CN112110645B

CN112110645B - Glass, glass product and manufacturing method thereof

Info

Publication number: CN112110645B
Application number: CN202011009699.XA
Authority: CN
Inventors: 马赫; 毛露路; 蔡冬雪
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2020-09-23
Filing date: 2020-09-23
Publication date: 2022-04-15
Anticipated expiration: 2040-09-23
Also published as: CN112110645A

Abstract

The invention provides glass, which comprises the following components in percentage by weight: SiO 2₂：41～65.5％；Al₂O₃：17.5～31％；Li₂O+Na₂O：5～14.5％；P₂O₅: 0.1 to 8% of Li₂O/(Li₂O+Na₂O) is 0.1 to 0.4. Through reasonable component design, the glass obtained by the invention is suitable for chemical strengthening and secondary thermal processing, and simultaneously has higher Young modulus. The glass product obtained by the invention has higher micro Vickers hardness and excellent mechanical property.

Description

Glass, glass product and manufacturing method thereof

Technical Field

The present invention relates to glass, and is especially one kind of glass suitable for chemical strengthening, glass product and its making process.

Background

In the prior art, glass materials are widely applied to the fields of panels, back plates, structural materials and the like of various electronic devices (such as mobile phones, smart watches and the like). In the above application fields, the glass material is primarily considered to have drop resistance and impact resistance. For example, CN110040982A, CN110627365A, CN106232541A and the like all disclose glasses having excellent drop resistance.

The impact resistance and scratch resistance of the glass material are not the same, for example, the impact resistance of the material can be effectively improved by constructing a two-phase composite structure, and the scratch resistance of the material can be improved by improving the hardness. In some applications, scratch resistance of the glass is a primary consideration. For example, in solar panel protection applications, glass needs to maintain a smooth surface under long term sand impact, wiper wiping, but is less likely to be impacted. In the field of increasingly developed wearable devices, parts of the wearable devices are light in weight, tightly combined with human bodies, and low in possibility of falling and damage in use. Therefore, the primary performance of protective glass for some wearable devices is scratch resistance. On the other hand, the glass should also have the ability of being post-thermoformed to make different shaped protective glasses for wearable devices. Furthermore, if the protective glass of the wearable equipment has higher pressure resistance and corrosion resistance, the wearable equipment is also beneficial to being applied in high-pressure environments such as deep submergence and the like, and the use value of the wearable equipment is improved.

Disclosure of Invention

The technical problem to be solved by the invention is to provide glass which is suitable for chemical strengthening and secondary hot forming, and a glass product prepared by chemical strengthening has excellent mechanical properties.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) glass, the composition of which, expressed in weight percent, comprises: SiO 2₂：41～65.5％；Al₂O₃：17.5～31％；Li₂O+Na₂O：5～14.5％；P₂O₅: 0.1 to 8% of Li₂O/(Li₂O+Na₂O) is 0.1 to 0.4.

(2) The glass according to (1), which comprises the following components in percentage by weight: k₂O: 0 to 7 percent; and/or ZnO: 0-6%; and/or MgO: 0 to 10 percent; and/or CaO: 0 to 8.5 percent; and/or SrO: 0 to 10 percent; and/or BaO: 0 to 15 percent; and/or B₂O₃: 0-6%; and/or ZrO₂: 0 to 7 percent; and/or La₂O₃: 0 to 15 percent; and/or Ag₂O: 0 to 4.5 percent; and/or Sb₂O₃: 0 to 1 percent; and/or SnO₂：0～3％。

(3) A glass having a composition, expressed in weight percent, of SiO₂：41～65.5％；Al₂O₃：17.5～31％；Li₂O+Na₂O：5～14.5％；P₂O₅：0.1～8％；K₂O：0～7％；ZnO：0～6％；MgO：0～10％；CaO：0～8.5％；SrO：0～10％；BaO：0～15％；B₂O₃：0～6％；ZrO₂：0～7％；La₂O₃：0～15％；Ag₂O：0～4.5％；Sb₂O₃：0～1％；SnO₂: 0 to 3% of a compound of Li₂O/(Li₂O+Na₂O) is 0.1 to 0.4.

(4) The glass according to any one of (1) to (3), which has a composition satisfying, in terms of weight percent, one or more of the following 4 conditions:

1)Li₂O/(Li₂O+Na₂o) is 0.15 to 0.35;

2)Li₂O+Na₂O+K₂O+Ag₂o is 6-16.5%;

3)P₂O₅/Al₂O₃is less than 0.4;

4)(ZnO+1.8×B₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃0.38 to 1.15.

(5) The glass according to any one of (1) to (3), which comprises the following components in percentage by weight: SiO 2₂: 45-58.5%; and/or Al₂O₃: 21-25.5%; and/or Li₂O+Na₂O: 6.5-12.5%; and/or P₂O₅: 0.3-4%; and/or K₂O: 0 to 4 percent; and/or ZnO: 0 to 3.5 percent; and/or MgO: 0 to 9 percent; and/or CaO: 0 to 4 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 5 percent; and/or B₂O₃: 0.5-3%; and/or ZrO₂: 0-2%; and/or La₂O₃: 0 to 5 percent; and/or Sb₂O₃: 0.02-0.7%; and/or SnO₂：0.01～3％。

(6) The glass according to any one of (1) to (3), which has a composition satisfying, in terms of weight percent, one or more of the following 4 conditions:

1)Li₂O/(Li₂O+Na₂o) is 0.15 to 0.3;

2)Li₂O+Na₂O+K₂O+Ag₂o is 9-14%;

3)P₂O₅/Al₂O₃0.05 to 0.25;

4)(ZnO+1.8×B₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃0.4 to 1.1.

(7) According to any of (1) to (3)The glass comprises the following components in percentage by weight: p₂O₅: 0.7-2.5%; and/or K₂O: 0-2%; and/or MgO: 3-7%; and/or Sb₂O₃: 0.05-0.4%; and/or SnO₂：0.4～1.5％。

(8) The glass according to any one of (1) to (3), which comprises the following components in percentage by weight: (ZnO +1.8 XB)₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃0.42 to 1.0.

(9) The glass according to any one of (1) to (3), which comprises the following components in percentage by weight: na (Na)₂O: 3-12.5%, preferably Na₂O: 4 to 11.5%, more preferably Na₂O: 5 to 10.5%, and/or Li₂O: 0.8 to 4%, preferably Li₂O: 1 to 3.8%, more preferably Li₂O：1.2～3.6％。

(10) The glass according to any one of (1) to (3), wherein the glass contains two or more components selected from the group consisting of ZnO, MgO, CaO, SrO and BaO at the same time, preferably contains two or three components selected from the group consisting of ZnO, MgO, CaO, SrO and BaO at the same time, more preferably contains two components selected from the group consisting of ZnO, MgO, CaO, SrO and BaO at the same time, and still more preferably contains ZnO and MgO at the same time.

(11) The glass according to any one of (1) to (3), wherein Ag is not contained in the glass₂O; and/or does not contain TiO₂(ii) a And/or does not contain CeO₂(ii) a And/or does not contain CaO; and/or does not contain SrO; and/or no BaO; and/or does not contain PbO; and/or does not contain As₂O₃。

(12) The glass according to any one of (1) to (3), wherein the glass has a refractive index n_d1.470 to 1.540, preferably 1.490 to 1.510; and/or light transmission T_550nm91.0% or more, preferably 91.4% or more, more preferably 91.8% or more; and/or a Young's modulus E of 7800X 10⁷Pa or more, preferably 8000X 10⁷Pa or more, more preferably 8200X 10⁷Pa or above.

The present invention also provides a glass article:

(13) a glass product comprising the glass according to any one of (1) to (12).

(14) The glass article of claim 13, having a microvickers hardness of 680 x 10⁷Pa or more, preferably 690X 10⁷Pa or more, more preferably 700X 10⁷Pa or above.

The present invention also provides a glass preform comprising:

(15) a glass preform made of the glass according to any one of (1) to (12), or the glass product according to (13) or (14).

The present invention also provides a glass element:

(16) a glass member made of the glass according to any one of (1) to (12), or the glass product according to (13) or (14).

The invention also provides a device:

(17) an apparatus comprising the glass according to any one of (1) to (12), and/or comprising the glass product according to (13) or (14), and/or comprising the glass element according to (16).

The invention also provides a manufacturing method of the glass product, which comprises the following steps:

(18) a method of making a glass article, the method comprising the steps of: forming the glass according to any one of (1) to (12), forming a glass product by the glass through a chemical strengthening process, or forming a glass product by forming a glass into a glass molded body through various processes and then performing a chemical strengthening process.

(19) The method for producing a glass product according to (18), wherein the glass is produced into a glass shaped body by a grinding or polishing process, or a glass shaped body by a hot bending or press molding process at a certain temperature.

(20) The method for manufacturing a glass article according to (18), wherein the chemical strengthening process is to immerse the glass or the glass shaped body in a single salt bath, or to immerse the glass or the glass shaped body in a plurality of salt baths having the same or different compositions.

(21) The method for manufacturing a glass product according to (18), wherein the chemical strengthening process is a 1-step ion exchange method, in the ion exchange method, the molten salt of the salt bath is composed of two or more compounds according to a certain proportion, at least one of the compounds contains K salt or Na salt, preferably K salt, the temperature of the salt bath is 400-510 ℃, preferably 420-500 ℃, and the time of the salt bath is 4-32 hours, preferably 8-24 hours.

(22) The method for manufacturing a glass product according to (18), wherein the chemical strengthening process is a 2-step ion exchange method, in the ion exchange method, the molten salt of the first-step salt bath is composed of two or more compounds according to a certain proportion, wherein the molten salt at least contains one or two of K salt and Na salt, preferably contains K salt and Na salt at the same time, the temperature of the first-step salt bath is 400-510 ℃, preferably 420-500 ℃, and the time of the first-step salt bath is 4-32 hours, preferably 8-24 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound contains K salt or Na salt, preferably K salt, the temperature range of the second-step salt bath is 400-510 ℃, preferably 420-500 ℃, and more preferably the same as the temperature of the first-step salt bath; the time range of the second-step salt bath is 0.5-16 h, preferably 0.5-8 h, and more preferably 0.5-4 h.

The invention has the beneficial effects that: through reasonable component design, the glass obtained by the invention is suitable for chemical strengthening and secondary thermal processing, and simultaneously has higher Young modulus. The glass product obtained by the invention has higher micro Vickers hardness and excellent mechanical property.

In some embodiments, the glass articles obtained by the present invention have a lower total amount of stress while having a higher surface lamination stress and a deeper depth of stress layer. Therefore, on the premise of good mechanical properties of the glass product, the possibility of glass fracture caused by unstable propagation of surface cracks and glass self-explosion caused by self-stress release is greatly reduced.

Detailed Description

The following describes in detail embodiments of the glass and glass product of the present invention, but the present invention is not limited to the embodiments described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the following, the glass of the present invention is referred to as "glass" before being chemically strengthened, and the glass after being chemically strengthened is referred to as "glass product".

[ glass ]

The ranges of the respective components (ingredients) of the glass of the present invention are explained below. In the present invention, the contents and total contents of the respective components are all expressed in weight percent (wt%), that is, the contents and total contents of the respective components are expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

< essential Components and optional Components >

Na₂O is an essential component of the glass of the present invention, and Na is used in the chemical strengthening process₂O provides ions involved in chemical strengthening, and functions to provide a surface compressive stress layer. At the same time, Na₂O also has the effect of improving the meltability of glass and lowering the softening temperature of glass. However, Na₂A high O content lowers the chemical durability of the glass and is not favorable for the improvement of the glass strength. Thus, Na₂The content of O is 3 to 12.5%, preferably 4 to 11.5%, and more preferably 5 to 10.5%.

Li₂O is an essential component of the glass of the invention, Li being an essential component in the chemical strengthening process₂O provides ions involved in chemical strengthening, and functions to provide a surface compressive stress layer. All in oneWhen Li is present₂O has strong fluxing action and is beneficial to improving the content of other components which are beneficial to the strength in the glass. But Li₂The content of O is too high, and the glass is easy to crystallize, so that the subsequent thermal processing is not facilitated. Thus, Li₂The content of O is 0.8 to 4%, preferably 1 to 3.8%, and more preferably 1.2 to 3.6%.

Li₂O and Na₂O functions to provide ions that participate in chemical strengthening. Since Li has a smaller ionic radius than Na, the diffusion rate of Li ions is much faster than Na ions during chemical strengthening, and the diffusion of Li ions is a major source of deep lamination stress in glass. Control of Li₂O and Li₂O and Na₂Total content of O Li₂O+Na₂Ratio of O Li₂O/(Li₂O+Na₂O), has a key role in optimizing the stress distribution of the glass article. Through a large number of experimental researches of the inventor, Li₂O/(Li₂O+Na₂O) and stress distribution characteristics are not continuously changing. In particular, Li₂O/(Li₂O+Na₂O) is not less than 0.1, and a glass product obtained by chemically strengthening the glass can have an optimized stress layer distribution. But if Li₂O/(Li₂O+Na₂And O) is too high, the glass is easy to crystallize, and the subsequent thermal processing is not facilitated. Therefore, Li is preferable₂O/(Li₂O+Na₂O) is in the range of 0.1 to 0.4, more preferably 0.15 to 0.35, and still more preferably 0.15 to 0.3.

In some embodiments, if Li₂O and Na₂Total content of O Li₂O+Na₂O is less than 5%, and the chemical strengthening effect of the glass is poor; if Li₂O+Na₂With O higher than 14.5%, the hardness of the resulting glass article decreases, making it difficult to satisfy the object of the present invention. Thus, Li₂O+Na₂The range of O is preferably 5 to 14.5%, more preferably 6.5 to 12.5%.

K₂O is an optional component of the glass of the invention, K is K during the chemical strengthening process₂O can provide ion exchange for ion participation in the chemical strengthening process, but cannot provide a surface compressive stress layer. In thatGlass containing Li₂O、Na₂Based on O, a small amount of K₂O can significantly improve the meltability of the glass. Thus K₂The content of O is 0 to 7%, preferably 0 to 4%, more preferably 0 to 2%.

The glass contains a small amount of Ag₂O does not significantly affect the strength and appearance of the glass, Ag₂O can also make glass antibacterial, but Ag₂The cost of O is high. Thus, Ag in the present invention₂The content of O is 0-4.5%, preferably not containing Ag₂O。

Li₂O、Na₂O、K₂O、Ag₂O has the function of reducing the integrity of the glass network, and if the total content of O is too high, the strength and the chemical stability of the glass are not improved. Thus, in some embodiments of the invention, Li is preferred₂O、Na₂O、K₂O、Ag₂Total content of O Li₂O+Na₂O+K₂O+Ag₂The range of O is 6 to 16.5%, more preferably 9 to 14%.

ZnO has the greatest tendency to enter the glass network relative to other alkaline earth metal components. Meanwhile, ZnO also has the function of enabling the appearance of the glass to have luster. When the content of ZnO is lower, the ZnO has the functions of reducing the melting temperature and the crystallization tendency of glass, and can not obviously influence the ion exchange diffusion coefficient of the glass. However, if the content of ZnO is too high, devitrification of the glass occurs and the chemical strengthening property of the glass is lowered. Therefore, the content of ZnO is in the range of 0 to 6%, preferably 0 to 3.5%.

MgO has a strengthening effect on a glass network, and simultaneously has the effects of improving the meltability of glass liquid and reducing the softening temperature of glass. However, an excessive content of MgO may degrade the chemical strengthening properties of the glass. Therefore, the content of MgO in the glass is 0 to 10%, preferably 0 to 9%, and more preferably 3 to 7%.

CaO has the functions of strengthening the glass network, improving the meltability of molten glass and reducing the softening temperature of the glass. CaO has an effect of improving the Young's modulus of glass better than MgO, but CaO-containing glass releases Ca ions in a salt bath for chemical strengthening, and a trace amount of Ca ions will make the salt bath for chemical strengthening ineffective. Therefore, the content of CaO is in the range of 0 to 8.5%, preferably 0 to 4%, and more preferably, CaO is not contained.

At lower contents of SrO and BaO, the glass has the effect of lowering the melting temperature of the glass. However, SrO and BaO have the adverse effect of promoting phase separation of the glass and reducing the chemical stability of the glass. Therefore, the content of SrO is 0-10%, preferably 0-3%, and more preferably, SrO is not contained; the content of BaO is in the range of 0 to 15%, preferably 0 to 5%, and more preferably no BaO.

In some embodiments of the present invention, it is preferable that the glass contains two or more components of ZnO, MgO, CaO, SrO, and BaO at the same time, which contributes to the establishment of a mixed alkaline earth effect in the glass, and can improve the strength of the glass and the meltability of the molten glass, and it is more preferable that the glass contains two or three components of ZnO, MgO, CaO, SrO, and BaO at the same time, it is further preferable that the glass contains two components of ZnO, MgO, CaO, SrO, and BaO at the same time, and it is still further preferable that the glass contains ZnO and MgO at the same time.

Al₂O₃Can improve the chemical stability of the glass, is beneficial to forming loose glass grids, and enables the glass to be easy to improve the strength through a chemical strengthening process. Meanwhile, the glass contains higher Al content₂O₃And the glass also has the function of reducing the possibility of the glass breaking under the conditions of scratching, pressing in of hard objects and the like. However, Al₂O₃Too much content causes difficulty in glass melting. Therefore, Al in the present invention₂O₃The content of (b) is in the range of 17.5 to 31%, preferably 21 to 25.5%.

B₂O₃The melting process of the glass batch can be improved, and the high-temperature viscosity of the molten glass can be obviously reduced; but B₂O₃Too high a content of (b) may significantly reduce the chemical strengthening effect of the glass. Thus, B₂O₃The content of (b) is in the range of 0 to 6%, preferably 0.5 to 3%.

To achieve the optimized stress distribution properties of the glass articles of the present invention, it is also desirable to perform ion exchange rates during chemical strengtheningAnd (5) controlling. If the ion exchange rate is too fast, the specific shape of the glass is not easily maintained during the chemical strengthening process, and it is not favorable to obtain reasonable stress distribution. If the ion exchange speed is too slow, the chemical strengthening time is prolonged, which is not beneficial to reducing the production cost, and the too slow ion exchange speed can also reduce the pressure stress on the surface of the glass product and reduce the strength of the glass product. Through a great deal of experimental research of the inventor, the inventor finds that in order to obtain a proper ion exchange speed, the glass product has excellent stress distribution and higher compressive stress, has a better specific shape and reduces the production cost, and the control of (ZnO +1.8 xB) is preferable₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃The value of (A) is 0.38 to 1.15, more preferably (ZnO +1.8 XB)₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃The value of (A) is 0.4 to 1.1, and (ZnO +1.8 XB) is more preferable₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃The value of (b) is 0.42 to 1.0.

SiO₂Has the effects of maintaining the stability of the glass, adapting to the forming viscosity of the molten glass and improving the chemical durability of the glass. But if SiO₂Too high a content of (b) may result in glass being refractory. Thus, SiO₂The content of (B) is in the range of 41 to 65.5%, preferably 45 to 58.5%.

ZrO₂Has the functions of improving the chemical stability of the glass and increasing the ion diffusion coefficient of the glass, ZrO₂And also has an effect of improving the anti-falling performance of the glass. In a large amount of Al₂O₃In the case of (2), ZrO₂The solubility in the glass is reduced, and the glass is prone to generate defects such as stones. Thus, ZrO₂The content of (b) is in the range of 0 to 7%, preferably 0 to 2%.

In the high aluminosilicate glass system of the present invention, a small amount of P is contained₂O₅Has the effects of improving the meltability of the glass and reducing the crystallization of the glass. P₂O₅And the glass network can be modified, so that the effect of chemically strengthening the glass is improved. At the same time, a small amount of P₂O₅The hardness and the corrosion resistance of the glass cannot be obviously influenced; suitably comprisesP₂O₅And the glass has the beneficial effect of improving the light transmittance of the glass. However, P₂O₅Volatile in continuous production, volatile falls into molten glass to cause ingredient nonuniformity, and contains P₂O₅The glass is easy to generate phase separation at the lower temperature of the electric melting and all-platinum continuous melting production line, and is not beneficial to the production of the glass. Thus, P in the present invention₂O₅The content of (b) is in the range of 0.1 to 8%, preferably 0.3 to 4%, more preferably 0.7 to 2.5%.

P₂O₅Solubility in glass is influenced by Al₂O₃The influence of the content is large, and therefore, in order to ensure that the glass does not exhibit opacification, it is preferable to control P₂O₅/Al₂O₃Is 0.4 or less, more preferably P₂O₅/Al₂O₃0.05 to 0.25.

La₂O₃The ionic field intensity is large, and the method has a remarkable effect on improving the glass hardness. However, La₂O₃The softening temperature of the glass can be raised, and the secondary hot processing of the glass is not facilitated. Thus, La₂O₃The content of (b) is in the range of 0 to 15%, preferably 0 to 5%.

Sb₂O₃And SnO₂Can be used as a clarifying agent and can improve the clarifying effect in glass. The invention defines Sb₂O₃In an amount of 0 to 1%, preferably 0.02 to 0.7%, more preferably 0.05 to 0.4%, and/or SnO₂The content of (b) is in the range of 0 to 3%, preferably 0.01 to 3%, more preferably 0.4 to 1.5%.

CeO₂Can be used as a clarifying agent, but contains CeO₂The ultraviolet absorption ray of the glass can be shifted to the right, the color of the glass is yellow, and the appearance of the glass is not ideal. Therefore, CeO is preferably not contained in the present invention₂。

TiO₂The ion diffusion coefficient of the glass can be increased, but TiO₂The glass has the function of a nucleating agent, and is not beneficial to secondary pressing of the glass. Therefore, the present invention preferably does not contain TiO₂。

In order to realize environmental protection, the invention glassThe glass preferably does not contain PbO and As₂O₃。

"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.

< method for producing glass >

The glass manufacturing method comprises the following steps: common raw materials for glass (such as oxides, hydroxides, carbonates, sulfates, nitrates, phosphates, metaphosphates, etc.) are weighed and mixed correspondingly according to the composition of the glass, and the mixed raw materials are placed in a melting apparatus (such as a platinum crucible) and heated and melted. After the above raw materials are completely melted and vitrified, the temperature of the molten glass is raised and the glass is refined. Homogenizing the clarified molten glass by stirring of a stirrer, or continuously supplying the molten glass to a glass outflow pipeline for outflow, and carrying out rapid cooling and solidification on a glass mold to obtain glass; or pouring the glass into a mold with a specific shape from a melting container, and carrying out processes of quenching, solidification and annealing to obtain the glass. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

[ glass product and Process for producing the same ]

Forming a glass product by the glass through a chemical strengthening process; or the glass is made into a glass forming body through various processes and then is formed into a glass product through a chemical strengthening process.

The glass shaped body is obtained by cold working and/or hot working the glass. For example, the glass of the present invention may be produced into a glass shaped body by a method such as grinding or polishing, but the production of the glass shaped body is not limited to these methods. The glass of the present invention can be produced into glass shaped articles of various shapes by a method such as hot bending or press molding at a certain temperature, but the production of the glass shaped articles is not limited to these methods. The glass shaped body includes, but is not limited to, a sheet, a block, a curved body, and the like, wherein the "curved body" means that the surface of the glass shaped body includes one or more curved surfaces of any shape. The glass shaped bodies of the present invention can have any reasonably useful size range, such as thickness or diameter.

In some embodiments, the glass described herein can be manufactured into glass shaped bodies including, but not limited to, sheets by various processes including, but not limited to, slot draw, float, roll, and other processes of forming sheets. Alternatively, the glass may be formed by a float process or a roll process, and a glass shaped body is formed.

In some embodiments, the glass may be processed into sheets, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or swept, and chemically strengthened by a chemical strengthening process.

In some embodiments, the chemical strengthening process of the present invention comprises ion exchange.

The ion exchange method according to the present invention is a method in which when a glass or a glass molded body is immersed in a molten salt having a predetermined composition, monovalent metal cations (for example, Li) in the glass or the glass molded body⁺、Na⁺、K⁺、Ag⁺Etc.) to replace other monovalent metal cations near the glass or glass forming body.

In some embodiments, the ion exchange process of the present invention is to immerse the glass or glass shaped body in a single salt bath, or to immerse the glass or glass shaped body in multiple salt baths of the same or different compositions. When ion exchange is performed in multiple salt baths of different compositions, there may be washing and/or annealing steps between immersions.

The preferred ion exchange method of the present invention is a 1-step ion exchange method or a 2-step ion exchange method.

In some embodiments, the molten salt of the salt bath in the 1-step ion exchange process of the present invention may be composed of two or more compounds in a ratio wherein at least one of the compounds contains a K salt (e.g., KNO)₃) Or Na salt (e.g. NaNO)₃) Preferably KSalt (e.g. KNO)₃) The temperature range of the salt bath is 400-510 ℃, the preferable range is 420-500 ℃, and the time range of the salt bath is 4-32 hours, and the preferable range is 8-24 hours.

In some embodiments, the molten salt of the first salt bath in the 2-step ion exchange process of the present invention may be composed of two or more compounds in a ratio that includes at least a K salt (e.g., KNO)₃) And Na salts (e.g., NaNO)₃) Preferably containing both K salts (e.g. KNO)₃) And Na salts (e.g., NaNO)₃) The temperature range of the first-step salt bath is 400-510 ℃, the preferable range is 420-500 ℃, and the time range of the first-step salt bath is 4-32 hours, and the preferable range is 8-24 hours. The molten salt of the second salt bath may be composed of one or more compounds in a certain proportion, wherein at least one of them contains K salt (such as KNO)₃) Or Na salt (e.g. NaNO)₃) Preferably a K salt (e.g. KNO)₃). The temperature range of the second-step salt bath is 400-510 ℃, preferably 420-500 ℃, and more preferably the same as the temperature of the first-step salt bath; the time range of the second-step salt bath is 0.5-16 h, preferably 0.5-8 h, and more preferably 0.5-4 h.

In some embodiments, the chemical strengthening process of the present invention comprises an ion implantation process for implanting ions into a surface layer of a glass or glass shaped body.

In some embodiments, the chemical strengthening process of the present invention comprises a thermal strengthening process in which the glass or glass shaped body is heated and then rapidly cooled.

The properties of the glass and glass product of the present invention will be described below.

< refractive index >

Refractive index (n) of glass_d) The test was carried out according to the method specified in GB/T7962.1-2010.

In some embodiments, the refractive index (n) of the glasses of the invention_d) Is 1.470 to 1.540, preferably 1.490 to 1.510.

< light transmittance >

The invention adopts' T_550nm"means the light transmittance of the glass, i.e., the glass corresponding to a light wavelength of 550nmGlass transmittance.

“T_550nm"test as follows: spectral transmittance obtained from incident light in a direction perpendicular to the ground surfaces using a sample having surfaces parallel to each other ground to a thickness of 5.0 ± 0.1 mm. The spectral transmission also includes reflection loss of light on the sample surface. The polishing means that the surface roughness is smoothed to be sufficiently small with respect to the wavelength in the measurement wavelength range. T is_550nmThe error range of the measurement was. + -. 0.2%.

In some embodiments, the light transmittance (T) of the glasses of the invention_550nm) 91.0% or more, preferably 91.4% or more, and more preferably 91.8% or more.

< Young's modulus >

Young's modulus (E) was measured according to the method specified in GB/T7962.6-2010.

In some embodiments, the glasses of the invention have a Young's modulus (E) of 7800X 10⁷Pa or more, preferably 8000X 10⁷Pa or more, more preferably 8200X 10⁷Pa or above.

The glass product of the invention has the following properties besides the excellent properties of the glass:

< micro Vickers hardness >

The micro vickers hardness was measured according to the following method: the test was carried out using a microhardness tester with a microscopic observation device. Using a rectangular parallelepiped sample having a plane of grinding and polishing, the area of the polishing plane of the sample should be larger than 1cm²And should be much larger than the indenter tip size for the vickers hardness test. A standard vickers hardness indenter, i.e., a vickers hardness diamond indenter with an apex angle of 136 °, was used. And applying a test force of 200g on the indenter to enable the indenter to vertically contact with the polished plane of the sample, keeping for 20 seconds, removing the indenter, and converting the Vickers hardness according to the length of the diagonal line of the indentation. The test error of vickers hardness was 5% of the measured value.

In some embodiments, the glass article of the present invention has a micro vickers hardness of 680 x 10⁷Pa or more, preferably 690X 10⁷Pa or more, more preferably Pa700×10⁷Pa or above.

[ glass preform and glass Member ]

The glass preform can be produced from the glass or glass product produced by means of, for example, grinding or press molding such as reheat press molding or precision press molding. That is, a glass preform may be produced by machining a glass or a glass product by grinding, polishing, or the like, or a glass preform may be produced by producing a preform for press molding from a glass or a glass product, reheat-pressing the preform, and then polishing, or a glass preform may be produced by precision press-molding the preform obtained by polishing. It should be noted that the means for producing the glass preform is not limited to the above means.

The glass or glass articles of the present invention, as well as glass preforms, can be used to make glass components including, but not limited to, glass cover plates, prisms, lenses, and the like. As described above, the glass or glass product of the present invention is useful for cover glass for applications such as mobile phones, wearable devices, display screens, solar panels, and the like, and among them, it is particularly preferable to form a glass molded product from the glass of the present invention, and then produce the glass product by the chemical strengthening process of the present invention to produce a glass element such as a cover glass (e.g., a panel or a back plate of a mobile phone, a smart watch, a computer, and the like). The glass and glass product of the present invention can be used to form a preform, and the preform can be used to produce a glass element such as a lens or a prism by reheat press forming, precision press forming or the like.

Both the glass preform and the glass element of the present invention can be formed from the glass or glass article of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by glass or glass products; the glass member of the present invention has excellent characteristics possessed by glass or glass products.

[ apparatus ]

The glass or glass product and the glass element made of the glass or glass product can be used for manufacturing equipment such as electronic equipment, portable communication equipment (such as a mobile phone), intelligent wearing equipment, photographic equipment, camera equipment, display equipment, monitoring equipment and the like.

Examples

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

< glass examples >

The present invention provides glasses having compositions shown in tables 1 to 3, which are obtained by the above-mentioned glass production method. The characteristics of each glass were measured by the test method described in the present invention, and the test results are shown in tables 1 to 3.

Table 1.

Table 2.

Table 3.

< glass article examples >

Glass products were produced by the glass production method using the glasses shown in tables 1 to 3, and chemical strengthening processes are shown in tables 4 to 8. The characteristics of each glass product were measured by the test method described in the present invention, and the test results are shown in tables 4 to 8.

Table 4.

Table 5.

Table 6.

Table 7.

Table 8.

Claims

1. Glass, characterized in that its composition, expressed in weight percentages, comprises: SiO 2₂：41～65.5％；Al₂O₃：17.5～31％；Li₂O+Na₂O：5～14.5％；P₂O₅: 0.1 to 8% of Li₂O/(Li₂O+Na₂O) is 0.1 to 0.4, P₂O₅/Al₂O₃0 to 0.004.

2. According to claimThe glass according to claim 1, characterized in that it further comprises, in percentages by weight: k₂O: 0 to 7 percent; and/or ZnO: 0-6%; and/or MgO: 0 to 10 percent; and/or CaO: 0 to 8.5 percent; and/or SrO: 0 to 10 percent; and/or BaO: 0 to 15 percent; and/or B₂O₃: 0-6%; and/or ZrO₂: 0 to 7 percent; and/or La₂O₃: 0 to 15 percent; and/or Ag₂O: 0 to 4.5 percent; and/or Sb₂O₃: 0 to 1 percent; and/or SnO₂：0～3％。

3. A glass, characterized in that its composition, expressed in weight percentage, is represented by SiO₂：41～65.5％；Al₂O₃：17.5～31％；Li₂O+Na₂O：5～14.5％；P₂O₅：0.1～8％；K₂O：0～7％；ZnO：0～6％；MgO：0～10％；CaO：0～8.5％；SrO：0～10％；BaO：0～15％；B₂O₃：0～6％；ZrO₂：0～7％；La₂O₃：0～15％；Ag₂O：0～4.5％；Sb₂O₃：0～1％；SnO₂: 0 to 3% of a compound of Li₂O/(Li₂O+Na₂O) is 0.1 to 0.4, P₂O₅/Al₂O₃0 to 0.004.

4. The glass according to any one of claims 1 to 3, wherein the composition, expressed in weight percent, satisfies one or more of the following 3 conditions:

1)Li₂O/(Li₂O+Na₂o) is 0.15 to 0.35;

2)Li₂O+Na₂O+K₂O+Ag₂o is 6-16.5%;

3)(ZnO+1.8×B₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃0.38 to 1.15.

5. A glass according to any one of claims 1 to 3, characterised in that it isThe components are expressed by weight percentage, wherein: SiO 2₂: 45-58.5%; and/or Al₂O₃: 21-25.5%; and/or Li₂O+Na₂O: 6.5-12.5%; and/or P₂O₅: 0.3-4%; and/or K₂O: 0 to 4 percent; and/or ZnO: 0 to 3.5 percent; and/or MgO: 0 to 9 percent; and/or CaO: 0 to 4 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 5 percent; and/or B₂O₃: 0.5-3%; and/or ZrO₂: 0-2%; and/or La₂O₃: 0 to 5 percent; and/or Sb₂O₃: 0.02-0.7%; and/or SnO₂：0.01～3％。

6. The glass according to any one of claims 1 to 3, wherein the composition, expressed in weight percent, satisfies one or more of the following 3 conditions:

1)Li₂O/(Li₂O+Na₂o) is 0.15 to 0.3;

2)Li₂O+Na₂O+K₂O+Ag₂o is 9-14%;

3)(ZnO+1.8×B₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃0.4 to 1.1.

7. A glass according to any one of claims 1 to 3, characterised in that it has the composition, expressed in weight percent, in which: p₂O₅: 0.7-2.5%; and/or K₂O: 0-2%; and/or MgO: 3-7%; and/or Sb₂O₃: 0.05-0.4%; and/or SnO₂：0.4～1.5％。

8. A glass according to any one of claims 1 to 3, characterised in that it has the composition, expressed in weight percent, in which: (ZnO +1.8 XB)₂O₃+0.7×MgO+2×CaO+SrO+BaO)/Al₂O₃0.42 to 1.0.

9. A glass according to any one of claims 1 to 3, characterised in that it isThe components are expressed by weight percentage, wherein: na (Na)₂O: 3-12.5%; and/or Li₂O：0.8～4％。

10. A glass according to any one of claims 1 to 3, characterised in that it has the composition, expressed in weight percent, in which: na (Na)₂O: 4-11.5%; and/or Li₂O：1～3.8％。

11. A glass according to any one of claims 1 to 3, characterised in that it has the composition, expressed in weight percent, in which: na (Na)₂O: 5-10.5%; and/or Li₂O：1.2～3.6％。

12. A glass according to any one of claims 1 to 3, wherein the glass contains two or more components selected from ZnO, MgO, CaO, SrO and BaO at the same time.

13. A glass according to any one of claims 1 to 3, wherein the glass contains two or three components selected from ZnO, MgO, CaO, SrO and BaO.

14. A glass according to any one of claims 1 to 3, wherein the glass contains both ZnO, MgO, CaO, SrO and BaO.

15. A glass according to any one of claims 1 to 3, wherein the glass contains both ZnO and MgO.

16. The glass according to any one of claims 1 to 3, wherein the glass does not contain Ag₂O; and/or does not contain TiO₂(ii) a And/or does not contain CeO₂(ii) a And/or does not contain CaO; and/or does not contain SrO; and/or no BaO; and/or does not contain PbO; and/or does not contain As₂O₃。

17The glass according to any one of claims 1 to 3, wherein the glass has a refractive index n_d1.470 to 1.540; and/or light transmission T_550nmMore than 91.0 percent; and/or a Young's modulus E of 7800X 10⁷Pa or above.

18. The glass according to any one of claims 1 to 3, wherein the glass has a refractive index n_d1.490 to 1.510; and/or light transmission T_550nmMore than 91.4 percent; and/or a Young's modulus E of 8000X 10⁷Pa or above.

19. The glass according to any one of claims 1 to 3, wherein the glass has a light transmittance T_550nmMore than 91.8 percent; and/or a Young's modulus E of 8200X 10⁷Pa or above.

20. A glass article characterized by being made of the glass according to any one of claims 1 to 19.

21. The glass article of claim 20, wherein the glass article has a micro vickers hardness of 680 x 10⁷Pa or above.

22. The glass article of claim 20, wherein the glass article has a micro vickers hardness of 690 x 10⁷Pa or above.

23. The glass article of claim 20, wherein the glass article has a micro vickers hardness of 700 x 10⁷Pa or above.

24. A glass preform made from the glass according to any one of claims 1 to 19 or the glass product according to any one of claims 20 to 23.

25. A glass element made of the glass according to any one of claims 1 to 19 or the glass product according to any one of claims 20 to 23.

26. An apparatus comprising a glass according to any one of claims 1 to 19, and/or comprising a glass product according to any one of claims 20 to 23, and/or comprising a glass element according to claim 25.

27. A method of making a glass article, comprising the steps of: forming the glass according to any one of claims 1 to 19, forming a glass product by a chemical strengthening process, or forming a glass product by a chemical strengthening process after manufacturing the glass into a glass forming body by various processes.

28. The method of claim 27, wherein the glass is formed into a glass shaped body by a grinding or polishing process or by a hot bending or pressing process at a certain temperature.

29. The method of manufacturing a glass article according to claim 27, wherein the chemical strengthening process is immersing the glass or glass shaped body in a single salt bath or immersing the glass or glass shaped body in multiple salt baths having the same or different compositions.

30. The method for manufacturing a glass product according to claim 27, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt of a salt bath is composed of two or more compounds in a certain ratio, at least one of the compounds contains a K salt or a Na salt, the temperature of the salt bath is 400 to 510 ℃, and the time of the salt bath is 4 to 32 hours.

31. The method for manufacturing a glass product according to claim 27, wherein the chemical strengthening process is a 1-step ion exchange method in which a molten salt of a salt bath is composed of two or more compounds in a certain ratio, at least one of the compounds contains a K salt, the temperature of the salt bath is 420 to 500 ℃, and the time of the salt bath is 8 to 24 hours.

32. The method for manufacturing a glass product according to claim 27, wherein the chemical strengthening process is a 2-step ion exchange method in which the molten salt of the first-step salt bath is composed of two or more compounds in a certain ratio, wherein the molten salt at least contains one or two of a K salt and a Na salt, the temperature of the first-step salt bath is 400 to 510 ℃, and the time of the first-step salt bath is 4 to 32 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound contains K salt or Na salt, and the temperature range of the second-step salt bath is 400-510 ℃; the time range of the second-step salt bath is 0.5-16 h.

33. The method for manufacturing a glass product according to claim 27, wherein the chemical strengthening process is a 2-step ion exchange method in which a molten salt in a first-step salt bath is composed of two or more compounds in a certain proportion, wherein the molten salt contains a K salt and a Na salt, the temperature of the first-step salt bath is 420 to 500 ℃, and the time of the first-step salt bath is 8 to 24 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound is K salt, and the temperature range of the second-step salt bath is 420-500 ℃; the time range of the second-step salt bath is 0.5-8 h.

34. The method for manufacturing a glass product according to claim 27, wherein the chemical strengthening process is a 2-step ion exchange method in which a molten salt in a first-step salt bath is composed of two or more compounds in a certain proportion, wherein the molten salt contains a K salt and a Na salt, the temperature of the first-step salt bath is 420 to 500 ℃, and the time of the first-step salt bath is 8 to 24 hours; the molten salt of the second-step salt bath is composed of one or more than one compound according to a certain proportion, wherein at least one compound is K salt, and the temperature of the second-step salt bath is the same as that of the first-step salt bath; the time range of the second-step salt bath is 0.5-4 h.