CN115108721A - Composition for preparing high-aluminosilicate glass, and preparation method and application thereof - Google Patents
Composition for preparing high-aluminosilicate glass, and preparation method and application thereof Download PDFInfo
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- CN115108721A CN115108721A CN202210601004.XA CN202210601004A CN115108721A CN 115108721 A CN115108721 A CN 115108721A CN 202210601004 A CN202210601004 A CN 202210601004A CN 115108721 A CN115108721 A CN 115108721A
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- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 39
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 239000008395 clarifying agent Substances 0.000 claims abstract description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 21
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 11
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000012768 molten material Substances 0.000 claims description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010128 melt processing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000013001 point bending Methods 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000003426 chemical strengthening reaction Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding Methods 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
- 238000005498 polishing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 239000002310 Isopropyl citrate Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004293 potassium hydrogen sulphite Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of glass, and discloses a composition for preparing high-aluminosilicate glass, the high-aluminosilicate glass, and a preparation method and application of the high-aluminosilicate glass. Based on the total mass of the composition, the composition contains 45-70 wt% of SiO 2 20-40 wt% of Al 2 O 3 1-5 wt% of B 2 O 3 0-5 wt% of P 2 O 5 3-12 wt% of Na 2 O, 2-10 wt% of Li 2 O, 0-5 wt% of K 2 O, 1-5 wt% of MgO, 0-5 wt% of CaO, 0-5 wt% of ZrO 2 0-3 wt% of TiO 2 And not more than 1 wt% of clarifying agent. The invention providesThe high-aluminosilicate glass material prepared by the composition has long performance, small crystallization tendency, four-point bending strength of more than 780MPa, and can protect mobile equipment when being scratched by sharp objects.
Description
Technical Field
The invention relates to the technical field of glass, in particular to a composition for preparing high-aluminosilicate glass, the high-aluminosilicate glass, and a preparation method and application thereof.
Background
With the advent of the 5G communication era, smart phones, smart wearable devices, and tablet computers have been developed towards the trend of being thinner and more functional while providing convenience for the life of people, and under such a trend, higher requirements have been put forward on the mechanical properties of cover plate protective glass of smart devices. In the field of display screen protection glass, high aluminosilicate electronic glass subjected to chemical strengthening is generally adopted, and the glass subjected to chemical strengthening has excellent drop resistance and scratch resistance.
The prior art generally adopts one-step or two-step ion exchange to perform chemical strengthening, so that the glass has high surface Compressive Stress (CS) and compressive stress depth of layer (DOL), and generally, the greater the surface Compressive Stress (CS) and the compressive stress depth of layer (DOL) is, the greater the strength of the glass is.
However, the one-step strengthening method mostly needs long-time ion exchange, the depth of a stress layer is far less than 100 μm, and a salt bath for a long time can generate certain stress recession, so that the glass can not meet the use requirement; the two-step strengthening method can enable the glass to obtain ideal surface compressive stress and stress layer depth, but the strengthening process in a short time can enable the average central tensile stress of the glass to be larger, the glass can generate spontaneous explosion risks in the using process, and certain danger can be generated by broken particles.
Meanwhile, the mechanical performance of the traditional cover plate glass needs to be further improved, and in the scratch resistance performance tests of different loads, the threshold value (C) of the scratch width is higher, so that the mobile equipment cannot be completely protected when the mobile equipment is damaged by sharp objects. In addition, the traditional high-aluminosilicate glass has short material property, small liquidus viscosity and larger crystallization risk in the production process.
Therefore, the development of the aluminosilicate glass which can reduce the crystallization tendency and can completely protect mobile equipment when being scratched by a sharp object is of great significance to the intelligent equipment industry.
Disclosure of Invention
The invention aims to overcome the defects of high devitrification tendency and poor sharp object scratch resistance of high-aluminosilicate glass in the prior art.
In order to achieve the above object, the present invention provides in a first aspect a composition for producing a high aluminosilicate glass, the composition containing 45 to 70 wt% of SiO based on the total mass of the composition 2 20-40 wt% of Al 2 O 3 1-5 wt% of B 2 O 3 0-5 wt% of P 2 O 5 3-12 wt% of Na 2 O, 2-10 wt% of Li 2 O, 0-5 wt% of K 2 O, 1-5 wt% of MgO, 0-5 wt% of CaO, 0-5 wt% of ZrO 2 0-3 wt% of TiO 2 A clarifying agent not more than 1 wt%;
the clarifying agent is at least one selected from sulfate, nitrate, halide, stannic oxide and stannous oxide; and
definition K1 ═ Na 2 Mass percent of O/(Li) 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 The mass percentage of O) and K1 is 0.42-0.8;
definition K2 ═ (B) 2 O 3 Mass percentage of (B) + Al 2 O 3 Mass ofFractional content)/(Li 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 The mass percentage of O) and K2 is 1.5-2.9;
definition K3 ═ Li 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 O, and K3 is 6-15 wt%.
Preferably, the composition contains 50-65 wt% of SiO based on the total mass of the composition 2 23-35 wt.% of Al 2 O 3 1-4 wt% of B 2 O 3 0-3 wt% of P 2 O 5 5-10 wt% of Na 2 O, 3-6 wt% of Li 2 O, 0.05-1 wt% of K 2 O, 1-4 wt% of MgO, 0-1 wt% of CaO, 0.5-1.5 wt% of ZrO 2 0-1 wt% of TiO 2 And 0.05-0.8 wt% of a clarifying agent.
Preferably, the K1 is 0.55-0.7.
Preferably, the K2 is 2.1 to 2.9.
Preferably, the fining agent is tin oxide and the tin oxide is present in an amount of 0.1 to 0.3 wt%, based on the total mass of the composition.
In a second aspect, the present invention provides a method of making a high aluminosilicate glass, the method comprising:
(1) melting each component of the composition of the first aspect to obtain a molten material;
(2) sequentially carrying out forming treatment and annealing treatment on the molten material to obtain a glass precursor;
(3) carrying out a first contact reaction on the glass precursor and a metal salt combination I, and carrying out a second contact reaction on a product obtained after the first contact reaction and a metal salt combination II;
wherein the metal salt composition I is a composition of sodium nitrate and potassium nitrate with the dosage mass ratio of 4-8: 1;
the metal salt composition II is prepared from the following components in a dosage-mass ratio of 1: 15-20 of a combination of sodium nitrate and potassium nitrate.
Preferably, in step (1), the conditions of the melt processing include at least: the temperature is 1600 ℃ and 1700 ℃, and the time is 4-8 h.
Preferably, in the step (2), the annealing treatment conditions at least include: the temperature is 550-650 ℃ and the time is 1-3 h.
Preferably, in step (3), the conditions of the first contact reaction and the second contact reaction each independently include: the temperature is 390-450 ℃, and the time is 1-6 h.
In a third aspect, the present invention provides a high aluminosilicate glass produced by the method of the second aspect.
In a fourth aspect, the invention provides a use of the high aluminosilicate glass of the third aspect in a display screen of a smart device.
The high-aluminosilicate glass prepared by the composition provided by the invention has long performance, small crystallization tendency and four-point bending strength over 780MPa, and can protect mobile equipment when being scratched by sharp objects.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the room temperature or the room temperature both represent 25. + -. 2 ℃.
As described above, the first aspect of the present invention provides a composition for producing a high aluminosilicate glass, which contains 45 to 70% by weight of SiO based on the total mass of the composition 2 20-40 wt% of Al 2 O 3 1-5 wt% of B 2 O 3 0-5 wt% of P 2 O 5 3-12 wt% of Na 2 O, 2-10 wt% of Li 2 O, 0-5 wt% of K 2 O, 1-5 wt% of MgO, 0-5 wt% of CaO, 0-5 wt% of ZrO 2 、0-3wt％Of TiO (2) 2 A clarifying agent not more than 1 wt%;
the clarifying agent is at least one selected from sulfate, nitrate, halide, stannic oxide and stannous oxide; and
definition K1 ═ Na 2 Mass percent of O/(Li) 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 The mass percentage of O) and K1 is 0.42-0.8;
definition K2 ═ (B) 2 O 3 Mass percentage of (B) + Al 2 O 3 Mass percent of (C)/(Li) 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 The mass percentage of O) and K2 is 1.5-2.9;
definition K3 ═ Li 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 O, and K3 is 6-15 wt%.
Preferably, the composition contains 50-65 wt% of SiO based on the total mass of the composition 2 23-35 wt.% of Al 2 O 3 1-4 wt% of B 2 O 3 0-3 wt% of P 2 O 5 5-10 wt% of Na 2 O, 3-6 wt% of Li 2 O, 0.05-1 wt% of K 2 O, 1-4 wt% of MgO, 0-1 wt% of CaO, 0.5-1.5 wt% of ZrO 2 0-1 wt% of TiO 2 And 0.05-0.8 wt% of a clarifying agent. The inventors have found that the aforementioned objects are perfectly achieved with this preferred embodiment in order to obtain a high aluminosilicate glass having a low tendency to devitrify while ensuring the resistance to sharp object scratching.
Preferably, the K1 is 0.55-0.7. In the process of research, the inventor finds that by adopting the embodiment in the preferable case, the obtained glass product has more excellent four-point bending strength and can better protect mobile equipment when being scratched by a sharp object.
Preferably, the K2 is 2.1-2.9. By adopting the specific embodiment under the preferable condition, the glass product with stronger capability of resisting the scratch of the sharp object can be obtained, and the four-point bending strength of the glass product exceeds 760 MPa.
According to a particularly preferred embodiment of the invention, the refining agent is tin oxide and the content of tin oxide is 0.1 to 0.3 wt.%, based on the total mass of the composition. In the process of research, the inventor finds that the high-aluminosilicate glass prepared by adopting the embodiment under the preferable condition has the advantages of higher liquidus viscosity, Young modulus and mechanical strength.
As previously mentioned, a second aspect of the invention provides a method of making a high aluminosilicate glass, the method comprising:
(1) melting each component of the composition of the first aspect to obtain a molten material;
(2) sequentially carrying out forming treatment and annealing treatment on the molten material to obtain a glass precursor;
(3) carrying out a first contact reaction on the glass precursor and a metal salt combination I, and carrying out a second contact reaction on a product obtained after the first contact reaction and a metal salt combination II;
wherein the metal salt composition I is a composition of sodium nitrate and potassium nitrate with the dosage mass ratio of 4-8: 1;
the metal salt composition II is prepared from the following components in a dosage-mass ratio of 1: 15-20 of a combination of sodium nitrate and potassium nitrate.
The invention has no special requirements on the specific operation mode of the melting treatment, and illustratively, the components in the composition can be mixed firstly, and then the mixed materials obtained by mixing are subjected to melting treatment simultaneously; or directly adding each component in the composition into a melting furnace for melting treatment.
In order to obtain a molten material with better uniformity, the method comprises the following steps: firstly, the components in the composition are contacted and mixed to obtain a mixed material, and the mixed material is subjected to melting treatment.
Preferably, in step (1), the conditions of the contact mixing at least include: stirring speed is 20-50rpm, temperature is 20-30 deg.C, and time is 5-20 min.
Preferably, in step (1), the conditions of the melt processing include at least: the temperature is 1600 ℃ and 1700 ℃, and the time is 4-8 h.
Preferably, in the step (2), the annealing treatment conditions at least include: the temperature is 550-650 ℃ and the time is 1-3 h.
The method of the molding treatment of the present invention has no particular requirement, and only the requirements of the present invention need to be satisfied, and illustratively, the molten material may be placed in a mold for molding treatment.
Preferably, in the step (2), the conditions of the molding process at least include: the temperature is 1000-1200 ℃, and the time is 1-60 min.
Preferably, in step (2), the method further comprises: and carrying out mechanical processing treatment on the annealed material to obtain the glass precursor.
The mechanical processing treatment is not particularly required by the invention, the mechanical processing method known in the art can be adopted, and illustratively, the material subjected to the annealing treatment can be subjected to the operation steps of cutting, grinding, polishing and the like in sequence.
Preferably, in the step (3), the metal salt combination I is a combination of sodium nitrate and potassium nitrate in an amount mass ratio of 4-6: 1. The inventors have found that with this preferred embodiment, the resulting high aluminosilicate glass has more excellent scratch resistance.
Preferably, in the step (3), the metal salt combination II is used in an amount of 1: 18-20 of a combination of sodium nitrate and potassium nitrate. The inventors have found that, with this preferred embodiment, high aluminosilicate glass having even higher four-point bending strength can be produced.
Preferably, in step (3), the conditions of the first contact reaction and the second contact reaction each independently include: the temperature is 390-450 ℃, and the time is 1-6 h.
The invention has no special requirements on the dosage of the metal salt, and only needs to be capable of completely soaking the glass precursor.
As previously mentioned, a third aspect of the invention provides a high aluminosilicate glass produced by the method of the second aspect.
As previously mentioned, a fourth aspect of the invention provides the use of the high aluminosilicate glass of the third aspect in a display screen of a smart device.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
In the following examples, tin oxide is the analytically pure chemical.
Example 1
This example illustrates the composition of the present invention for making a high aluminosilicate glass according to the formulation and process parameters set forth in table 1, and the high aluminosilicate glass made as described below.
The method for preparing the high-aluminosilicate glass comprises the following steps:
(1) the method comprises the following steps of (1) carrying out contact mixing on all components in the composition for preparing the high-aluminosilicate glass shown in the table 1 to obtain a mixed material, and carrying out melting treatment on the mixed material to obtain a molten material;
wherein the contact mixing conditions are as follows: stirring at 20rpm at 25 deg.C for 5 min;
the conditions of the melt processing were: the temperature is 1700 ℃, and the time is 5 hours;
(2) pouring the prepared molten material into a stainless steel cast iron mold for molding to form a block-shaped glass product (20cm multiplied by 70cm multiplied by 200cm), annealing the block-shaped glass product, cooling to room temperature, sequentially cutting, grinding and polishing, cleaning with deionized water, and drying to obtain a glass precursor with the thickness of 0.9 mm;
wherein the molding treatment conditions are as follows: the temperature is 1050 ℃ and the time is 5 min;
the conditions of the annealing treatment are as follows: the temperature is 580 ℃ and the time is 2 hours;
(3) soaking the prepared glass precursor in a metal salt combination I to perform a first contact reaction, and soaking a product obtained after the first contact reaction in a metal salt combination II to perform a second contact reaction to obtain high-aluminosilicate glass, wherein the name of the high-aluminosilicate glass is S1;
wherein the metal salt composition I is a composition of sodium nitrate and potassium nitrate with the dosage mass ratio of 85: 15;
the metal salt composition II is a composition of sodium nitrate and potassium nitrate with the dosage mass ratio of 1: 19;
the conditions of the first contact reaction are as follows: the temperature is 390 ℃, and the time is 2 hours;
the conditions of the second contact reaction are as follows: the temperature was 400 ℃ and the time was 1 hour.
The remaining examples and comparative examples were carried out using the same procedure as in example 1, except that the formulation of the composition for preparing the high aluminosilicate glass and the process parameters for preparing the high aluminosilicate glass were different, without specific reference, in table 1.
TABLE 1
Table 1 (continuation watch)
Table 1 (continuation watch)
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| SiO 2 /g | 56.98 | 56.97 | 58.26 |
| Al 2 O 3 /g | 27.6 | 25.98 | 23.54 |
| B 2 O 3 /g | 3.5 | 2.65 | 4.32 |
| P 2 O 5 /g | / | 0.9 | 0.2 |
| Na 2 O/g | 4.01 | 3.74 | 3.56 |
| Li 2 O/g | 4.85 | 4.65 | 5.21 |
| K 2 O/g | 0.9 | 1 | 0.6 |
| MgO/g | 1.76 | 2.2 | 2.81 |
| CaO/g | / | 0.5 | 0.8 |
| ZrO 2 /g | 0.2 | 1.21 | / |
| TiO 2 /g | / | / | 0.5 |
| SnO 2 /g | 0.2 | 0.2 | 0.2 |
| K1 | 0.41 | 0.4 | 0.38 |
| K2 | 3.19 | 3.05 | 2.97 |
| K3/wt％ | 9.76 | 9.39 | 9.37 |
| Contact mixing | |||
| Stirring speed | Same as example 1 | Same as example 1 | Same as example 1 |
| Temperature of | Same as example 1 | Same as example 1 | Same as example 1 |
| Time | Same as example 1 | Same as example 1 | Same as example 1 |
| Melt processing | |||
| Temperature of | Same as example 1 | Same as example 1 | Same as example 1 |
| Time | Same as example 1 | Same as example 1 | Same as example 1 |
| Shaping process | |||
| Temperature of | Same as example 1 | Same as example 1 | Same as example 1 |
| Time | Same as example 1 | Same as example 1 | Same as example 1 |
| Annealing treatment | |||
| Temperature of | Same as example 1 | Same as example 1 | Same as example 1 |
| Time | Same as example 1 | Same as example 1 | Same as example 1 |
| First contact reaction | |||
| Metal salt combination I | Same as example 1 | Same as example 1 | Same as example 1 |
| Temperature of | Same as example 1 | Same as example 1 | Same as example 1 |
| Time | Same as example 1 | Same as example 1 | Same as example 1 |
| Second contact reaction | |||
| Metal salt combination II | Same as example 1 | Same as example 1 | Same as example 1 |
| Temperature of | Same as example 1 | Same as example 1 | Same as example 1 |
| Time | Same as example 1 | Same as example 1 | Same as example 1 |
| Name of | |||
| DS1 | DS2 | DS3 |
Test example
The high aluminosilicate glasses prepared in the examples and the comparative examples are subjected to performance tests, and specific test results are shown in table 2.
Wherein the glass density is determined with reference to ASTM C-693;
determining the coefficient of thermal expansion of the glass at 50-350 ℃ using a horizontal dilatometer, with reference to ASTM E-228;
determining the Young's modulus of the glass using a Material mechanical tester with reference to ASTM C-623;
the Vickers hardness of the glass is determined using a Vickers hardness tester in accordance with ASTM E-384;
four-point bending strength (hereinafter, referred to as 4 PB) was measured by a universal testing machine with reference to ASTM E-1820;
determining the strain point of the glass using an annealing point strain point tester with reference to ASTM C-336;
the glass high temperature viscosity-temperature curve was measured by using a rotary high temperature viscometer with reference to ASTM C-965, wherein the 40000P viscosity corresponds to the forming temperature T 4 ；
The upper limit temperature of devitrification of the glass is determined by the gradient temperature furnace method with reference to ASTM C-829, in which the liquidus temperature T L ；
The FSM-6000LE surface stress meter was used to measure the compressive stress on the glass surface, the depth of layer of the compressive stress, the partial compressive stress at a depth of 30 μm from the glass surface (hereinafter referred to as CS-30), and the partial compressive stress at a depth of 50 μm from the glass surface (hereinafter referred to as CS-50);
k of glass measured by SLP-2000 surface stress meter + 、Na + Depth of ion exchange of (DOL-Na is hereinafter used individually) + 、DOL_K + Expressed) and central tensile stress (hereinafter CT);
the threshold value of the width head end of the 1kg load scratch and the threshold value of the width head end of the 1.8kg load scratch are both tested by a microscope;
the 4.5kg load crush was tested using a pencil hardness tester.
TABLE 2
Table 2 (continuation watch)
Table 2 (continuation watch)
The results in table 2 show that the high aluminosilicate glass frit provided by the present invention has long glass frit property, small devitrification tendency, four-point bending strength exceeding 780MPa, and can protect mobile devices when being scratched by sharp objects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composition for producing a high aluminosilicate glass, characterized in that the composition contains 45-70 wt.% SiO, based on the total mass of the composition 2 20-40 wt% of Al 2 O 3 1-5 wt% of B 2 O 3 0-5 wt% of P 2 O 5 3-12 wt% of Na 2 O, 2-10 wt% of Li 2 O, 0-5 wt% of K 2 O, 1-5 wt% of MgO, 0-5 wt% of CaO, 0-5 wt% of ZrO 2 0-3 wt% of TiO 2 A clarifying agent not more than 1 wt%;
the clarifying agent is at least one selected from sulfate, nitrate, halide, stannic oxide and stannous oxide; and
definition K1 ═ Na 2 Mass percent of O/(Li) 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 The mass percentage of O) and K1 is 0.42-0.8;
definition K2 ═ (B) 2 O 3 Mass percentage of (B) + Al 2 O 3 Mass percent of (C)/(Li) 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 The mass percentage of O) and K2 is 1.5-2.9;
definition K3 ═ Li 2 The mass percentage of O + Na 2 The mass percentage of O + K 2 O, and K3 is 6-15 wt%.
2. The composition of claim 1, wherein the composition comprises 50-65 wt% SiO, based on the total mass of the composition 2 23-35 wt.% of Al 2 O 3 1-4 wt% of B 2 O 3 0-3 wt% of P 2 O 5 5-10 wt% of Na 2 O, 3-6 wt% of Li 2 O, 0.05-1 wt% of K 2 O, 1-4 wt% of MgO, 0-1 wt% of CaO, 0.5-1.5 wt% of ZrO 2 0-1 wt% of TiO 2 And 0.05-0.8 wt% of a clarifying agent.
3. The composition of claim 1 or 2, wherein the K1 is 0.55 to 0.7.
4. The composition according to any one of claims 1 to 3, wherein the K2 is 2.1 to 2.9.
5. Composition according to any one of claims 1 to 4, characterized in that the refining agent is tin oxide and the content of tin oxide is 0.1 to 0.3 wt.%, based on the total mass of the composition.
6. A method of making a high aluminosilicate glass, the method comprising:
(1) melting the components of the composition of any one of claims 1-5 to obtain a molten mass;
(2) sequentially carrying out forming treatment and annealing treatment on the molten material to obtain a glass precursor;
(3) carrying out a first contact reaction on the glass precursor and a metal salt combination I, and carrying out a second contact reaction on a product obtained after the first contact reaction and a metal salt combination II;
wherein the metal salt composition I is a composition of sodium nitrate and potassium nitrate with the dosage mass ratio of 4-8: 1;
the metal salt composition II is prepared from the following components in a dosage mass ratio of 1: 15-20 of a combination of sodium nitrate and potassium nitrate.
7. The method according to claim 6, wherein in step (1), the conditions of the melt processing comprise at least: the temperature is 1600-; and/or
In the step (2), the annealing treatment conditions at least include: the temperature is 550-650 ℃, and the time is 1-3 h.
8. The method according to claim 6 or 7, wherein in step (3), the conditions of the first contact reaction and the second contact reaction each independently comprise: the temperature is 390-450 ℃, and the time is 1-6 h.
9. A high aluminosilicate glass produced by the method of any one of claims 6-8.
10. Use of the high aluminosilicate glass of claim 9 in a display screen of a smart device.
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