Glass article and method of making the same, chemical strengthening method of lithium-containing microcrystalline glass, and strengthened lithium-containing microcrystalline glass

Abstract

The application discloses a kind of glass products and its preparation method, chemical strengthening method and strengthened lithium-containing microcrystalline glass of lithium-containing microcrystalline glass, belong to chemical strengthening field.The application is designed by the component of glass base composition, cooperate preparation process, obtain a kind of absorption function glass product to lithium ion, the glass product can be applied to the chemical strengthening process of lithium-containing microcrystalline glass, absorb lithium ion in fused salt, maintain the component stability of fused salt, prevent the chemical strengthening ion exchange process from being unstable due to lithium ion concentration is too high, solve the problem of pollution fused salt in the chemical strengthening ion exchange process, affect the service life of fused salt, improve the chemical strengthening effect of lithium-containing microcrystalline glass, in turn improve the performance of strengthened lithium-containing microcrystalline glass.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass chemical strengthening, in particular to a glass product and a preparation method thereof, a chemical strengthening method of lithium-containing microcrystalline glass and a strengthened lithium-containing microcrystalline glass. BACKGROUND

[0002] In the chemical strengthening process of the microcrystalline glass, with the increase of the amount of the strengthening material, the lithium ion concentration in the salt melt will increase accordingly, and the excessive lithium ion concentration will seriously weaken the sodium-lithium exchange degree, affecting the strengthening performance of the microcrystalline glass after chemical strengthening.

[0003] In the prior art, in order to ensure the chemical strengthening performance of the microcrystalline glass, the lithium ion concentration in the melt salt needs to be controlled. For example, when the lithium ion concentration in the melt salt Li + exceeds the critical value, the new melt salt is replaced, but this method will cause downtime, easily increase the cost and reduce the production efficiency. In addition, there is also a prior art which controls the lithium ion concentration in the melt salt by adding sodium phosphate into the melt salt to absorb the lithium ions, and the main principle is that the sodium phosphate will dissolve in the salt bath to generate phosphate, and the phosphate will form lithium phosphate precipitate with the lithium ions. However, because the lithium phosphate precipitate is formed after the sodium phosphate is added into the melt salt, it needs to be clarified for a long time before it can be used. At the same time, the lithium phosphate will make the salt bath turbid, which is easy to adhere to the surface of the strengthened glass and cause defects.

[0004] Therefore, a product is needed which can maintain the stable absorption of lithium ions for a long time in the chemical strengthening process of the microcrystalline glass, so as to stably control the lithium ion concentration in the chemical strengthening melt salt, and will not have other effects on the melt salt and the microcrystalline glass. SUMMARY

[0005] The main purpose of the present application is to provide a glass product and a preparation method thereof, a chemical strengthening method of lithium-containing microcrystalline glass and a strengthened lithium-containing microcrystalline glass, which can maintain the stable absorption of lithium ions for a long time, so as to stably control the lithium ion concentration in the chemical strengthening melt salt, and solve the technical problem that the increase of the lithium ion concentration in the melt salt during the chemical strengthening ion exchange process of the lithium-containing microcrystalline glass will cause the instability of the chemical strengthening process, easily affecting the chemical strengthening effect of the lithium-containing microcrystalline glass and then affecting the quality thereof.

[0006] To achieve the above-mentioned purpose, the present application provides a glass product, which comprises the following components in percentage by mass:

[0007] SiO2: 28% to 50%,

[0008] Al2O3: 20% to 35%,

[0009] B2O3: 1% to 6%,

[0010] Na2O: 15% to 30%,

[0011] K2O: 1% to 9%,

[0012] ZrO2: 0% to 5%,

[0013] wherein the components of the glass product satisfy 0.38≤(Al2O3-B2O3) / SiO2≤1.04, and / or, 1.7≤Na2O / K2O≤30.

[0014] In some embodiments of the present application, the glass product comprises the following components in mass percentage:

[0015] SiO2: 33% to 47%,

[0016] Al2O3: 22% to 32%,

[0017] B2O3: 2% to 5%,

[0018] Na2O: 17% to 27%,

[0019] K2O: 2% to 8%,

[0020] ZrO2: 1% to 4%.

[0021] In some embodiments of the present application, the components of the glass product satisfy 0.43≤(Al2O3-B2O3) / SiO2≤0.82;

[0022] and / or, the components of the glass product satisfy 2.1≤Na2O / K2O≤13.5.

[0023] In some embodiments of the present application, the shape of the glass product comprises granular and / or sheet.

[0024] In some embodiments of the present application, the shape of the glass product is granular, and the particle size of the glass product in the granular shape ranges from 0.2mm to 2mm;

[0025] and / or, the shape of the glass product is sheet, and the size of the glass product in the sheet shape is ≥1mm×1mm, and the thickness is 0.2mm to 2mm.

[0026] In some embodiments of the present application, the glass product can absorb lithium ions, and the lithium ion absorption efficiency of the glass product is (2-6.8)×10 -2 , the lithium ion absorption efficiency is the ratio of the mass of lithium ions absorbed by the glass product to the mass of the glass product.

[0027] To achieve the above-mentioned purpose, the present application further provides a preparation method of the glass product as described above, comprising the following steps:

[0028] Weighing the component raw materials of the glass product, melting, cooling to obtain a preliminary shaped glass;

[0029] Rapidly cooling the preliminary shaped glass to obtain the glass product, which is in the form of particles and / or sheets.

[0030] In some embodiments of the present application, the melting temperature is 1400-1600℃;

[0031] And / or, the cooling temperature is 1150-1300℃.

[0032] In some embodiments of the present application, in the step of rapidly cooling the preliminary shaped glass to obtain the glass product, the preliminary shaped glass is subjected to water-cooled mechanical shaping to form sheet glass and / or water quenching to form particle glass under the condition of 0-50℃ to obtain the glass product.

[0033] In some embodiments of the present application, the glass product is also subjected to drying treatment, and the temperature of the drying is 80-150℃.

[0034] To achieve the above-mentioned purpose, the present application further provides a chemical strengthening method of lithium-containing microcrystalline glass, comprising the following steps:

[0035] The glass product and the lithium-containing microcrystalline glass as described above are simultaneously placed in molten salt for chemical strengthening to obtain strengthened lithium-containing microcrystalline glass.

[0036] In some embodiments of the present application, the lithium-containing microcrystalline glass contains the following components in terms of mass percentage:

[0037] SiO2: 70-75%,

[0038] Al2O3: 5-12%,

[0039] Li2O: 9-13%,

[0040] P2O5: 1.5-5%,

[0041] Na2O: 0.1-5%,

[0042] ZrO2: 2-7%,

[0043] B2O3: 0.1-5%.

[0044] In some embodiments of the present application, the molten salt contains NaNO3 with a mass concentration of 10-40% and KNO3 with a mass concentration of 60-90%.

[0045] In some embodiments of the present application, the molten salt contains LiNO3, and the LiNO3 maintains a mass concentration in the molten salt ranging from 0.02% to 0.15%.

[0046] In some embodiments of the present application, the glass product and the lithium-containing microcrystalline glass are heated and held at a temperature ranging from 350°C to 400°C before being chemically strengthened.

[0047] In some embodiments of the present application, the glass product and the lithium-containing microcrystalline glass are heated and held for a time ranging from 30 min to 90 min before being chemically strengthened.

[0048] In some embodiments of the present application, the chemical strengthening is performed at a temperature ranging from 450°C to 510°C for a time ranging from 4 h to 8 h.

[0049] In some embodiments of the present application, the glass product is added in an amount ranging from 200 g / m 2 to 700 g / m 2 per unit area of the lithium-containing microcrystalline glass.

[0050] To achieve the above object, the present application further provides a strengthened lithium-containing microcrystalline glass prepared by the chemical strengthening method of the lithium-containing microcrystalline glass.

[0051] In some embodiments of the present application, the strengthened lithium-containing microcrystalline glass has a CS-30≥100 MPa.

[0052] In some embodiments of the present application, the strengthened lithium-containing microcrystalline glass has a strengthening depth DOL≥100 μm.

[0053] The present application can achieve the following beneficial effects:

[0054] The present application designs the components of a glass base composition, and combines a preparation process to obtain a glass product having an absorption function for lithium ions. The glass product can be applied to a chemical strengthening process of a lithium-containing microcrystalline glass, stably absorbs lithium ions in a molten salt for a long time, maintains the composition of the molten salt stable, prevents the chemical strengthening ion exchange process from being unstable due to a too high concentration of lithium ions, solves the problem of contaminating the molten salt and affecting the service life of the molten salt during the chemical strengthening ion exchange process, and improves the chemical strengthening effect of the lithium-containing microcrystalline glass, thereby improving the performance of the strengthened lithium-containing microcrystalline glass.

[0055] The glass product of the present application has a loose network structure, which can further increase the voids of the glass, is beneficial to accelerate the ion exchange speed and the depth of ion exchange, is suitable for the stable absorption of a large number of lithium ions generated in the long-time chemical strengthening process of the lithium-containing glass ceramic, and can also help the glass product to maintain good structural stability in the high-temperature molten salt chemical strengthening process, thereby prolonging the service life of the glass product. BRIEF DESCRIPTION OF DRAWINGS

[0056] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description are briefly introduced as follows. Obviously, the drawings in the following description only represent some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative effort on the basis of the drawings shown.

[0057] Figure 1 The flowchart of preparing the glass product of an embodiment of the present application is shown.

[0058] The implementation, functional features and advantages of the present application will be further described with reference to the embodiments and the drawings. DETAILED DESCRIPTION

[0059] It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0060] The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments only represent some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative effort fall within the scope of protection of the present application.

[0061] In the present application, the description such as "first", "second" and the like is only for the purpose of description, and cannot be understood as indicating or implying the relative importance of the indicated technical features or implicitly indicating the number of the indicated technical features. Therefore, the features limited by "first", "second" can explicitly or implicitly include at least one of the features. In addition, the technical solutions of various embodiments can be combined with each other, but it must be based on the fact that the technical solutions can be realized by those skilled in the art. When the combination of technical solutions appears contradictory or unachievable, it should be considered that the combination of technical solutions does not exist, and is not within the scope of protection claimed by the present application.

[0062] The present application provides a glass product, which comprises the following components in percentage by mass:

[0063] SiO2: 28% to 50%,

[0064] Al203: 20% to 35%,

[0065] B203: 1% to 6%,

[0066] Na20: 15% to 30%,

[0067] K20: 1% to 9%,

[0068] Zr02: 0% to 5%,

[0069] wherein the components of the glass article satisfy 0.38 ≤ (Al203 - B203) / Si02≤ 1.04, and / or, 1.7 ≤ Na20 / K20≤ 30.

[0070] In some embodiments, the glass article comprises, in mass percent:

[0071] Si02: 33% to 47%,

[0072] Al203: 22% to 32%,

[0073] B203: 2% to 5%,

[0074] Na20: 17% to 27%,

[0075] K20: 2% to 8%,

[0076] Zr02: 1% to 4%.

[0077] In some embodiments, the components of the glass article satisfy 0.43 ≤ (Al203 - B203) / Si02≤ 0.82.

[0078] In some embodiments, the components of the glass article satisfy 2.1 ≤ Na20 / K20≤ 13.5.

[0079] In the components of the glass article of the present invention:

[0080] SiO2 is a component constituting the glass framework, which can be used as the main body of the glass network structure. If the content of SiO2 is low, it is difficult to form glass, the strain point decreases, the expansion coefficient increases, and the glass stability is poor. Therefore, increasing the content of SiO2 can improve the mechanical strength of the glass, reduce the expansion coefficient, and improve the stability of the glass. However, too high content of SiO2 can increase the high-temperature viscosity of the glass, which is not conducive to the melting of the glass. Therefore, in order to balance the mechanical strength, expansion coefficient, stability and high-temperature viscosity of the glass, the content of SiO2 in the glass product of the present application is 28% to 50% by mass percentage, and is further preferably 33% to 47% by mass percentage. In some embodiments, the content of SiO2 in the glass product of the present application can be any one of 28%, 29%, 30%, 31%, 33%, 35%, 38%, 40%, 42%, 45%, 46%, 47%, 48%, 50%, etc. within the range of 28% to 50% by mass percentage.

[0081] The Al2O3 component in the glass product of the present application is used to improve the strength of the glass structure. Non-bridging oxygen forms aluminum oxygen tetrahedron with Al ions, and the volume of aluminum oxygen tetrahedron is larger than that of silicon oxygen tetrahedron, which can produce larger gaps in the glass structure, thereby facilitating ion exchange. However, too high content of Al2O3 is difficult to melt. Therefore, in consideration of the above factors, the content of Al2O3 in the glass product of the present application is 20% to 35% by mass percentage, and is further preferably 22% to 32% by mass percentage. In some embodiments, the content of Al2O3 in the glass product of the present application can be any one of 20%, 22%, 25%, 27%, 29%, 30%, 31%, 32%, 34%, 35%, etc. within the range of 20% to 35% by mass percentage.

[0082] B2O3 in the glass product of the present application can improve the glass network structure, reduce the high-temperature melting viscosity, and improve the melting characteristics of the glass. In some embodiments, the content of B2O3 in the glass product of the present application is 1% to 6% by mass percentage, and is further preferably 2% to 5% by mass percentage, for example, can be any one of 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, etc. within the range of 1% to 6% by mass percentage.

[0083] The Na2O and K2O introduced in the glass product of the present application are the main components for absorbing lithium ions during ion exchange in the chemical strengthening process. Na2O belongs to the network outside body and plays a fluxing role, which can reduce the glass melting temperature and improve the chemical stability of the glass. K2O mainly plays a fluxing role, which helps to reduce the viscosity and improve the melting property of the glass, but if too much K2O is introduced, it will hinder the ion exchange speed. In some embodiments, the content of Na2O in the glass product of the present application is 15% to 30% by mass percentage, and is further preferably 17% to 27%, for example, it can be any one content value in the range of 15% to 30%, such as 15%, 16%, 17%, 18%, 19%, 20%, 22%, 24%, 25%, 27%, 28%, 29%, 30%, etc. In order to balance the melting property of the glass and the ion exchange speed, in some embodiments, the content of K2O in the glass product of the present application can be 1% to 9% by mass percentage, and is further preferably 2% to 8%, for example, it can be any one content value in the range of 1% to 9%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.

[0084] The ZrO2 introduced in the glass product of the present application is in the network space, which plays an accumulation role on the surrounding silicon oxygen tetrahedron, can further increase the voids of the glass, and is beneficial to improve the ion exchange speed and exchange depth. In some embodiments, the content of ZrO2 in the glass product of the present application is 0% to 5% by mass percentage, and is further preferably 1% to 4%, for example, it can be any one content value in the range of greater than 0% and less than or equal to 5%, such as 0%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, 2.5%, 3%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.7%, 4.8%, 4.9%, 5%, etc. By adding ZrO2, the glass product of the present application can further improve the ion exchange speed and exchange depth.

[0085] In some embodiments, the present application controls the ratio of SiO2, Al2O3, B2O3, Na2O, K2O, ZrO2 in the glass product, and the ratio of network-forming components and intermediate components SiO2, Al2O3, B2O3 satisfies 0.38≤(Al2O3-B2O3) / SiO2≤1.04, and further preferably 0.43≤(Al2O3-B2O3) / SiO2≤0.82, for example, (Al2O3-B2O3) / SiO2 can be 0.38, 0.40, 0.42, 0.43, 0.45, 0.48, 0.50, 0.53, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.82, 0.85, 0.90, 0.92, 0.95, 0.98, 1.0, 1.02, 1.04, etc. any one value in the range of 0.38 to 1.04. Under the above ratio condition, boron exists in the form of triangle at high temperature, which plays a role in breaking the network and can reduce the glass viscosity; boron exists in the form of tetrahedron at low temperature, which can enhance the glass network structure. Through the special process of the present application, the glass product retains the structure at high temperature, i.e. boron exists in the form of triangle, and at the same time, Zr 4+ The ion aggregation produces voids, and the overall glass structure presents a porous loose structure, which is beneficial to absorbing lithium ions in the molten salt, effectively solving the problem that mutual diffusion no longer occurs due to the same chemical potential difference between alkali metal ions in the molten salt and alkali metal ions in the glass.

[0086] In some embodiments, the ratio of Na2O / K2O in the glass product is reasonably controlled to be 1.7≤Na2O / K2O≤30, and further preferably 2.1≤Na2O / K2O≤13.5, for example, the ratio of Na2O / K2O can be 1.7, 2, 2.1, 5, 8, 9, 10, 12, 13, 13.5, 15, 16, 18, 20, 22, 25, 26, 29, 30, etc. any one value in the range of 1.7 to 30 in terms of mass ratio. Under the above condition, it is beneficial to the melting of the glass at high temperature, and improves the stability of the glass; at low temperature, it can promote the exchange speed of lithium, sodium, potassium ions in the molten salt and ions in the glass.

[0087] In some embodiments, by adjusting the composition of the glass product, the glass product has a loose network structure. It can be understood that the glass product has both a loose structure and a network structure, and the loose structure contains more pores, which can further increase the voids of the glass product, which is beneficial to speed up the exchange speed and depth of ion exchange, and improve the absorption efficiency of lithium ions by the glass product. The network structure can help the glass product maintain good structural stability during high-temperature molten salt chemical strengthening, prolong the service life of the glass product, reduce the frequency of replacement, and also reduce the probability of pollution of the molten salt due to poor structural stability of the glass product.

[0088] The present application does not limit the shape of the glass product, and in some embodiments, the shape of the glass product includes granular and / or sheet-shaped. The granular and sheet-shaped glass product has a large specific surface area, which can increase the contact area with lithium ions in the molten salt, quickly absorb lithium ions separated from the lithium-containing microcrystalline glass in the chemical strengthening ion exchange, prevent the lithium ion concentration in the molten salt from being too high, maintain the composition stability of the molten salt, improve the efficiency and effect of lithium-containing microcrystalline glass and molten salt ion exchange, and improve the performance of the strengthened lithium-containing microcrystalline glass.

[0089] The granular glass product can be uniformly distributed around the lithium-containing microcrystalline glass, increase the contact area with the lithium-containing microcrystalline glass, quickly absorb lithium ions separated from the lithium-containing microcrystalline glass, maintain the stability of the lithium ion content in the bath salt, improve the efficiency of lithium-containing microcrystalline glass and molten salt ion exchange, and improve the chemical strengthening effect of the lithium-containing microcrystalline glass. In some embodiments, the particle size of the granular glass product is in the range of 0.2mm to 2mm, which can be any one of 0.2mm, 0.5mm, 0.8mm, 1mm, 1.2mm, 1.5mm, 1.8mm, 1.9mm, 2mm, etc. in the range of 0.2mm to 2mm.

[0090] The sheet-shaped glass product can increase the contact area with the lithium-containing microcrystalline glass during the molten salt chemical strengthening of the lithium-containing microcrystalline glass, quickly absorb lithium ions separated from the lithium-containing microcrystalline glass, maintain the stability of the lithium ion content in the bath salt, improve the efficiency of lithium-containing microcrystalline glass and molten salt ion exchange, and improve the chemical strengthening effect of the lithium-containing microcrystalline glass. The present application does not limit the size of the sheet-shaped glass product, which can be greater than or equal to 1mm x 1mm, and the thickness is 0.2mm to 2mm. It can be understood that the 1mm x 1mm in the above size refers to the surface area of one side of the glass product.

[0091] The glass product of the present application can absorb lithium ions and can be applied to absorb lithium ions in the molten salt to maintain the composition stability of the molten salt in the chemical strengthening process.

[0092] In some embodiments, the lithium ion absorption efficiency of the glass product is (2-6.8) x 10 -2 It can be understood that the above lithium ion absorption efficiency refers to the ratio of the mass of lithium ions absorbed by the glass product to the mass of the glass product. The glass product of the present application has a high absorption efficiency for lithium ions, and can be applied to stably absorb a large amount of lithium ions generated in the long-term chemical strengthening process of the lithium-containing microcrystalline glass.

[0093] The present application also provides a preparation method of the above glass product, comprising the following steps:

[0094] Step S10, weighing the component raw materials of the glass product, melting and cooling to obtain a preliminary formed glass;

[0095] Step S20, rapidly cooling the preliminary shaped glass to obtain the glass product, the glass product is in granular and / or sheet shape.

[0096] In some embodiments, the melting temperature is 1400-1600℃, for example, the melting temperature can be 1400℃, 1420℃, 1450℃, 1480℃, 1500℃, 1530℃, 1550℃, 1580℃, 1600℃, or any temperature value in the range of 1400-1600℃.

[0097] In some embodiments, the cooling temperature of step S10 is 1150-1300℃. The present application does not limit the way of cooling, in some embodiments, the cooling process of step S10 is a slow cooling process, under the above slow cooling condition, the phenomenon of uneven heating and explosion of the glass product due to too fast cooling speed can be prevented, which affects the loose network structure of the glass product and then affects its stability and absorption efficiency of lithium ions.

[0098] In some embodiments, in step S20, the preliminary shaped glass is subjected to water-cooled mechanical shaping to form sheet-shaped glass and / or water quenching to form granular glass to obtain the glass product. Through the above rapid cooling shaping method, it is beneficial to obtain granular and / or sheet-shaped glass products with small volume, and the granular and / or sheet-shaped glass products can increase the contact area with lithium-containing microcrystalline glass in the molten salt chemical strengthening process, quickly absorb lithium ions separated from the lithium-containing microcrystalline glass, maintain the stability of lithium ion content in the bath salt, improve the efficiency of lithium-containing microcrystalline glass and molten salt ion exchange, and improve the chemical strengthening effect of lithium-containing microcrystalline glass.

[0099] In some embodiments, the glass product can also be subjected to drying treatment, and the drying temperature is 80-150℃.

[0100] The present application also provides a chemical strengthening method of lithium-containing microcrystalline glass, comprising the following steps:

[0101] The glass product and the lithium-containing microcrystalline glass are simultaneously placed in the molten salt to obtain the strengthened lithium-containing microcrystalline glass.

[0102] It should be noted that the present application does not limit the composition of the lithium-containing microcrystalline glass, and the composition of the lithium-containing microcrystalline glass does not constitute a limitation on the application of the glass product of the present application in the chemical strengthening of the lithium-containing microcrystalline glass.

[0103] In some embodiments, the lithium-containing microcrystalline glass contains the following components in terms of mass percentage:

[0104] SiO2: 70-75%,

[0105] Al203: 5% to 12%,

[0106] Li20: 9% to 13%,

[0107] P205: 1.5% to 5%,

[0108] Na20: 0.1% to 5%,

[0109] Zr02: 2% to 7%,

[0110] B203: 0.1% to 5%.

[0111] In some embodiments, the molten salt further contains NaN03 with a mass concentration of 10% to 40% and KNO3 with a mass concentration of 60% to 90% in the formula of the molten salt.

[0112] In some embodiments, the molten salt contains LiN03, and the LiN03 is maintained in the molten salt at a mass concentration ranging from 0.02% to 0.15%, for example, the mass concentration of LiN03 can be 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.13%, 0.14%, 0.15%, or any value within the range of 0.02% to 0.15%. It can be understood that the LiN03 is maintained in the molten salt at a mass concentration ranging from 0.02% to 0.15% means that, in the chemical strengthening, the glass product can absorb lithium ions replaced into the molten salt in the chemical strengthening process, maintain the stability of the original lithium ion mass concentration in the molten salt, and even maintain the stability of the lithium ion mass concentration in the molten salt throughout the chemical strengthening process, thereby preventing the effect of the chemical strengthening from being affected due to the excessively high lithium ion mass concentration.

[0113] In some embodiments, the glass product and the lithium-containing microcrystalline glass are further subjected to a heating and holding treatment before being subjected to the chemical strengthening. The heating and holding temperature is 350°C to 400°C, and the heating and holding time is 30 min to 90 min. The glass product and the lithium-containing microcrystalline glass are subjected to the chemical strengthening after the heating and holding, so that the explosion due to uneven heating can be avoided.

[0114] In some embodiments, the chemical strengthening temperature is 450°C to 510°C, for example, the chemical strengthening temperature can be 450°C, 460°C, 480°C, 500°C, 505°C, 510°C, or any value within the range of 450°C to 510°C.

[0115] In some embodiments, the chemical strengthening time is 4 h to 8 h, for example, the chemical strengthening time can be 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, or any value within the range of 4 h to 8 h.

[0116] It is understandable that the above restrictions on chemical strengthening temperature and chemical strengthening time can be satisfied by only one condition or by both conditions. When both conditions are met, it is more conducive to controlling the ion exchange rate of lithium-containing glass crystals to ensure that it is not too slow or too fast, thus ensuring the stability and good mechanical properties of lithium-containing glass crystals after chemical strengthening.

[0117] In some embodiments, the amount of lithium-containing microcrystalline glass added is 200 g / m², based on the area of ​​the microcrystalline glass. 2 ~700g / m 2 For example, the amount added to glass products can be 200g / m³. 2 250g / m 2 300g / m 2 400g / m 2 500g / m 2 550g / m 2 600g / m 2 630g / m 2 650g / m 2 680g / m 2 700g / m 2 200g / m 2 ~700g / m 2 Any amount added within the range. It can be understood that the area of ​​lithium-containing microcrystalline glass is defined as the surface area of ​​one side of the lithium-containing microcrystalline glass sheet, and the amount introduced into the glass product designed based on the area of ​​the lithium-containing microcrystalline glass is 200 g / m². 2 ~700g / m 2 It can effectively regulate the absorption of lithium ions in molten salt, avoiding an imbalance in the lithium ion content in the salt bath caused by excessive or insufficient absorption.

[0118] The addition of the glass product of this invention to the chemical strengthening process of lithium-containing microcrystalline glass of this invention can control the concentration of lithium ions in the molten salt. The resulting strengthened lithium-containing microcrystalline glass has good mechanical properties, a drop height of up to 160 mm, CS-30 ≥ 100 MPa, and a strengthening depth DOL ≥ 100 μm.

[0119] It should be noted that the glass products of the present invention can be added to molten salt during the chemical strengthening of lithium-containing microcrystalline glass, and can enter and exit the molten salt together with the lithium-containing microcrystalline glass. During the chemical strengthening process, the concentration of lithium ions in the molten salt can be controlled to ensure the stability of the composition of the molten salt and enhance the effect of chemical strengthening.

[0120] Furthermore, the glass articles of the present invention can also control the stability of lithium ions in the molten salt by purifying the molten salt. After the lithium-containing microcrystalline glass has undergone chemical strengthening, the glass articles are added to the molten salt to absorb the increased concentration of lithium ions in the molten salt.

[0121] A purification method of fused salt is provided, comprising the following steps:

[0122] Step one: heating and holding the glass product of the present application;

[0123] Step two: adding the glass product after the heating and holding treatment into the fused salt to purify the fused salt, which is the process of absorbing lithium ions in the fused salt by the glass product.

[0124] In the process of purifying the fused salt, the amount of the glass product added can be determined according to the content of lithium ions in the fused salt. As the content of lithium ions in the fused salt increases, the amount of the glass product added can be appropriately increased.

[0125] In some embodiments, the formula of the fused salt further contains NaNO3 with a mass percentage of 2% to 40% and KNO3 with a mass percentage of 60% to 98%.

[0126] In some embodiments, the temperature of the heating and holding is 350°C to 400°C, for example, the temperature of the heating and holding can be any one temperature value in the range of 350°C to 400°C, such as 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, etc. The glass product is less likely to burst after being heated and then purifying the fused salt.

[0127] The technical solutions of the present application are further described in detail in combination with specific embodiments. It should be understood that the following specific embodiments are only used to explain the present application and do not limit the present application.

[0128] In the disclosure of the present application, the following performance tests of the examples and comparative examples are not otherwise stated:

[0129] 1. The CS and DOL of the strengthened lithium-containing microcrystalline glass were tested using Japan OZAWA FSM-6000LE+SLP1000 surface stress meter.

[0130] 2. The birefringence imaging system was used, the specific wavelength of the polarized light passed through the glass with stress gradient to produce the refractive path difference, and the related stress distribution indexes: CS-30, DOL were calculated.

[0131] 3. The whole machine sandpaper drop performance was measured by a mobile phone controlled drop tester, and the specific test conditions were: 80 mesh sandpaper, 195g total weight, 60cm base height, 10cm increment, 1 time per height, until broken.

[0132] 4. Atomic absorption spectrophotometer was used to test the lithium ion content before and after the chemical strengthening of the fused salt.

[0133] The lithium-containing microcrystalline glass used in the following examples and comparative examples comprises the following components in mass percentage:

[0134] SiO2: 73%, Al2O3: 8%, Li2O: 11%, P2O5: 4%, Na2O: 0.5%, ZrO2: 2%, B2O3: 1.5%.

[0135] Example 1

[0136] Preparation of glass products

[0137] Step S10: Glass raw materials were weighed according to the component composition of the glass products in Table 1, and then melted at 1400-1600°C, and then slowly cooled to 1150-1300°C to obtain 7 groups of preliminary shaped glasses.

[0138] Step S20: The 7 groups of preliminary shaped glasses were respectively formed into granular or sheet-shaped glass products by water quenching at 0-50°C, and then the 7 groups of glass products were dried at 80-150°C.

[0139] The particle size of the granular glass product was controlled in the range of 0.2-2 mm, and the size of the sheet-shaped glass product was ≥1 mm×1 mm, and the thickness was in the range of 0.2-2 mm.

[0140] Comparative Example 1

[0141] Preparation of glass products

[0142] Step S10: Glass raw materials were weighed according to the component composition of the glass products in Table 1, and then melted at 1400-1600°C, and then slowly cooled to 1150-1300°C to obtain 2 groups of preliminary shaped glasses.

[0143] Step S20: The 2 groups of preliminary shaped glasses were respectively formed into granular or sheet-shaped glass products by water quenching at 0-50°C, and then the 2 groups of glass products were dried at 80-150°C.

[0144] The particle size of the granular glass product was controlled in the range of 0.2-2 mm, and the size of the sheet-shaped glass product was ≥1 mm×1 mm, and the thickness was in the range of 0.2-2 mm.

[0145] Performance Test 1: Purification experiment of molten salt for Example 1 and Comparative Example 1

[0146] The 7 groups of glass products of Example 1 and the 2 groups of glass products of Comparative Example 1 were added into the same formula molten salt respectively with the same addition amount, and the lithium ions in the molten salt were absorbed at 470℃ for 6h. After the purification of the molten salt was completed, the content of lithium ions in the purified molten salt was determined, and the absorption efficiency of lithium ions in the molten salt by the glass products was calculated, and the results are shown in Table 1.

[0147] wherein,

[0148] The formula of the molten salt: the lithium ion content is 2000ppm, and contains 30% of NaNO3+70% of KNO3 by mass concentration;

[0149] The addition amount of the glass product: 1.5% of the total mass of the molten salt, and the mass of the molten salt is 30kg.

[0150] The absorption efficiency of lithium ions: the ratio of the mass of the lithium ions absorbed by the glass product to the mass of the glass product.

[0151] Table 1

[0152]

[0153]

[0154] As shown in Table 1, the 7 groups of glass products of Example 1 have high absorption efficiency of lithium ions in the molten salt, and the glass product of comparative component 1 in Comparative Example 1 does not contain B2O3, and the glass product of comparative component 2 (Al2O 3- B2O3) / SiO 2, 0.22, which do not meet the process requirements of the present application, and the absorption efficiency of lithium ions is relatively poor compared with Example 1.

[0155] Example 2

[0156] The glass products of component 1 and component 7 in Example 1 were used to purify the molten salt under different conditions.

[0157] Comparative Example 2

[0158] The glass products of comparative component 1 and comparative component 2 in Comparative Example 1 were used to purify the molten salt under different conditions.

[0159] Performance test 2: test of the absorption efficiency of lithium ions of Example 2 and Comparative Example 2

[0160] The content of lithium ions in the molten salt before and after the purification of the molten salt by the glass products of component 1 and component 7 of Example 2 and the glass products of comparative component 1 and comparative component 2 of Comparative Example 2 under 6 different purification conditions was determined, and the absorption efficiency of lithium ions in the molten salt by the glass products was calculated, and the test results are shown in Table 2.

[0161] Table 2

[0162]

[0163]

[0164] From Table 2, the glass product of Example 2 was purified by molten salt under 6 different conditions respectively, and the absorption efficiency of lithium ion was between 2.09 x 10 -2 and 6.80 x 10 -2 , which was relatively high, while the absorption efficiency of lithium ion of the glass product of Comparative Example 2 was relatively low, between 0.31 x 10 -2 and 1.37 x 10 -2 .

[0165] Example 3

[0166] The glass product and the 1 m2 lithium-containing microcrystalline glass to be strengthened were heated and kept at 350-400°C for 30-90 min, and then were simultaneously placed in molten salt to perform chemical strengthening to obtain strengthened lithium-containing microcrystalline glass, and the chemical strengthening conditions are shown in Table 3.

[0167] The glass product of this example was the glass product of component 1 and the glass product of component 7 in Example 1 respectively.

[0168] Comparative Example 3

[0169] Comparative Example 3 was based on Example 3, without adding the glass product, and directly heating and keeping the 1 m2 lithium-containing microcrystalline glass to be strengthened at 350-400°C for 30-90 min, and then placing it in molten salt to perform chemical strengthening to obtain strengthened lithium-containing microcrystalline glass, and the chemical strengthening conditions are shown in Table 3.

[0170] Comparative Example 4

[0171] The glass product and the 1 m2 lithium-containing microcrystalline glass to be strengthened were heated and kept at 350-400°C for 30-90 min, and then were simultaneously placed in molten salt to perform chemical strengthening to obtain strengthened lithium-containing microcrystalline glass.

[0172] The glass product of this example was the glass product of component 1 and the glass product of component 7 in Example 1 respectively.

[0173] In addition, the chemical strengthening molten salt formula used in Example 3 and Comparative Examples 3-4 was 0.15% LiNO3+39.85% NaNO3+60% KNO3 by mass concentration;

[0174] The glass product addition amount and the chemical strengthening temperature and time are shown in Table 3.

[0175] Performance test 3: test of the effect of lithium-containing microcrystalline glass chemical strengthening of example 3, comparative example 3 and comparative example 4

[0176] The content of lithium ions in the molten salt before and after chemical strengthening of example 3, comparative example 3 and comparative example 4 was determined, and the CS-30 / MPa, DOL / μm and drop performance / mm of the strengthened lithium-containing microcrystalline glass obtained after the lithium-containing microcrystalline glass completed chemical strengthening were determined, and the test results are shown in Table 3.

[0177] Table 3

[0178]

[0179] As shown in Table 3, the content of lithium ions in the molten salt after the chemical strengthening ion exchange of example 3 does not fluctuate much under different time conditions, indicating that the lithium ions ion-exchanged out of the lithium-containing microcrystalline glass are almost absorbed by the glass product, and the content of lithium ions in the molten salt is stable during the entire chemical strengthening process. The strengthened lithium-containing microcrystalline glass obtained after the lithium-containing microcrystalline glass is chemically strengthened has good mechanical properties, CS-30≥100MPa, DOL≥100μm, and the drop height reaches 160mm.

[0180] The lithium-containing microcrystalline glass of comparative example 3 does not add a glass product for absorbing lithium ions in the molten salt, and the content of lithium ions in the molten salt after the chemical strengthening ion exchange is≥0.19%, and the content of lithium ions in the molten salt increases continuously as the strengthening time increases, and the CS-30, DOL and mechanical properties of the obtained strengthened lithium-containing microcrystalline glass are greatly reduced.

[0181] The glass product of comparative component 1 does not contain B2O3, which does not meet the requirements of the present application, and the concentration of lithium ions in the molten salt continuously increases after ion exchange at different times, indicating that it cannot absorb all the lithium ions ion-exchanged out of the lithium-containing microcrystalline glass, and the CS-30, DOL and mechanical properties of the strengthened lithium-containing microcrystalline glass obtained after the lithium-containing microcrystalline glass completes chemical strengthening are greatly reduced.

[0182] The (Al2O3-B2O3) / SiO2 of the glass product of comparative component 2 is 0.22, which does not meet the requirements of the present application, and the concentration of lithium ions in the molten salt continuously increases after ion exchange at different times, indicating that it cannot absorb all the lithium ions ion-exchanged out of the lithium-containing microcrystalline glass, and the CS-30, DOL and mechanical properties of the strengthened lithium-containing microcrystalline glass obtained after the lithium-containing microcrystalline glass completes chemical strengthening are greatly reduced.

[0183] The above is only a preferred embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent flow conversion using the content of the present application specification and drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A glass article, characterized by, The glass product comprises the following components in percentage by mass: SiO2: 28%-50%, Al2O3: 20%-35%, B2O3: 1%-6%, Na2O: 15%-30%, K2O: 1%-9%, ZrO2: 0.1%-5%, wherein the components of the glass product satisfy 0.38≤(Al2O3-B2O3) / SiO2≤1.04 and 1.7≤Na2O / K2O≤30; The glass article can absorb lithium ions, the lithium ion absorption efficiency of the glass article being (2-6.8) x 10 -2 -4, the lithium ion absorption efficiency being a ratio of a mass of the lithium ions absorbed by the glass article to a mass of the glass article.

2. The glass article of claim 1, wherein, The glass product comprises the following components in percentage by mass: SiO2: 33%-47%, Al2O3: 22%-32%, B2O3: 2%-5%, Na2O: 17%-27%, K2O: 2%-8%, ZrO2: 1%-4%.

3. The glass article of claim 1, wherein, The components of the glass product satisfy 0.43≤(Al2O3-B2O3) / SiO2≤0.82 in percentage by mass; And / or, the components of the glass product satisfy 2.1≤Na2O / K2O≤13.

5.

4. The glass article of claim 1, wherein, The shape of the glass product is granular, and the particle size of the glass product in the granular shape ranges from 0.2 mm to 2 mm; And / or, the shape of the glass product is sheet-shaped, and the size of the glass product in the sheet-shaped is ≥1 mm×1 mm, and the thickness is 0.2 mm-2 mm.

5. A method of making the glass article of any one of claims 1 to 4, wherein the method comprises: The method comprises the following steps: Weighing the component raw materials of the glass product, melting and cooling to obtain a preliminary formed glass; The preliminary formed glass is rapidly cooled to obtain the glass product, which is granular and / or sheet-shaped.

6. The method of making a glass article according to claim 5, wherein, The melting temperature is 1400-1600°C; And / or, the cooling temperature is 1150-1300°C.

7. The method of making a glass article according to claim 5, wherein, In the step of rapidly cooling the preliminary formed glass to obtain the glass product, the preliminary formed glass is subjected to water-cooling mechanical forming to form sheet-shaped glass and / or water quenching to form granular glass under the condition of 0-50°C to obtain the glass product.

8. The method of making a glass article according to claim 5, wherein, The glass product is also subjected to drying treatment, and the drying temperature is 80-150°C.

9. A method of chemically strengthening a lithium-containing glass-ceramic, characterized in that, The method comprises the following steps: The glass product of any one of claims 1-4 and the lithium-containing microcrystalline glass are simultaneously placed in a molten salt to perform chemical strengthening to obtain a strengthened lithium-containing microcrystalline glass.

10. The method of chemically strengthening a lithium-containing microcrystalline glass according to claim 9, wherein The lithium-containing microcrystalline glass comprises the following components in percentage by mass: SiO2: 70%-75%, Al2O3: 5%-12%, Li2O: 9%-13%, P2O5: 1.5%-5%, Na2O: 0.1%-5%, ZrO2: 2%-7%, B2O3: 0.1%-5%.

11. The method of chemically strengthening a lithium-containing microcrystalline glass according to claim 9, wherein The molten salt contains NaNO3 with a mass concentration of 10%-40% and KNO3 with a mass concentration of 60%-90%.

12. The method of chemically strengthening a lithium-containing microcrystalline glass according to claim 9, wherein The molten salt contains LiNO3, and the mass concentration of LiNO3 in the molten salt ranges from 0.02% to 0.15%.

13. The method of chemically strengthening a lithium-containing microcrystalline glass according to claim 9, wherein The glass product and the lithium-containing microcrystalline glass are heated and kept at a temperature of 350-400°C before chemical strengthening. And / or, the glass product and lithium-containing microcrystalline glass are heated and kept for 30 min to 90 min before chemical strengthening.

14. The method of chemically strengthening a lithium-containing microcrystalline glass according to claim 9, wherein The temperature of the chemical strengthening is 450 DEG C to 510 DEG C. And / or, the time of the chemical strengthening is 4 h to 8 h.

15. The method of chemically strengthening a lithium-containing microcrystalline glass according to claim 9, wherein The glass product is added in an amount of 200 g / m 2 700 g / m 2 .

16. A strengthened lithium-containing microcrystalline glass prepared by the method of any one of claims 9 to 15.

17. The strengthened lithium-containing microcrystalline glass of claim 16, wherein, The CS-30 of the strengthened lithium-containing microcrystalline glass is greater than or equal to 100 MPa. And / or, the depth of the strengthening DOL of the strengthened lithium-containing microcrystalline glass is greater than or equal to 100 μm.

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