1.7% B2O3, 10 to 12% Li2O, 0.1 to 2% Na2O, 0.1 to 1.5% CaO, and 3 to 5% ZrO2.

[0054] The present application provides a glass composition, and the glass-ceramics produced from the glass composition can effectively solve the problems of a large b value and high haze, as well as the problems of a decrease in crystalline content and destruction of the interlocking structure of twin phases that occur during chemical strengthening.

[0055] The glass composition contains, in mass %, 72 to 74.3% SiO2, 7 to 8.5% Al2O3, 1.8 to 3% P2O5, 10.2 to 12.5% ​​Li2O, 0.5 to 2% Na2O, and 3.5 to 4.7% ZrO2.

[0056] First, the petalite molecular formula of the preferred glass-ceramic crystalline phase of the present invention is LiAlSiO 10 and the molecular formula of lithium disilicate is Li2Si2O5. When calculating the mass percentage of each component, the sum of the masses of SiO2, Al2O3, P2O5, B2O3, Li2O, Na2O, and ZrO2 in the glass composition is used as the basis, or the sum of the masses of SiO2, Al2O3, P2O5, Li2O, Na2O, and ZrO2 in the glass composition is used as the basis.

[0057] The glass composition of the present invention incorporates SiO2, which constitutes a component of the glass skeleton. SiO2, as the main component of the glass network structure, can impart excellent chemical stability, mechanical properties, and molding performance to the base glass and glass-ceramics. During the glass microcrystallization process, Li2Si2O5 and LiAlSi4O 10 SiO2 provides a source for forming crystalline phases, and excessive SiO2 promotes the formation of quartz and quartz solid solution during the glass crystallization process. Therefore, considering all factors, the SiO2 content should be selected to be 71.5 wt% to 74.5 wt%, or 72 wt% to 74.3 wt%, or 71.5 wt% to 74 wt%.

[0058] The glass composition of the present invention incorporates Al2O3, a network intermediate oxide. The non-bridging oxygen atoms form aluminum oxygen tetrahedra with Al, which have a larger volume than silicon oxygen tetrahedra. This creates larger gaps in the glass structure, which is favorable for ion exchange, thereby improving the chemical strengthening effect and the mechanical properties of the glass. However, Al2O3 is an oxide with a very high melting point, which can rapidly increase the high-temperature viscosity of the glass, making it difficult to refine and homogenize the glass and significantly increasing the concentration of bubble defects in the glass. A high Al2O3 content significantly increases the microcrystallization temperature of the glass, suppressing the crystallization ability of the base glass. This makes it difficult to form lithium disilicate, resulting in the formation of glass LiAlSiO4O during the crystallization process. 10 This promotes the excessive formation of LiAlSi2O6, which in turn forms a LiAlSi2O6 crystalline phase in the base glass, thereby reducing the transmittance of the glass. Therefore, taking all factors into consideration, the Al2O3 content should be selected to be 7.3 wt% to 8.7 wt%, or the Al2O3 content should be selected to be 6.2 wt% to 8.5 wt%, or the Al2O3 content should be selected to be 7 wt% to 8.5 wt%.

[0059] P2O5 is introduced into the glass composition of the present application, and P2O5 is more likely to promote the crystallization of lithium disilicate crystals. 5+ The ions have a very large electric field strength and have a strong ability to take away oxygen, which tends to strengthen the phosphorus-oxygen network structure. 5+ The ion is Si 4+ Since the electric field strength is greater than that of ions, P 5+ Li2O and P2O5 react to form Li3PO4 crystalline phase, which induces the reaction between Li2O and SiO2 in the glass to form Li2SiO3, and finally forms Li2Si2O5 crystalline phase. Furthermore, P2O5 is connected to the network by [PO4] tetrahedra, so that the glass network structure is loose and the network voids are large. + Ions and K in molten salts+ It is favorable for interdiffusion with ions, promoting ion strengthening during the glass tempering process and playing an important role in obtaining a high compressive stress layer. However, if the P2O5 content is too high, it promotes the precipitation of lithium metasilicate during the crystallization process, resulting in an excessively small glass phase, insufficient formation of Li2Si2O5 crystalline phase, and promotion of quartz phase precipitation, making it difficult to obtain high-transmittance crystallized glass. Therefore, taking all factors into consideration, the P2O5 content should be selected to be 1.7 wt% to 3 wt%, or 1.8 wt% to 3 wt%, or 1.7 wt% to 2.6 wt%.

[0060] The addition of B2O3 to the glass composition of the present application improves the meltability and melting point of the glass, and also improves the scratch resistance of the glass surface. Research conducted in this application has shown that B2O3, present in the glass-ceramic structure in the form of a dense [BO4], effectively suppresses the problem of increased haze in the glass-ceramic due to petalite growth during lithium disilicate nucleation (>580°C), while restricting the migration of alkali metal ions in the glass-ceramic, stabilizing the crystalline structure of the glass-ceramic. Therefore, taking all factors into consideration, the B2O3 content is selected to be 0.1 wt% to 1.7 wt%, or 0.1 wt% to 1 wt%.

[0061] The glass composition of the present invention incorporates Li2O, which belongs to the outer network oxide, to reduce the viscosity of the glass and promote the melting and fining of the glass. + Li is the main exchange ion in the chemical strengthening process. + The ion has a small radius and is + The faster ion exchange rate of the Li-containing glass allows the glass to develop a thicker strengthening layer in a shorter time. + Na ions and the melt + ions are exchanged, and the rate is + and K. +The exchange rate with ions is faster than that with Li2O. The high Li2O concentration promotes the formation of Li3PO4 in the base microcrystallization process, which is beneficial to the formation of lithium disilicate and petalite crystal phases in the crystallization process. In order to achieve a microcrystalline glass and obtain a deep ion-strengthened layer, the Na2O3 concentration is also beneficial to the chemical strengthening process. + and Li, which mutually reinforces the surface of the glass-ceramic and reduces cracks. + A sufficient amount of Li2O must be present in the glass to provide the mechanical strength of the glass-ceramic. However, if the Li2O content is too high, the viscosity of the glass will be too low, making it difficult to obtain a chemically stable glass composition. The compressive stress value during the ion strengthening process will be too low, and raw material costs will increase. Therefore, taking all factors into consideration, the Li2O content should be selected to be 10.2 wt% to 12 wt%, or 10.2 wt% to 12.5 wt%, or 10 wt% to 12 wt%.

[0062] The incorporation of Na2O into the glass composition of the present invention significantly reduces the viscosity of the base glass, promotes melting and fining of the base glass, and lowers the crystallization temperature of the glass. + By promoting the strengthening of glass-ceramics by ions, high compressive stress is generated on the glass surface, improving the strength of the glass and adding Na to the glass. + Therefore, taking all factors into consideration, the Na2O content should be selected to be 0.1 wt% to 2 wt%, or the Na2O content should be selected to be 0.4 wt% to 1.5 wt%, or the Na2O content should be selected to be 0.5 wt% to 2 wt%.

[0063] ZrO2 is introduced into the glass composition of the present application. On the one hand, the high potential energy of zirconium ions can strengthen the glass network structure, and ZrO2 has a tendency to promote the crystallization of petalite crystals. On the other hand, ZrO2 helps reduce the size of crystal grains during the crystallization process, thereby improving the transmittance of the glass and rapidly improving the chemical stability of the glass. Secondly, it improves the fracture toughness and bending strength of the glass, and generates stress induction through the crystalline phase transition of zirconia itself, thereby improving the fracture toughness after crystallization. If the ZrO2 content is too high, unmelted ZrO2 will remain in the glass, preventing uniform crystallization of the glass. Therefore, taking all factors into consideration, the ZrO2 content should be selected to be 3 wt% to 5 wt%, or 3.1 wt% to 5 wt%, or 3.5 wt% to 4.7 wt%.

[0064] In the technical solution of this application, the components SiO2, Al2O3, P2O5, B2O3, Li2O, Na2O and ZrO2 in the glass composition are combined with a specific specific gravity, and combined with a crystallization process and a tempering process of the crystallized glass, thereby significantly reducing the b value and haze and obtaining a crystallized glass with excellent tempering performance.

[0065] Furthermore, the incorporation of CaO into the glass composition of the present invention can improve the chemical stability and mechanical strength of the glass. CaO more easily combines with acidic Al2O3 in the glass structure, thereby affecting the boron coordination state. Furthermore, because CaO is more alkaline than Na2O, it can compensate for the negative charge of the [AlO4] tetrahedron, stabilizing the crystalline phase structure in the glass-ceramic. However, a high CaO content can cause a decrease in devitrification resistance. Therefore, taking all factors into consideration, the CaO content should be selected to be 0.1 wt% to 1.5 wt%.

[0066] In the technical solution provided in this application, the components SiO2, Al2O3, P2O5, B2O3, Li2O, Na2O, CaO and ZrO2 in the glass composition are combined with a specific specific gravity and combined with the crystallization process and strengthening process of the crystallized glass, thereby significantly improving the situation of a decrease in crystalline content and destruction of the interlocking structure of the twin phase that occurs during the chemical strengthening process, and obtaining a crystallized glass with excellent strengthening performance.

[0067] In one embodiment, the components of the glass composition include SiO2, Al2O3, P2O5, Li2O, Na2O, and ZrO2, and the relationship between each component of the glass composition satisfies 2.9≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦5.2. A=W(SiO2)−6×W(Al2O3)−2×W(Li2O), where W represents the mass% of the component relative to the total mass of all oxide components, and the A value is the molecular value of mass% calculated using this formula. When the A value is low, all of the SiO2 is in the crystalline phase, whereas Al2O3 or Li2O is in excess. When the A value is too high, all of the Al2O3 or Li2O is in the crystalline phase, with the remaining SiO2 existing as a network framework in the glass phase, resulting in a low total crystalline phase content of the crystallized glass. By controlling the A value within the above range, excess Al2O3 or Li2O can be avoided and the total crystalline phase content of the glass-ceramics can be effectively improved. Preferably, 4.5≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦5.2.

[0068] The relationship between the components of the glass composition satisfies 0.26≦[W(LiO)−W(AlO)] / [W(P0)+W(ZrO)]≦0.85. The formula is B=[W(LiO)−W(AlO)] / [W(P0)+W(ZrO)], where W represents the mass% of the component relative to the total mass of all oxide components. If the B value is too low, undesirable crystalline phases such as β-quartz are likely to occur, and the petalite crystalline phase is likely to form, resulting in grain growth, leading to the crystallite fraction becoming translucent or devitrified. If the B value is too high, the glass phase fraction in the crystallized glass becomes too high, preventing the crystallized glass from fully utilizing its superior performance. Thus, by controlling the B value within the above range, the crystallized glass's superior performance can be fully utilized, preventing the crystallite fraction from becoming translucent or devitrified. Preferably, 0.42≦[W(Li2O)−W(Al2O3)] / [W(P2O5)+W(ZrO2)]≦0.66.

[0069] The relationship between the components of the glass composition satisfies 1.17≦W(ZrO2) / W(P2O5)≦2.61. It is expressed as C1=W(ZrO2) / W(P2O5), where W represents the mass % of the component relative to the total mass of all oxide components. By controlling the C1 value within the above range, the activation energy of the liquid-liquid surface is reduced, causing phase separation and enabling nucleation and crystallization at low temperatures. Furthermore, the development of a phase interface due to the crystallization and unstable decomposition of the liquid phase is realized, lowering the activation energy or energy barrier for nucleation and lowering the nucleation temperature and crystallization temperature. The two types of crystalline phases compete for silicon and lithium sources, i.e., destroying the crystalline phase structure already formed by the other crystalline phase and using it to form their own crystalline phase. The amount of the formed petalite and lithium disilicate crystalline phases is (W(Li2SiO5) / W(LiAlSiO4)). 10) = 0.91 to 1.06 (details will be described later), and the crystallite size is uniform and less than 100 nm, satisfying the basic requirement for optical visibility. If the C1 value is too high or too low, the amount of single crystal phase increases and it is easy to grow, which reduces the visible light transmittance of the crystallites and increases haze. Preferably, 1.5≦W(ZrO2) / W(P2O5)≦2.1.

[0070] The relationship between the components of the glass composition satisfies 2.5≦[W(SiO2)−6×W(Al2O3)−2×W(Li2O)] / W(Na2O)≦5.8. The formula D is expressed as D=[W(SiO2)−6×W(Al2O3)−2×W(Li2O)] / W(Na2O), where W represents the mass percent of the component relative to the total mass of all oxide components. Controlling the D value within the above range helps stabilize the glass crystalline structure, particularly inhibiting lithium ion migration during the tempering process. This further maintains the interlocking structure formed by the petalite and lithium disilicate glass-ceramics, improving the performance of the glass-ceramics. If the D value is too high, the chemical strengthening ions in the glass-ceramics are difficult to exchange. If the D value is too low, the interlocking structure formed by the petalite and lithium disilicate glass-ceramics cannot be maintained, resulting in the destruction of the microcrystalline structure during the chemical tempering process. Preferably, 3.57≦[W(SiO2)−6×W(Al2O3)−2×W(Li2O)] / W(Na2O)≦5.

[0071] In one embodiment, the components of the glass composition preferably satisfy the conditions of SiO2 72.8-73.9%, Al2O3 7.4-8%, P2O5 2.1-2.6%, Li2O 10.7-11.7%, Na2O 0.9-1.4%, and ZrO2 3.9-4.4%, which further optimizes the performance of the glass-ceramics obtained from the glass composition.

[0072] In one embodiment, the components of the glass composition include SiO2, Al2O3, P2O5, BO3, Li2O, Na2O, and ZrO2, and the relationship between each component of the glass-ceramics satisfies -1.1≦W(SiO2)-6×W(Al2O3)-2×W(Li2O)≦6.7. A is expressed as W(SiO2)-6×W(Al2O3)-2×W(Li2O), where W represents the mass% of the component relative to the total mass of all components, and the A value is the molecular value of the mass% calculated by the formula. When the A value is low, all of the SiO2 enters the crystalline phase. In contrast, there is an excess of Al2O3 or Li2O, which results in a high proportion of petalite crystalline phase formation and easy grain growth, resulting in a low proportion of microcrystalline, leading to translucency or devitrification. If the A value is too high, Al2O3 or Li2O will all enter the crystalline phase, and the remaining SiO2 will exist as a network structure in the glass phase, resulting in a low total crystalline phase content of the glass-ceramics. Thus, by controlling the A value within the above range, the proportion of microcrystals in the glass-ceramics can be prevented from becoming translucent or devitrified, and the total crystalline phase content of the glass-ceramics can be effectively improved.

[0073] The relationship between the components of the glass-ceramics satisfies 0.19≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.98. It is expressed as B=[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)], where W represents the mass% of the component relative to the total mass of all components. If the B value is too low, the proportion of the glass phase in the glass-ceramics increases, and the superior performance of the glass-ceramics cannot be fully demonstrated. If the B value is too high, undesirable crystalline phases such as β-quartz are likely to occur, and the proportion of petalite crystalline phase is high, which facilitates grain growth, resulting in the proportion of microcrystallines becoming translucent or devitrified. Thus, by controlling the B value within the above range, the superior performance of the glass-ceramics can be fully demonstrated and the proportion of microcrystallines in the glass-ceramics can be prevented from becoming translucent or devitrified.

[0074] The relationship between each component of the crystallized glass satisfies 0.06≦[W(ZrO2)-3×W(B2O3)] / W(P2O5)≦1.57. It is expressed as C2=[W(ZrO2)-3×W(B2O3)] / W(P2O5), where W represents the mass percentage of the component relative to the total mass of all components. By controlling the C2 value within the above range, the activation energy of the liquid-liquid surface is reduced, causing phase separation and enabling nucleation and crystallization at low temperatures. The development of a phase interface due to crystallization and unstable decomposition of the liquid phase is realized, lowering the activation energy or energy barrier for nucleation and lowering the nucleation temperature and crystallization temperature. The two crystalline phases compete for silicon and lithium sources, i.e., destroy the crystalline phase structure already formed by the other crystalline phase and use it to form their own crystalline phase. The crystalline phase amounts of the formed petalite and lithium disilicate are similar, and the crystallite size is uniform and less than 100 nm, meeting the basic requirement of optical visibility. If the C2 value is too high or too low, the amount of single crystalline phase will increase and it will be easy to grow, which will reduce the visible light transmittance of the microcrystals and increase haze.

[0075] In one embodiment, the components of the glass composition preferably satisfy the following conditions: 72-74% SiO2, 7.5-8.4% Al2O3, 2-2.8% P2O5, 0.3-0.8% B2O3, 10.5-11.8% Li2O, 0.5-1.3% Na2O, and 3.4-4.7% ZrO2, which further optimizes the performance of the glass-ceramics obtained from the glass composition.

[0076] With regard to the blending ratio of each component of the glass composition, it is more preferable that the relationships between each component of the crystallized glass satisfy 0.6≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦5.4, 0.28≦[W(Li2O)−W(Al2O3)] / [W(P2O5)+W(ZrO2)]≦0.8, and 0.5≦[W(ZrO2)−3×W(B2O3)] / W(P2O5)≦1.36.

[0077] In one embodiment, the components of the glass composition satisfy the following conditions: 72.5-73.5% SiO2, 7.7-8% Al2O3, 2.1-2.5% P2O5, 0.5-0.7% B2O3, 11-11.5% Li2O, 0.7-1.1% Na2O, and 3.8-4.4% ZrO2, thereby improving the performance of the crystallized glass obtained from the glass composition.

[0078] With regard to the blending ratio of each component of the glass composition, it is more preferable that the ratios between each component of the crystallized glass satisfy 2.5≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦4.3, 0.43≦[W(Li2O)−W(Al2O3)] / [W(P2O5)+W(ZrO2)]≦0.64, and 0.81≦[W(ZrO2)−3×W(B2O3)] / W(P2O5)≦1.16.

[0079] In one embodiment, the components of the glass composition preferably satisfy the following conditions: 72-73.5% SiO2, 6.8-8.2% Al2O3, 2-2.4% P2O5, 0.4-1.1% B2O3, 10.8-11.7% Li2O, 0.4-1.7% Na2O, 0.3-1% CaO, and 3.3-4.4% ZrO2, which further optimizes the performance of the glass-ceramics obtained from the glass composition.

[0080] In one embodiment, the components of the glass composition include SiO2, Al2O3, P2O5, BO3, Li2O, Na2O, CaO, and ZrO2, and the relationship between the components of the glass composition satisfies 2.3≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦10.3. A=W(SiO2)−6×W(Al2O3)−2×W(Li2O), where W represents the mass percent of the component, and the A value is the molecular weight value calculated by the formula. When the A value is low, all of the SiO2 enters the crystalline phase. In contrast, there is an excess of Al2O3 or Li2O, resulting in a high proportion of petalite crystalline phase formation, which facilitates grain growth and results in a low proportion of microcrystalline crystals, leading to translucency or devitrification. When the A value is too high, all of the Al2O3 or Li2O enters the crystalline phase, and the remaining SiO2 exists as a network framework in the glass phase, resulting in a low total crystalline phase content in the crystallized glass. By controlling the A value within the above range, the proportion of microcrystals in the crystallized glass can be prevented from becoming translucent or devitrifying, and the total crystalline phase content of the crystallized glass can be effectively improved. In one embodiment, it is preferable that 2.7≦W(SiO2)−6×W(Al2O3)−2×W(Li2O)≦7.8.

[0081] The relationship between the components of the glass composition satisfies 0.27≦[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)]≦0.87. The formula is B=[W(LiO)−W(AlO)] / [W(PO)+W(ZrO)], where W represents the mass percent of the component. If the B value is too low, the proportion of the glass phase in the crystallized glass increases, preventing the crystallized glass from fully demonstrating its superior performance. If the B value is too high, undesirable crystalline phases such as β-quartz are likely to form, and the proportion of petalite crystal phase is high, resulting in the growth of crystal grains, leading to the crystallite fraction becoming translucent or devitrified. Thus, by controlling the B value within the above range, the crystallized glass can fully demonstrate its superior performance and prevent the crystallite fraction becoming translucent or devitrified. In one embodiment, it is preferred that 0.46≦[W(Li2O)−W(Al2O3)] / [W(P2O5)+W(ZrO2)]≦0.77.

[0082] The relationship between the components of the glass composition satisfies 2≦[W(ZrO2)−W(CaO)] / [W(P2O5)−W(B2O3)]≦3.22. The formula C3 is expressed as [W(ZrO2)−W(CaO)] / [W(P2O5)−W(B2O3)], where W represents the mass percent of the component. Controlling the C3 value within the above range reduces the activation energy at the liquid-liquid surface, allowing phase separation and nucleation and crystallization at low temperatures. The resulting crystalline phases of petalite and lithium disilicate are close in amount, with uniform crystallite sizes of less than 100 nm, meeting the basic requirements for optical visibility. On the other hand, it stabilizes the glass crystal structure, inhibits lithium ion migration, especially during chemical strengthening, and improves the crystal content of the glass-ceramics after chemical strengthening. A high or low C3 value can also affect the microcrystalline visible light transmittance, b value, and haze. In one embodiment, it is preferred that 2.06≦[W(ZrO2)−W(CaO)] / [W(P2O5)−W(B2O3)]≦2.31.

[0083] In the embodiment of the present application, there is further provided a crystallized glass comprising the glass composition as described above. The crystallized glass comprises all the technical features of the glass composition as described above, and therefore has all the technical effects of the glass composition as described above, and therefore will not be described one by one here.

[0084] In one embodiment, the thickness of the crystallized glass is 0.3 to 1.5 mm. The thinner the thickness of the crystallized glass, the lighter the crystallized glass can be.

[0085] In one embodiment, the crystalline phase of the glass-ceramics is mainly lithium disilicate and petalite, the total content of the crystalline phase of the glass-ceramics is 60%-90%, the content of the lithium disilicate is greater than 30%, and the content of the petalite is greater than 30%.By ensuring that the lithium disilicate and petalite are within this range, the crystalline phase content of the glass-ceramics is increased and the ratio of the two crystalline phases is well balanced, so that the strengthening performance of the glass-ceramics is improved.

[0086] In one embodiment, the thickness of the crystallized glass is 0.3 to 1.5 mm. The thinner the thickness of the crystallized glass, the lighter the crystallized glass can be.

[0087] In an embodiment of the present application, there is further provided a crystallized glass containing the glass composition as described above, wherein the crystallized glass contains a crystalline phase Li2Si2O5 and a crystalline phase LiAlSi4O 10 The glass-ceramics includes all the technical features of the above glass composition, and therefore has all the technical effects of the above glass composition, and therefore will not be described here one by one.

[0088] The crystallized glass has a W(Li2Si2O5) / W(LiAlSi4O 10 )≦1.06. E=W(Li2Si2O5) / W(LiAlSi4O 10 ), where W represents the mass percent of the crystalline phase in question relative to the glass-ceramics. By controlling the E value within the above range, it is ensured that the amounts of the formed petalite and lithium disilicate crystalline phases are similar, further improving the performance of the glass-ceramics. 0.97≦W(Li2Si2O5) / W(LiAlSiO 10 )≦1.03 is more preferred.

[0089] The glass-ceramics must also satisfy 10.44≦M≦12.54, where M=1.3×[W(Li2Si2O5) / W(LiAlSi4O 10)] × {0.86 × [W(SiO2)-6 × W(Al2O3)-2 × W(Li2O)] + 1.83 × [(W(Li2O)-W(Al2O3)) / (W(P2O5) + W(ZrO2))] + 1.67 × [W(ZrO2) / W(P2O5)] + 0.25 × [(W(SiO2)-6 × W(Al2O3)-2 × W(Li2O)) / W(Na2O)]}. Research has shown that M has a linear relationship with the fracture toughness (KIC) of glass-ceramics. Based on this linear relationship, controlling the M value within the above range can help improve the fracture toughness of glass-ceramics, as shown in Figure 3. It is more preferable that 11.85≦M≦12.54.

[0090] In one embodiment, the thickness of the crystallized glass is 0.3 to 1.5 mm. The thinner the thickness of the crystallized glass, the lighter the crystallized glass can be.

[0091] Furthermore, the present application further provides a method for producing the above-mentioned crystallized glass, which includes steps S10 to S30 as shown in FIG.

[0092] In S10, the glass composition as described above is weighed.

[0093] In S20, the glass composition is mixed and melted, then refined, homogenized, formed, annealed, and finally cut to obtain a base glass.

[0094] Specifically, in step S20, the forming method includes float forming, overflow forming, calendar forming or slot downdraw forming. Other processes such as fining, homogenization, annealing and cutting are common processes in the field of glass technology, and detailed description is omitted here. After the above processes are obtained, the thickness of the obtained base glass is 0.3 to 1.5 mm.

[0095] In S30, the base glass is heat-treated to obtain crystallized glass.

[0096] Specifically, step S30 includes heating the base glass from room temperature to 510-540°C in 20-60 minutes, performing a first nucleation treatment for 3-8 hours, heating it to 580-610°C in 5-30 minutes, performing a second nucleation treatment for 3-8 hours, heating it to 650-680°C in 5-30 minutes, performing a crystallization treatment for 3-8 hours, and cooling it to room temperature to obtain crystallized glass.

[0097] In one embodiment, as shown in FIG. 2, after step S30, The method includes a step S40 in which the pre-treated glass-ceramics is placed in an ion exchange bath for salt bath treatment to obtain chemically strengthened glass-ceramics, where the ion exchange bath contains 20-40% NaNO3 and 60-80% KNO3 by mass, the salt bath strengthening temperature is 420-500°C, and the salt bath strengthening time is 3-8 hours.

[0098] Due to the high content of crystals in the crystallized glass, there is a structural difference between the glass phase and the crystal phase, forming structural cavities. When using molten salt containing >40 wt% NaNO3, NaNO3 is released within a short time during ion exchange. + / Li + can reach deep ion depths, but Na + tends to aggregate in the cavities of the microcrystalline phase and the glass phase, making it difficult to form compressive stress. + / Li + If the exchange rate is too fast, the difference between the glass phase and the microcrystalline phase will become larger over time, which is likely to cause an increase in the b value.

[0099] When the above strengthening system is adopted, Na in the crystalline phase + / Li + The exchange rate of Na can be slowed down, and the Na in the cavities of the microcrystalline and glassy phases can be prevented. +This is beneficial to reducing the aggregation of glass, effectively forming compressive stress, reducing the glass phase and exchange rate, reducing the difference between the glass phase and the crystalline phase, and further reducing the b value of the glass.

[0100] In step S40, the pretreatment step specifically includes keeping the crystallized glass at 300 to 330°C for 5 to 20 minutes. A detailed description of the general means in the technical field for pretreating the glass will be omitted here.

[0101] The present application further provides an electronic display terminal including the above-mentioned crystallized glass, the specific characteristics of which can be referred to in the above-mentioned embodiments, and since this electronic display terminal employs all the technical solutions of all the above-mentioned embodiments, it has at least all the beneficial effects of the technical solutions of the above-mentioned embodiments, and will not be described one by one here. Here, the crystallized glass is used as a protective glass or protective member of the electronic display terminal, or the crystallized glass is used as a protective glass of a smart terminal, or the crystallized glass is used as a protective glass of a solar cell. [Example]

[0102] The technical solution of the present application will be described in more detail below with reference to specific examples and drawings. It should be understood that the following examples are only for the purpose of interpreting the present application and are not intended to limit the present application.

[0103] (Example) (1) A glass composition was weighed and contained, by mass%, 72% SiO, 37% AlO, 53% PO, 12.5% ​​LiO, 2% NaO, and 3.5% ZrO.

[0104] (2) The glass composition was mixed and melted, then refined, homogenized, formed, annealed, and finally cut to obtain a base glass.

[0105] (3) The base glass was heated from room temperature to 530°C in 20 minutes, subjected to nucleation treatment for 3 hours, heated to 680°C in 30 minutes, subjected to crystallization treatment for 3 hours, and cooled to room temperature to obtain crystallized glass.

[0106] (4) An ion exchange bath containing 40% NaNO3 and 60% KNO3 by mass was prepared, and the crystallized glass was pretreated and then placed in the ion exchange bath for a salt bath treatment to obtain chemically strengthened crystallized glass. The salt bath strengthening temperature was 420°C, and the salt bath strengthening time was 3 hours.

[0107] The raw materials were weighed according to the glass composition component blending ratios of each example shown in Tables I1 and I2, and the other crystallized glasses and chemically strengthened crystallized glasses of Examples A2 to A14 were manufactured by referring to the manufacturing method of Example A1.

[0108] The raw materials were weighed according to the glass composition component blending ratios of Comparative Examples A1 to A5 shown in Table I3, and the crystallized glasses and chemically strengthened crystallized glasses of Comparative Examples A1 to A5 were manufactured by referring to the manufacturing method of Example A1.

[0109] The glass compositions of Examples A8 and A14 were subjected to steps (1) to (3) of the manufacturing method in Example A1 to manufacture crystallized glass. For specific process parameters during manufacturing, see Table I4.

[0110] The glass compositions of Examples A8 and A14 were subjected to steps (1) to (4) of the manufacturing method in Example A1 to produce chemically strengthened crystallized glass. The specific process parameters for manufacturing step (4) refer to Table I5, and the remaining steps (1) to (3) were the same as those of Example A1.

[0111] (Test example) The test method and test equipment are as follows:

[0112] The main crystalline phase was tested by X-ray diffraction analyzer.

[0113] The crystal appearance and morphology were observed using a scanning electron microscope.

[0114] Color b-values ​​were tested using a Datacolor 650 ultra-high precision desktop spectrophotometer.

[0115] Visible light transmittance tests were performed using a spectrophotometer according to standard ISO 13468-1:1996.

[0116] The haze of the glass was measured according to the ASTM D1003-92 test.

[0117] Glass fracture toughness KIC was measured in accordance with ASTM E-1820 and is expressed in MPa m 1 / 2 is.

[0118] The drop performance of the whole machine sandpaper is measured by a mobile phone control drop tester. The specific test conditions are: 180 mesh sandpaper, a total weight of 195g, a base height of 60cm, an increase of 5cm, one time for each height, until it breaks.

[0119] According to the test methods and test equipment of the test examples, the performance of the crystallized glass and chemically strengthened crystallized glass obtained in Examples B1 to B14, the crystallized glass and chemically strengthened crystallized glass obtained in Comparative Examples A1 to A5, the crystallized glass manufactured according to the process parameters in Table I4, and the chemically strengthened crystallized glass manufactured according to the process parameters in Table I5 was tested respectively, and the results were entered into the corresponding tables.

[0120] It should be understood that the above test methods and test equipment are methods commonly used in the art to evaluate the relevant performance of glass, and are merely one of the means for characterizing or evaluating the technical solutions and technical effects of the present application, and other test methods and test equipment may be adopted without affecting the final results.

[0121] [Table 1.1]

[0122] [Table 1.2]

[0123] [Table 1.3]

[0124] [Table 1.4]

[0125] Here, the time in the nucleation treatment and the crystallization treatment represents the time required for the temperature to rise, the temperature represents the target temperature to which the temperature is to be raised, and the time represents the treatment time.

[0126] [Table 1.5]

[0127] As can be seen from the test results of the performance of the glass-ceramics of each example shown in Tables I1, I2, I4 and I5, in Examples A1 to A14 using the technical solution of the present application, the glass-ceramics obtained after heat treatment contained crystalline phase lithium disilicate Li2Si2O5>30%, crystalline phase petalite LiAlSiO4>30%, and crystalline phase LiAlSiO5>30%. 10 The glass-ceramics had a 0.7 mm transmittance of >91%, a haze of <0.17, and a b-value of <0.4. The average crystallite size of the glass-ceramics was <100 nm. The glass-ceramics had a fracture toughness KIC of >1.1 MPa m 1 / 2 , the drop resistance height was >200cm.

[0128] As can be seen from Table I3, in Comparative Example A1, SiO2 = 71.5%, A = 0.5, and D = 0.42. This does not meet the requirements of the glass composition of the present application, and the heat-treated glass-ceramics is Li2Si2O5 / LiAlSi4O 10= 0.81, crystal size > 100 nm, transmittance was low, b value was too large, haze was large, and mechanical properties after chemical strengthening were poor.

[0129] In Comparative Example A2, A=8 and D=6.67. This does not meet the requirements of the glass composition of the present application, and the content of the microcrystalline phase in the heat-treated glass-ceramics is low, resulting in a Li2Si2O5 / LiAlSi4O 10 =0.6, and the mechanical properties after chemical strengthening were poor.

[0130] In Comparative Example A3, Li2O=10% and B=0.2, which does not meet the requirements of the glass composition of the present invention, the content of the microcrystalline phase in the heat-treated glass-ceramics was low, and the Li2Si2O5 / LiAlSi4O 10 = 0.74, crystal size > 100 nm, transmittance was low, b value was too large, haze was large, and mechanical properties after chemical strengthening were poor.

[0131] In Comparative Example A4, P2O5=1.7%, A=2.1, C1=2.82, and D=2.33. This does not meet the requirements of the glass composition of the present application, and the content of the microcrystalline phase in the heat-treated glass-ceramics is low, resulting in a Li2Si2O5 / LiAlSi4O 10 = 0.55, crystal size > 100 nm, transmittance was low, b value was too large, haze was large, and mechanical properties after chemical strengthening were poor.

[0132] In Comparative Example A5, P2O5=3.8%, A=2.7, C1=0.97, and D=2.45. This does not meet the requirements of the glass composition of the present application, and the content of the microcrystalline phase in the heat-treated glass-ceramics is low, resulting in a Li2Si2O5 / LiAlSi4O 10 = 1.7, crystal size > 100 nm, transmittance was low, b value was too large, haze was large, and mechanical properties after chemical strengthening were poor.

[0133] The fracture toughness KIC value (1.012 to 1.78 MPa m) of the chemically strengthened glass-ceramics in the examples of this application 1 / 2 ) is the fracture toughness KIC value (0.43 to 0.72 MPa m) of the chemically strengthened glass-ceramics in the comparative example.1 / 2 ), which explains that the reduction in crystalline content and the destruction of the interlocking structure of the twin phase that occur in the glass-ceramics of the examples of the present application during the chemical strengthening process are significantly improved; it is clear that the b value and haze of the glass-ceramics of the examples of the present application are lower than the high b value and high haze of the glass-ceramics of the comparative examples, which explains why the glass-ceramics of the examples of the present application achieve a reduction in b value and haze. Finally, the obtained chemically strengthened glass-ceramics has excellent strengthening performance.

[0134] (Example) (1) A glass composition was weighed and contained, in mass%, 71.5% SiO, 38.7% AlO, 53% PO, 0.1% BO, 10.2% LiO, 1.5% NaO, and 25% ZrO, with A=-1.1, B=0.19, and C=1.57.

[0135] (2) The glass composition was mixed and melted, then refined, homogenized, formed, annealed, and finally cut to obtain a base glass.

[0136] (3) The base glass was heated from room temperature to 510°C in 20 minutes, subjected to a first nucleation treatment for 3 hours, heated to 580°C in 5 minutes, subjected to a second nucleation treatment for 3 hours, heated to 650°C in 30 minutes, subjected to a crystallization treatment for 3 hours, and cooled to room temperature to obtain crystallized glass.

[0137] (4) After pre-treating the crystallized glass, it was placed in an ion exchange bath and subjected to a salt bath treatment to obtain chemically strengthened crystallized glass. The ion exchange bath contained, by mass %, 20% NaNO3 and 80% KNO3, the salt bath strengthening temperature was 420°C, and the salt bath strengthening time was 3 hours.

[0138] The raw materials were weighed according to the glass composition component blending ratios of each example shown in Tables II1 and II2, and the crystallized glasses and chemically strengthened crystallized glasses of Examples B2 to B15 were manufactured by referring to the manufacturing method of Example B1.

[0139] Raw materials were weighed according to the blending ratios of glass composition components of Comparative Examples B1 to B7 shown in Table II3, and the crystallized glasses and chemically strengthened crystallized glasses of Comparative Examples B1 to B7 were produced in accordance with the production method of Example B1.

[0140] The glass compositions of Examples B1 and B9 were subjected to steps (1) to (3) of the manufacturing method in Example B1 to manufacture crystallized glass. For specific process parameters during manufacturing, see Table II4.

[0141] (Test example) The test method and test equipment are as follows:

[0142] The main crystalline phase was tested by X-ray diffraction analyzer.

[0143] The crystal appearance and morphology were observed using a scanning electron microscope.

[0144] Color b-values ​​were tested using a Datacolor 650 ultra-high precision desktop spectrophotometer.

[0145] Visible light transmittance tests were performed using a spectrophotometer according to standard ISO 13468-1:1996.

[0146] The haze of the glass was measured according to the ASTM D1003-92 test.

[0147] The drop performance of the whole machine sandpaper was measured by a mobile phone control drop tester. The specific test conditions were: 180 mesh sandpaper, a total weight of 195g, a base height of 60cm, and an increase of 5cm, one drop per height, until it broke.

[0148] According to the test methods and test equipment of the test examples, the performance of the crystallized glass and chemically strengthened crystallized glass obtained in Examples B1 to B15, the crystallized glass and chemically strengthened crystallized glass obtained in Comparative Examples B1 to B7, and the crystallized glass produced according to the process parameters in Table II4 was tested respectively, and the results were recorded in the corresponding tables.

[0149] It should be understood that the above test methods and test equipment are methods commonly used in the art to evaluate the relevant performance of glass, and are merely one of the means for characterizing or evaluating the technical solutions and technical effects of the present application, and other test methods and test equipment may be adopted without affecting the final results.

[0150] [Table 2.1]

[0151] [Table 2.2]

[0152] [Table 2.3]

[0153] [Table 2.4]

[0154] Here, the time in the first nucleation treatment, the second nucleation treatment and the crystallization treatment indicates the time required for temperature increase, the temperature indicates the target temperature for temperature increase, and the time indicates the treatment time.

[0155] As can be seen from the test results of the glass performance of each example shown in Table II1, Table II2 and Table II4, in Examples B1 to B15 using the technical solution of the present application, lithium disilicate Li2Si2O5 accounts for 30% to 45% in the glass-ceramics, and petalite LiAlSi4O 10 The total crystalline phase accounts for 30% to 45% of the glass-ceramics, and the total crystalline phase accounts for 60% to 90% of the glass-ceramics. The crystallite size is uniform, with an average crystallite size of <100 nm. At a wavelength of 560 nm, the 0.7 mm glass-ceramics have a transmittance of >91%, a haze of <0.17, a b value of <0.5, and a drop resistance of >200 cm.

[0156] As can be seen from Table II3, in Comparative Example 1, B2O3 = 0% and C2 = 1.58. The heat-treated glass-ceramics did not meet the requirements of the glass composition of the present application, and had a low microcrystalline phase content, a crystallite size of > 100 nm, low transmittance, an excessively large b value, and high haze.

[0157] In Comparative Example B2, B2O3=1.1%, but C2=-0.22. The heat-treated crystallized glass did not meet the requirements of the glass composition of the present application, and had a low microcrystalline phase content, a crystallite size of >100 nm, low transmittance, an excessively large b value, high haze, and poor drop resistance.

[0158] In Comparative Example B3, Al2O3=9.5%, A=-4.8, and B=0.08. The heat-treated crystallized glass did not meet the requirements of the glass composition of the present application, and had a low microcrystalline phase content, a crystal size of >100 nm, low transmittance, an excessively large b value, high haze, and poor drop resistance.

[0159] In Comparative Example B4, SiO2=74.7% and A=12.1, which did not meet the requirements of the glass composition of the present invention, the content of the microcrystalline phase in the heat-treated crystallized glass was low, and the drop resistance was poor.

[0160] In Comparative Example B5, Li2O=13% and B=1.08. The heat-treated glass-ceramics did not meet the requirements of the glass composition of the present application, and had a low microcrystalline phase content, a crystallite size of >100 nm, low transmittance, an excessively large b value, and high haze.

[0161] Comparative Example B6 had Al2O3 = 9% and B = -0.06, which did not meet the requirements of the glass composition of the present invention, and the content of the microcrystalline phase in the heat-treated crystallized glass was low, resulting in poor drop resistance.

[0162] In Comparative Example B7, the glass components were within the requirements of the present application, but C2=1.91, which did not meet the requirements of the glass composition of the present application. The heat-treated crystallized glass had a low microcrystalline phase content, a crystallite size of >100 nm, low transmittance, an excessively large b value, and high haze.

[0163] The b value of the crystallized glass in the examples of the present application is significantly smaller than the b value and haze of the crystallized glass in the comparative examples, and the haze is significantly reduced. This demonstrates that the examples of the present application can effectively solve the problem of currently produced transparent crystallized glass having a large b value and high haze, and the obtained crystallized glass has excellent strengthening performance.

[0164] (Example) (1) A glass composition was weighed and contained, in mass%, 71.5% SiO, 6.2% AlO, 51.7% PO, 0.1% BO, 12% LiO, 2% NaO, 1.5% CaO, and 5% ZrO, with A=10.3, B=0.87, and C=2.19.

[0165] (2) The glass composition was mixed and melted, then refined, homogenized, formed, annealed, and finally cut to obtain a base glass.

[0166] (3) The base glass was heated from room temperature to 510°C in 20 minutes, subjected to a first nucleation treatment for 3 hours, heated to 580°C in 5 minutes, subjected to a second nucleation treatment for 3 hours, heated to 650°C in 30 minutes, subjected to a crystallization treatment for 3 hours, and cooled to room temperature to obtain crystallized glass.

[0167] (4) After pre-treating the crystallized glass, it was placed in an ion exchange bath and subjected to a salt bath treatment to obtain chemically strengthened crystallized glass. The ion exchange bath contained, by mass %, 40% NaNO3 and 60% KNO3, the salt bath strengthening temperature was 500°C, and the salt bath strengthening time was 8 hours.

[0168] The raw materials were weighed according to the glass composition component blending ratios of each example shown in Tables III1 and III2, and the crystallized glasses and chemically strengthened crystallized glasses of Examples C2 to C16 were manufactured by referring to the manufacturing method of Example C1.

[0169] Raw materials were weighed according to the blending ratios of glass composition components of Comparative Examples C1 to C6 shown in Table III3, and the crystallized glasses and chemically strengthened crystallized glasses of Comparative Examples C1 to C6 were manufactured according to the manufacturing method of Example C1.

[0170] The glass compositions of Examples C1 and C8 were subjected to steps (1) to (3) of the manufacturing method of Example C1 to manufacture crystallized glass. See Table III4 for specific process parameters during manufacturing.

[0171] The glass compositions of Examples C1 and C8 were subjected to steps (1) to (4) of the manufacturing method in Example C1 to produce chemically strengthened crystallized glass. The specific process parameters for step (4) during manufacturing are shown in Table III5, and the remaining steps (1) to (3) were the same as those of Example C1.

[0172] (Test example) The test method and test equipment are as follows:

[0173] The main crystalline phase was tested by X-ray diffraction analyzer.

[0174] The crystal appearance and morphology were observed using a scanning electron microscope.

[0175] Color b-values ​​were tested using a Datacolor 650 ultra-high precision desktop spectrophotometer.

[0176] Visible light transmittance tests were performed using a spectrophotometer according to standard ISO 13468-1:1996.

[0177] The haze of the glass was measured according to the ASTM D1003-92 test.

[0178] The drop performance of the whole machine sandpaper was measured by a mobile phone control drop tester. The specific test conditions were: 180 mesh sandpaper, a total weight of 195g, a base height of 60cm, and an increase of 5cm, one drop per height, until it broke.

[0179] According to the test methods and test equipment of the test examples, the performance of the crystallized glass and chemically strengthened crystallized glass obtained in Examples C1 to C16, the crystallized glass and chemically strengthened crystallized glass obtained in Comparative Examples C1 to C6, the crystallized glass manufactured according to the process parameters in Table III4, and the chemically strengthened crystallized glass manufactured according to the process parameters in Table III5 were tested respectively, and the results were entered into the corresponding tables.

[0180] It should be understood that the above test methods and test equipment are methods commonly used in the art to evaluate the relevant performance of glass, and are merely one of the means for characterizing or evaluating the technical solutions and technical effects of the present application, and other test methods and test equipment may be adopted without affecting the final results.

[0181] [Table 3.1]

[0182] [Table 3.2]

[0183] [Table 3.3]

[0184] [Table 3.4]

[0185] Here, the time in the first nucleation treatment, the second nucleation treatment and the crystallization treatment indicates the time required for temperature increase, the temperature indicates the target temperature for temperature increase, and the time indicates the treatment time.

[0186] [Table 3.5]

[0187] As can be seen from the test results of the glass performance of each example shown in Tables III1, III2, III4 and III5, in Examples C1 to C16 using the technical solution of the present application, the chemically strengthened glass-ceramics contained lithium disilicate Li2Si2O5>30%, petalite LiAlSiO4>30%, and 10 The total content of crystalline phases in the crystallized glass and the total content of crystalline phases in the chemically strengthened crystallized glass were both 60% to 90%, the average crystal size of the crystal grains in the crystallized glass was <100 nm, the crystallized glass had a 0.7 mm visible light transmittance of >91%, and a drop resistance of >200 cm.

[0188] As can be seen from Table III3, in Comparative Example C1, Al2O3 = 9%, A = -4, and C3 = 1. The heat-treated glass-ceramics did not meet the requirements of the glass composition of the present application, and had a low microcrystalline phase content, a crystallite size > 100 nm, low transmittance, an excessively large b value, and high haze.

[0189] In Comparative Example C2, Al2O3=5.5%, A=18.5, and C3=1.2. This did not meet the requirements of the glass composition of the present invention, and the content of the microcrystalline phase in the heat-treated crystallized glass was low, resulting in relatively poor drop resistance.

[0190] In Comparative Example C3, Li2O=12.5%, B=1.04, and C3=1.1. This did not meet the requirements of the glass composition of the present application, and the heat-treated crystallized glass crystal size was greater than 100 nm, and the transmittance was low, the b value was too large, and the haze was large.

[0191] In Comparative Example C4, Li2O=9%, B=0.15, and C3=1.22. This did not meet the requirements of the glass composition of the present application, and the glass-ceramics had a low crystalline phase content after tempering, resulting in relatively poor drop resistance.

[0192] Comparative Example C5 had CaO=1.6%, ZrO2=2.6%, and C3=0.43, which did not meet the requirements of the glass composition of the present application, and the heat-treated crystallized glass had a crystal size of >100 nm, low transmittance, too large b value, and high haze. After tempering, the crystallized glass had a low crystalline phase content and relatively poor drop resistance.

[0193] In Comparative Example C6, B2O3=0 and C3=1.64, which did not meet the requirements of the glass composition of the present application, the heat-treated crystallized glass had a crystal size of >100nm, low transmittance, too large b value, and high haze. After tempering, the crystallized glass had a low crystalline phase content and relatively poor drop resistance.

[0194] The reduction in the total content of the crystalline phase of the chemically strengthened glass-ceramics in the examples of the present application is smaller than the reduction in the total content of the crystalline phase of the chemically strengthened glass-ceramics in the comparative examples, which shows that the reduction in the crystalline content and the destruction of the twin phase c that occur in the glass-ceramics in the examples of the present application during the chemical strengthening process are significantly improved, and the obtained chemically strengthened glass-ceramics has excellent strengthening performance.

[0195] The above is only a preferred embodiment of the present application, and does not limit the patent scope of the present application, and various modifications and variations are possible for those skilled in the art. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the patent scope of the present application.

Claims

1. In mass%, 72.8 to 73.2% SiO ２ , 7.4-7.5% Al ２ O ３ , 2.4-2.6% P ２ O ５ , 11.5 to 11.7% Li ２ O, 1.3-1.4% Na ２ O, and 3.9 to 4.1% ZrO ２ Including, 5≦W(SiO) ２ )-6×W(All ２ Oh ３ )-2×W(LS ２ O)≦5.2、 0.61≦[W(L- ２ O)-W(AS ２ O ３ )] / [W (P ２ O ５ )+W(ZrO ２ )]≦0.66、 1.5≦W(ZrO ２ ) / W(P ２ O ５ )≦1.71、 3.57≦[W(SiO ２ ) -6 × W (Al ２ O ３ ) -2 × W(Li ２ O)] / W(Na ２ O)≦4.

2. A crystallized glass, 10. The glass composition according to claim 1, wherein the crystallized glass comprises a crystalline phase Li ２ Si ２ O ５ and crystalline phase LiAlSi ４ O １０ A crystallized glass containing

3. 0.91≦W(Li ２ Si ２ O ５ ) / W(LiAlSi ４ O １０ 3. The crystallized glass according to claim 2, wherein σ is 0.05 or less.

4. 0.97≦W(Li ２ Si ２ O ５ ) / W(LiAlSi ４ O １０ 4. The crystallized glass according to claim 3, wherein σ is 0.05 or less.

5. 10.44≦M≦12.54, Here, M = 1.3 × [W(Li ２ Si ２ O ５ ) / W(LiAlSi ４ O １０ )]×{0.86×[W(SiO ２ ) -6 × W (Al ２ O ３ ) -2 × W(Li ２ O)]+1.83×[(W(Li ２ O)-W(Al ２ O ３ )) / (W(P ２ O ５ ) + W(ZrO ２ ))]+1.67×[W(ZrO ２ ) / W(P ２ O ５ )]+0.25×[(W(SiO ２ ) -6 × W (Al ２ O ３ ) -2 × W(Li ２ O)) / W(Na ２ 4. The crystallized glass according to claim 3, wherein the formula is ##EQU1##

6. The crystallized glass according to claim 5, wherein 11.85≦M≦12.

54.

7. Weighing the glass composition of claim 1; mixing the glass composition, melting it, then fining, homogenizing, forming, annealing, and finally cutting it to obtain a base glass; and heat-treating the base glass to obtain crystallized glass.

8. The step of heat-treating the base glass to obtain crystallized glass includes: The base glass is heated from room temperature to 530 to 570 ° C. in 20 to 60 minutes, and a nucleation treatment is performed for 3 hours or more. The temperature is raised to 680 to 720 ° C. in 5 to 30 minutes, and crystallization treatment is carried out for 3 hours or more; and cooling the glass to room temperature to obtain the glass-ceramics.

9. After the step of heat-treating the base glass to obtain crystallized glass, the manufacturing method further comprises: Providing an ion exchange bath, the ion exchange bath comprising, by weight, 20 to 40% NaNO ３ and 60-80% KNO ３ and The method for producing crystallized glass according to claim 7, further comprising the steps of: pretreating the crystallized glass, then placing it in the ion exchange bath to carry out a salt bath treatment, thereby obtaining chemically strengthened crystallized glass, wherein the salt bath strengthening temperature is 420-500°C, and the salt bath strengthening time is 3-8 hours.

10. 8. The method for producing crystallized glass according to claim 7, wherein the steps of mixing the glass composition, melting it, then fining, homogenizing, forming, annealing, and finally cutting it to obtain a base glass include float forming, overflow forming, calendar forming, or slot downdraw forming.

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