CN115583793A - Non-fragile rapid ion exchange glass and preparation method and application thereof - Google Patents
Non-fragile rapid ion exchange glass and preparation method and application thereof Download PDFInfo
- Publication number
- CN115583793A CN115583793A CN202211319363.2A CN202211319363A CN115583793A CN 115583793 A CN115583793 A CN 115583793A CN 202211319363 A CN202211319363 A CN 202211319363A CN 115583793 A CN115583793 A CN 115583793A
- Authority
- CN
- China
- Prior art keywords
- glass
- percent
- ion exchange
- mole
- percentage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 163
- 238000005342 ion exchange Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 26
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 43
- 230000008018 melting Effects 0.000 claims description 43
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000008395 clarifying agent Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000007500 overflow downdraw method Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000156 glass melt Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000005357 flat glass Substances 0.000 abstract description 10
- 238000005728 strengthening Methods 0.000 abstract description 7
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000005345 chemically strengthened glass Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
The invention discloses non-fragile rapid ion exchange glass and a preparation method and application thereof, belonging to the technical field of glass preparation. The components of the fast ion exchange glass with non-fragility comprise the following components in mole percentage: 58.2 to 68 percent of SiO 2 8.9 to 15 percent of Al 2 O 3 10 to 16 percent of Na 2 O, 2 to 5 percent of MgO and 0.6 to 4 percent of B 2 O 3 0.4 to 2 percent of K 2 O, 1-4% of ZnO and 0.1-1% of SnO 2 (ii) a Wherein said Al is 2 O 3 、B 2 O 3 And ZnO in a molar percentage of more than 10% and less than 20%; b 2 O 3 Mole percent of and SiO 2 The ratio of the mole percent of (A) is more than 0.03 and less than 0.08; r 2 The mole percentage of O is more than that of Al 2 O 3 In a molar percentage of (b), wherein R 2 O is Na 2 O and K 2 And (O). The glass has a higher CT value after being subjected to ion exchange strengthening, belongs to non-fragile glass, has the characteristics of deeper ion exchange depth, high surface pressure stress and non-fragility, and is suitable for protective cover plate glass of mobile electronic equipment.
Description
Technical Field
The invention belongs to the technical field of electronic glass preparation, and particularly relates to non-fragile rapid ion exchange glass and a preparation method and application thereof.
Background
In recent years, with the development of 5G communication and other technologies in the mobile terminal market, new requirements such as light weight, high strength and strong crack expansion resistance are put forward on cover glass. The actual strength of the glass is much lower than the theoretical strength due to the existence of cracks on the surface of the glass, and the strength of the glass can be improved by reducing the generation of cracks and preventing the propagation of the cracks. At present, a method of chemical strengthening, also called chemical toughening, is mainly adopted to prevent crack expansion. The principle of chemical strengthening is as follows: smaller ions in the glass can be replaced with larger ions in a salt bath molten sample at high temperature, and the replaced larger ions can be tightly stacked on the surface of the glass to generate stronger compressive stress, so that higher strength is expressed. However, when the chemically strengthened glass obtained by chemically strengthening a specific glass raw material in the prior art falls from a high place, a breakage phenomenon may occur in a state of a large central tensile stress and a large strength, and the broken pieces generated by the breakage may cause a risk of injury to a user.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a non-fragile rapid ion exchange glass, a preparation method and application thereof, which are used for solving the technical problem that the chemically strengthened glass is easy to have a breakage phenomenon under the condition of larger central tensile stress and larger strength.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a non-fragile rapid ion exchange glass, which comprises the following components in percentage by mole: 58.2 to 68 percent of SiO 2 8.9 to 15 percent of Al 2 O 3 10 to 16 percent of Na 2 O, 2 to 5 percent of MgO and 0.6 to 4 percent of B 2 O 3 0.4 to 2 percent of K 2 O, 1 to 4 percent of ZnO and 0.1 to 1 percent of SnO 2 ；
Wherein said Al is 2 O 3 、B 2 O 3 And ZnO in a molar percentage of greater than 10% and less than 20%; b is 2 O 3 Mole percent of and SiO 2 The ratio of the mole percent of (A) is more than 0.03 and less than 0.08;
R 2 the mole percentage of O is more than that of Al 2 O 3 In a molar percentage of (B), wherein R 2 O is Na 2 O and K 2 O。
Further, the fast ion-exchanged glass having non-fragility has a maximum value of surface compressive stress of 945MPa; the maximum value of the depth of the compressive stress layer of the rapid ion exchange glass with non-frangibility is 42.6 mu m, the central tension is 79 MPa-90 MPa, and the average value of the number of fragments in the frangibility test is 0.5pcs/in 2 。
Further, the thickness of the non-brittle rapid ion exchange glass is 0.3mm to 3.0mm.
The invention also discloses a preparation method of the non-fragile rapid ion exchange glass, which comprises the following steps:
s1: mixing glass raw materials and a glass clarifying agent to obtain a mixture, melting the mixture to obtain glass melt, and carrying out molding treatment on the glass melt to obtain molded glass;
s2: and placing the formed glass in salt solution for salt bath chemical strengthening to obtain the non-fragile rapid ion exchange glass.
Further, the temperature of the chemical strengthening is 400-440 ℃, and the time of the chemical strengthening is not more than 240min.
Further, the components of the glass raw material comprise, in mole percentage: 58.2 to 68 percent of SiO 2 8.9 to 15 percent of Al 2 O 3 10 to 16 percent of Na 2 O, 2 to 5 percent of MgO and 0.6 to 4 percent of B 2 O 3 0.4 to 2 percent of K 2 O and 1 to 4 percent of ZnO; the glass refining agent is SnO 2 (ii) a The SnO 2 The mole percentage of (A) is 0.1% -1%;
wherein said Al is 2 O 3 、B 2 O 3 And ZnO in a molar percentage of more than 10% and less than 20%; b is 2 O 3 Mole percent of and SiO 2 The ratio of the mole percent of (A) is more than 0.03 and less than 0.08;
R 2 the mole percentage of O is more than that of Al 2 O 3 In a molar percentage of (b), wherein R 2 O is Na 2 O and K 2 O。
Further, the salt solution is one or two of a potassium salt solution and a sodium salt solution.
Further, the mixture is dissolved by a glass melting furnace, and the melting temperature is 1650-1780 ℃.
Further, the glass melt is molded by an overflow down-draw method to obtain molded glass.
The invention also discloses application of the non-fragile rapid ion exchange glass as a screen protection material of a flat panel display device.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a non-fragile rapid ion exchange glass, and SiO in the components of the non-fragile rapid ion exchange glass 2 Is the primary glass former and forms the network skeleton for the molten glass. SiO 2 2 Should be high enough to increase the chemical durability and mechanical strength of the glass sufficiently for use in touch screen applications. But excessive SiO 2 The glass transition temperature and the melting temperature are increased, the glass with long material property is difficult to obtain, and the content of the glass can meet the requirements of chemical durability and melting within 58.2 to 68 percent in molar percentage; al in the composition 2 O 3 Can be used as glass forming agent in glass, and is intermediate oxide when Al is used 3+ In the four coordinate state [ AlO4 ]]The tetrahedral form participates in network formation by the ratio of [ SiO ] 4 ]The tetrahedron has large volume, so that larger pores in a glass system are used as ion diffusion channels, and Na can be promoted during chemical strengthening + →K + In addition, since too large an amount of Al causes an increase in the softening temperature of the glass and makes it difficult to obtain a glass having long glass properties, al is used 2 O 3 The content of (A) is 10% -15%; na in the component 2 O and K 2 The O alkali metal oxide is a network exo-oxide, which mainly acts as a network breaking function, helps to lower the melting temperature and liquidus temperature, and at the same time, serves as an ion exchange source that promotes chemically strengthened ion exchange, but the addition of the alkali metal oxide dramatically increases the Coefficient of Thermal Expansion (CTE) of the glass and decreases chemical durability; the divalent alkaline earth oxides MgO and ZnO improve the melting behavior of the glass, but for ion exchange properties the presence of divalent cations tends to reduce the mobility of alkali ions, while also increasing the CTE and young's and shear moduli; b is 2 O 3 Is a glass forming oxide, is used to reduce viscosity, improve melting and glass forming ability, and may be present in the glass in a tridentate or tetradentate form, with tridentate B 2 O 3 Is a tetradentate [ BO4 ] for reducing Young's modulus and shear modulus]Is relatively dense and has an effect of inhibiting the migration of ions in the glass. Addition of B 2 O 3 To partially replace SiO 2 The network structure of the glass can be changed, and B is suitable 2 O 3 /SiO 2 Can reduce the thermal expansion coefficient, density and brittleness of the glass and improve the crack propagation resistance of the glass. B 2 O 3 /SiO 2 The ratio range of (A) is 0.03-0.08; snO 2 The glass refining agent is added into glass components as a glass refining agent, the adding amount of the glass refining agent is usually 0.1-1%, and bubbles in glass melt can be eliminated. According to the related experiment results, the glass compressive stress depth of layer (DOL) of the non-fragile rapid ion exchange glass disclosed by the invention can reach 42.6 mu m, the Compressive Stress (CS) is more than 900MPa, and the non-fragile rapid ion exchange glass has a better stress state and strength and is non-fragile.
The invention also discloses a preparation method of the non-fragile rapid ion exchange glass, because of adopting the specific glass raw materials disclosed in the application, the time required for chemical strengthening is short, the strengthening efficiency is high, the depth of a compressive stress layer (DOL) of a sample can reach 42.6 mu m within 4 hours, the Compressive Stress (CS) can reach 945MPa, the sample has good impact resistance, the integrity of the glass can be kept under the action of large impact force, the invention has the characteristics of deeper ion exchange depth, high surface compressive stress and non-fragile property, the situation of cracking is not generated, and the falling ball impact resistance E = m after the glass is subjected to ion exchange strengthening Falling ball gh Height of fall ≥0.5J。
The invention also discloses application of the non-fragile rapid ion exchange glass as a screen protection material of a flat panel display device, and the non-fragile rapid ion exchange glass has the characteristics of short time required for chemical strengthening, high strengthening efficiency, deep ion exchange depth, high surface compressive stress and non-fragility, can be used as outer layer protection cover plate glass of a touch screen device to reduce crushing damage caused by small glass sheets generated by self-accelerated high-degree fracture and crushing, and has good application prospect.
Drawings
FIG. 1 is a diagram of impact energy test ball drop points for a non-frangible rapid ion exchange glass made according to the present invention.
Detailed Description
To make the features and effects of the invention comprehensible to those skilled in the art, general description and definitions shall be provided below with respect to terms and words mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without being limited by any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are provided for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," "including," "having," or similar terms, shall mean "consisting of 8230; \8230, composition" and "consisting essentially of 8230; \8230, composition" such as "A comprises a" shall mean "A comprises a and the other" and "A comprises a only".
In the present context, for the sake of brevity, all possible combinations of various features in various embodiments or examples are not described. Therefore, as long as there is no contradiction between combinations of these technical features, any combinations of the technical features in the respective embodiments or examples may be made, and all possible combinations should be considered as the scope of the present specification.
The present invention uses methods known in the art to measure Compressive Stress (CS) and depth of stress layer (DOL), and the present patent uses a FSM-6000 instrument to measure CS and DOL. The impact resistance falling ball energy test adopts five-point one-time and limit crushing test according to E = m Falling ball gh Height of fall And calculating the shock resistance energy of the reinforced sample.
The chemical strengthening ion exchange is carried out by adopting a low-temperature method, namely, when the glass transition temperature Tg is lower, a glass sample is immersed in a molten salt bath, so that larger ions in the salt bath are exchanged with smaller ions in the glass to generate a 'squeezing effect', and thus, compressive stress is generated on the surface of the glass.
The "fragility" of glass is an inherent property of the sample, namely the branching of cracks due to the release of the internal energy stored by the sample during fracture. It is important to use only the minimum external force required for rupture, as the rupture mode is governed by the stored elastic energy in the sample and is not affected by significant excess energy. The main parameters for the test were time to break and breakage pattern, and the size evaluation was the number of fragments formed per unit area of the glass article.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Instrumentation conventional in the art is used in the following examples. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A method for preparing a non-brittle, fast ion-exchange glass comprising the steps of:
s1: mixing the glass raw material and the glass refining agent according to the mol percentage of 58.2 percent of SiO 2 13.2% of Al 2 O 3 14.3% of Na 2 O, 4.9% of MgO and 3.7% of B 2 O 3 1.9% of K 2 O, 2.8% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, and the others are glass raw materials; al (aluminum) 2 O 3 、B 2 O 3 And ZnO in a total of 19.7 mol%, B 2 O 3 /SiO 2 Is 0.06, R 2 The mole percentage of O is 16.2%, R 2 O is Na 2 O and K 2 O alkali metal oxide; melting the mixture in a glass melting furnace in an all-electric melting furnace mode, wherein the melting temperature is 1650 ℃, and the mixture is formed by an overflow down-draw method to obtain flat glass with the thickness of 0.7mm, and the cutting size is 146 multiplied by 70mm;
s2: placing the formed glass on KNO 3 Performing chemical strengthening on salt bath in a salt solution to obtain the non-fragile rapid ion exchange glass; the temperature of the chemical strengthening is 400 ℃, and the time of the chemical strengthening is 240min.
Example 2
A method for preparing a non-brittle, fast ion-exchange glass comprising the steps of:
s1: the glass raw material and the glass clarifying agent are mixed according to the mol percentage of 59.4 percent of SiO 2 11.5% of Al 2 O 3 15.4% of Na 2 O, 3.8% of MgO and 3.9% of B 2 O 3 1.6% of K 2 O, 2.8% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, the other is glass raw material, al 2 O 3 、B 2 O 3 And ZnO in a molar percentage of 18.8%, B 2 O 3 /SiO 2 Is 0.07, R 2 The mole percentage of O is 17.0%; melting the mixture in a glass melting furnace, wherein the melting mode can be an all-electric melting furnace, the melting temperature is 1650 ℃, and the mixture is molded by an overflow down-draw method to obtain the plate glass with the thickness of 0.7mm, and the cutting size is 146 multiplied by 70mm;
s2: placing the shaped glass on NaNO 3 Performing chemical strengthening on salt bath in a salt solution to obtain the non-fragile rapid ion exchange glass; the temperature of the chemical strengthening is 415 ℃, and the time of the chemical strengthening is 230min.
Example 3
A method for preparing a non-brittle, fast ion-exchange glass comprising the steps of:
s1: the glass raw material and the glass clarifying agent are mixed according to the mol percentage ratio, and SiO is 63.4 percent 2 12.0% of Al 2 O 3 13.5% of Na 2 O, 4.7% of MgO and 2.3% of B 2 O 3 1.3% of K 2 O, 1.8% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, the other is glass raw material, al 2 O 3 、B 2 O 3 And ZnO in a total of 16.1 mol%, B 2 O 3 /SiO 2 Is 0.04, R 2 The mole percentage of O is 14.8%; melting the mixture in a glass melting furnace, wherein the melting mode can be an all-electric melting furnace, the melting temperature is 1650 ℃, and the mixture is molded by an overflow down-draw method to obtain the plate glass with the thickness of 0.7mm, and the cutting size is 146 multiplied by 70mm;
s2: placing the formed glass on KNO 3 Chemically strengthening salt bath in salt solution to obtain non-fragile rapid ion exchange glass; the temperature of the chemical strengthening is 420 ℃, and the time of the chemical strengthening is 220min.
Example 4
A method for preparing a non-brittle, fast ion-exchange glass comprising the steps of:
s1: mixing glass raw material and glass refining agent according to the mol percentage of 64.2 percent of SiO 2 11.9% of Al 2 O 3 12.5% of Na 2 O, 3.1% of MgO and 3.5% of B 2 O 3 1.7% of K 2 O, 2.1% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, and the rest is glass raw material, al 2 O 3 、B 2 O 3 And ZnO in a total of 17.5 mol%, B 2 O 3 /SiO 2 Is 0.05, R 2 The mole percentage of O is 14.2%; melting the mixture in a glass furnaceThe melting mode can adopt an all-electric melting furnace mode, the melting temperature is 1650 ℃, the sheet glass with the thickness of 0.7mm is obtained by adopting an overflow down-draw method, and the cutting size is 146 multiplied by 70mm;
s2: placing the formed glass on KNO 3 Performing chemical strengthening on salt bath in a salt solution to obtain the non-fragile rapid ion exchange glass; the temperature of the chemical strengthening is 425 ℃, and the time of the chemical strengthening is 215min.
Example 5
A method for preparing a non-brittle, fast ion-exchange glass comprising the steps of:
s1: the glass raw material and the glass clarifying agent are mixed according to the mol percentage of SiO 6% 2 9.3% of Al 2 O 3 13.8% of Na 2 O, 4.0% of MgO and 3.5% of B 2 O 3 1.0% of K 2 O, 2.9% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, and the rest is glass raw material, al 2 O 3 、B 2 O 3 And ZnO in a total of 15.1 mol%, B 2 O 3 /SiO 2 Is 0.054, R 2 The mole percentage of O is 14.8%; melting the mixture in a glass melting furnace, wherein the melting mode can be an all-electric melting furnace, the melting temperature is 1650 ℃, and the mixture is molded by an overflow down-draw method to obtain the plate glass with the thickness of 0.7mm, and the cutting size is 146 multiplied by 70mm;
s2: placing the formed glass on KNO 3 Performing chemical strengthening on salt bath in a salt solution to obtain the non-fragile rapid ion exchange glass; the temperature of the chemical strengthening is 430 ℃, and the time of the chemical strengthening is 215min.
Example 6
A method for preparing a non-brittle, fast ion-exchanged glass comprising the steps of:
s1: the glass raw material and the glass clarifying agent are mixed according to the mol percentage of SiO 59 percent 2 11.4% of Al 2 O 3 11.8% of Na 2 O、2.8％MgO of (2) and 4% of B 2 O 3 1.1% of K 2 O, 3.7% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, and the rest is glass raw material, al 2 O 3 、B 2 O 3 And ZnO in a molar percentage of 17.6% in total, B 2 O 3 /SiO 2 Is 0.067, R 2 The mole percentage of O is 12.9%; melting the mixture in a glass melting furnace, wherein the melting mode can be an all-electric melting furnace mode, the melting temperature is 1650 ℃, the mixture is molded by adopting an overflow down-draw method to obtain sheet glass with the thickness of 0.7mm, and the cutting size is 146 x 70mm;
s2: placing the formed glass on KNO 3 Performing chemical strengthening on salt bath in a salt solution to obtain the non-fragile rapid ion exchange glass; the temperature of the chemical strengthening is 435 ℃, and the time of the chemical strengthening is 210min.
Example 7
A method for preparing a non-brittle, fast ion-exchanged glass comprising the steps of:
s1: the glass raw material and the glass clarifying agent are mixed according to the mol percentage of 68.0 percent of SiO 2 8.9% of Al 2 O 3 12.8% of Na 2 O, 3.4% of MgO and 3.9% of B 2 O 3 0.8% of K 2 O, 3.0% ZnO and 1.0% SnO 2 Mixing to obtain a mixture, wherein SnO 2 Is glass clarifying agent, the other is glass raw material, al 2 O 3 、B 2 O 3 And ZnO in a total of 14.0 mol%, B 2 O 3 /SiO 2 Is 0.0057, R 2 The mole percentage of O is 13.6%; melting the mixture in a glass melting furnace, wherein the melting mode can be an all-electric melting furnace, the melting temperature is 1650 ℃, and the mixture is molded by an overflow down-draw method to obtain the plate glass with the thickness of 0.7mm, and the cutting size is 146 multiplied by 70mm;
s2: placing the formed glass on KNO 3 Salt bath in salt solution is chemically strengthened to obtain a toolFast ion exchange glass with non-fragility; the temperature of the chemical strengthening is 440 ℃, and the time of the chemical strengthening is 210min.
Table 1 shows the data of the performance test of the non-brittle rapid ion-exchange glass prepared in examples 1-7, wherein the surface Compressive Stress (CS) and the depth of layer (DOL) of the compressive stress of the glass are tested by FSM-6000 LE; the Vickers hardness of the glass is tested by an HXD-1000 Vickers hardness tester; the impact energy of the glass passes the falling ball impact test, five points once. Placing glass in a special grinding tool, setting the position of a falling point 10mm away from each edge and the center point to be five points, testing the falling ball point bitmap by impact resistance energy, wherein the falling ball point bitmap is shown in figure 1, each 64g steel ball is once, the initial height is 30cm, the steel ball is raised by 10cm each time, observing whether a sample generates cracks or is cracked, carrying out limit test, and testing and calculating the falling ball impact resistance energy E = m of the glass Falling ball gh。
As can be seen from Table 1, the non-brittle rapid ion exchange glass sample of the present invention has a depth of compressive stress layer (DOL) of 42.6 μm and a Compressive Stress (CS) of 945MPa, has good impact resistance, can maintain the integrity of the glass under the action of large impact force, does not crack, and has a ball drop impact resistance E = m after ion exchange strengthening Falling ball gh Height of fall ≥0.5J。
Table 1: performance test data for non-brittle, fast ion-exchanged glasses prepared in various examples
Table 2 shows the friability test data for the non-friable fast ion exchange glasses prepared in examples 1-7, the glass friability test passing the relevant equipment test. Firstly, determining proper impact force according to a piezoelectric sensor test program, and observing the delayed crushing state of glass; next, the sample was impacted at the center with an appropriate impact force, and the diamond indenter was freely dropped from a height of 4mm to observe the sample fracture morphology. If the sample did not rupture within 1min of impact, it would be impacted again at the same location; finally, the time required from the last impact of the indenter to the breakage of the sample and the number of broken pieces were recorded to calculate the number of pieces formed per unit area of the glass article, and the fragility of the sample was evaluated.
As can be seen from Table 2, the non-frangible rapid ion exchange glass samples of the present invention have an average frangibility test of 0.5pcs/in 2 The glass belongs to non-fragile glass, has high drop resistance, and is suitable for protective cover plate glass of mobile electronic equipment.
Table 2: friability test data for non-friable fast ion exchange glasses prepared in different examples
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The non-fragile rapid ion exchange glass is characterized in that the mixed raw materials of the non-fragile rapid ion exchange glass comprise the following components in percentage by mole: 58.2 to 68 percent of SiO 2 8.9 to 15 percent of Al 2 O 3 10 to 16 percent of Na 2 O, 2 to 5 percent of MgO and 0.6 to 4 percent of B 2 O 3 0.4 to 2 percent of K 2 O, 1 to 4 percent of ZnO and 0.1 to 1 percent of SnO 2 ；
Wherein said Al is 2 O 3 、B 2 O 3 And ZnO in a molar percentage of more than 10% and less than 20%; b is 2 O 3 Mole percent of and SiO 2 Is greater than 0.03Less than 0.08;
R 2 the mole percentage of O is more than that of Al 2 O 3 In a molar percentage of (b), wherein R 2 O is Na 2 O and K 2 O。
2. The non-brittle rapid ion-exchange glass according to claim 1, wherein the non-brittle rapid ion-exchange glass has a maximum surface compressive stress of 945MPa; the maximum value of the depth of a compressive stress layer of the rapid ion exchange glass with non-frangibility is 42.6 mu m, the central tension is 79 MPa-90 MPa, and the average value of the number of fragments tested by the frangibility is 0.5pcs/in 2 。
3. The non-brittle rapid ion exchange glass according to claim 1, wherein the non-brittle rapid ion exchange glass has a thickness of 0.3mm to 3.0mm.
4. A method of making a non-brittle, fast ion-exchange glass according to any of claims 1-3, comprising the steps of:
s1: mixing a glass raw material and a glass clarifying agent to obtain a mixed raw material, melting the mixed raw material to obtain glass melt, and carrying out molding treatment on the glass melt to obtain molded glass;
s2: and (3) placing the formed glass in a salt solution for salt bath chemical strengthening to obtain the non-fragile rapid ion exchange glass.
5. The method for preparing a non-brittle, fast ion-exchange glass according to claim 4, wherein the temperature of the chemical strengthening is 400 ℃ to 440 ℃ and the time of the chemical strengthening is not more than 240min.
6. The method of claim 4, wherein the fast ion exchange glass is produced by a process comprising the steps ofThe glass raw material comprises the following components in percentage by mole: 58.2 to 68 percent of SiO 2 8.9 to 15 percent of Al 2 O 3 10 to 16 percent of Na 2 O, 2 to 5 percent of MgO and 0.6 to 4 percent of B 2 O 3 0.4 to 2 percent of K 2 O and 1 to 4 percent of ZnO; the glass refining agent is SnO 2 (ii) a The SnO 2 The mole percentage of (A) is 0.1% -1%;
wherein said Al is 2 O 3 、B 2 O 3 And ZnO in a molar percentage of more than 10% and less than 20%; b is 2 O 3 Mole percent and SiO 2 The ratio of the mole percent of (A) is more than 0.03 and less than 0.08;
R 2 the mole percentage of O is more than that of Al 2 O 3 In a molar percentage of (b), wherein R 2 O is Na 2 O and K 2 O。
7. The method of claim 4, wherein the salt solution is one or both of a potassium salt solution and a sodium salt solution.
8. The method of claim 4, wherein the mixture is melted in a glass melting furnace at a temperature of 1650-1780 ℃.
9. The method according to claim 4, wherein the overflow downdraw method is used to shape the glass melt to obtain the shaped glass.
10. Use of the non-brittle fast ion-exchange glass according to any of claims 1-3, characterized in that the non-brittle fast ion-exchange glass is used as a screen protection material for flat panel displays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211319363.2A CN115583793A (en) | 2022-10-26 | 2022-10-26 | Non-fragile rapid ion exchange glass and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211319363.2A CN115583793A (en) | 2022-10-26 | 2022-10-26 | Non-fragile rapid ion exchange glass and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115583793A true CN115583793A (en) | 2023-01-10 |
Family
ID=84782177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211319363.2A Pending CN115583793A (en) | 2022-10-26 | 2022-10-26 | Non-fragile rapid ion exchange glass and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115583793A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105939975A (en) * | 2013-11-26 | 2016-09-14 | 康宁股份有限公司 | Fast ion exchangeable glasses with high indentation threshold |
| CN109020192A (en) * | 2018-10-17 | 2018-12-18 | 科立视材料科技有限公司 | It is a kind of with high strain-point, can fast ion exchange and weak acid resistant zinc phosphorus alumina silicate glass |
| CN113135655A (en) * | 2021-04-21 | 2021-07-20 | 彩虹集团（邵阳）特种玻璃有限公司 | Boron-containing aluminosilicate glass capable of realizing rapid ion exchange |
| CN114573228A (en) * | 2013-08-29 | 2022-06-03 | 康宁股份有限公司 | Ion exchangeable glass containing boron and phosphorus |
-
2022
- 2022-10-26 CN CN202211319363.2A patent/CN115583793A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573228A (en) * | 2013-08-29 | 2022-06-03 | 康宁股份有限公司 | Ion exchangeable glass containing boron and phosphorus |
| CN105939975A (en) * | 2013-11-26 | 2016-09-14 | 康宁股份有限公司 | Fast ion exchangeable glasses with high indentation threshold |
| CN109020192A (en) * | 2018-10-17 | 2018-12-18 | 科立视材料科技有限公司 | It is a kind of with high strain-point, can fast ion exchange and weak acid resistant zinc phosphorus alumina silicate glass |
| CN113135655A (en) * | 2021-04-21 | 2021-07-20 | 彩虹集团（邵阳）特种玻璃有限公司 | Boron-containing aluminosilicate glass capable of realizing rapid ion exchange |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110799467B (en) | Chemically strengthened glass, method for producing same, and glass for chemical strengthening | |
| KR102024126B1 (en) | Chemically strengthened glass and glass for chemical strengthening | |
| TWI491571B (en) | Glass plate for display device, plate glass for display device and production process thereof | |
| KR102391152B1 (en) | Fast ion exchangeable glasses with high indentation threshold | |
| JP5088717B1 (en) | Tempered glass substrate and manufacturing method thereof | |
| US20110014475A1 (en) | Reinforced glass, reinforced glass substrate, and method for producing the same | |
| CN111995243A (en) | High-strength and low-brittleness aluminosilicate glass and strengthening method and application thereof | |
| JP2012184118A (en) | Glass plate for display device | |
| CN103992032B (en) | Be suitable for chemical enhanced glass and enhancement method thereof | |
| CN114929641A (en) | Chemically strengthened glass article and method for producing same | |
| CN113135655A (en) | Boron-containing aluminosilicate glass capable of realizing rapid ion exchange | |
| CN112010552A (en) | Aluminosilicate glass and strengthening method thereof | |
| CN107531563B (en) | Tempered glass | |
| CN115583793A (en) | Non-fragile rapid ion exchange glass and preparation method and application thereof | |
| WO2024014305A1 (en) | Chemically strengthened glass | |
| TW202408959A (en) | chemically strengthened glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |