CN117585900A - Tempered glass and preparation method and application thereof - Google Patents
Tempered glass and preparation method and application thereof Download PDFInfo
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- CN117585900A CN117585900A CN202311476926.3A CN202311476926A CN117585900A CN 117585900 A CN117585900 A CN 117585900A CN 202311476926 A CN202311476926 A CN 202311476926A CN 117585900 A CN117585900 A CN 117585900A
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- 239000005341 toughened glass Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000002834 transmittance Methods 0.000 claims abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000006058 strengthened glass Substances 0.000 claims abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 19
- 238000005342 ion exchange Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011325 microbead Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 239000008395 clarifying agent Substances 0.000 claims description 2
- 239000006025 fining agent Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 28
- 239000000395 magnesium oxide Substances 0.000 abstract description 19
- 239000011787 zinc oxide Substances 0.000 abstract description 14
- 150000001768 cations Chemical class 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006004 Quartz sand Substances 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 239000000292 calcium oxide Substances 0.000 description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000006121 base glass Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000002241 glass-ceramic Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000006133 sodium aluminosilicate glass Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000003238 silicate melt Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a tempered glass, a preparation method and application thereof, wherein the tempered glass is prepared from quartz sand and Al 2 O 3 、MgO、TiO 2 The glass is prepared by taking potassium carbonate, sodium carbonate, calcium carbonate and ZnO as main raw materials through the preparation of a glass matrix, the heat treatment process and the chemical strengthening process, and the vickers hardness of the strengthened glass is 890kgf/mm 2 The transmittance was 87% or more. Therefore, the reinforced glass has higher transmittance and hardness. The invention obtains the split-phase glass after heat treatment by controlling the oxide content and proportion of different cations, and strengthens the split-phase glass, thereby improving the hardness of the glass without reducing the transmittance of the glass.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to reinforced glass and a preparation method and application thereof.
Background
With the trend of mobile electronic devices such as notebook computers, portable navigators, smartphones, etc., to be lighter and more powerful, people have a higher and higher dependence on them. The increase in frequency of use has placed higher demands on glass materials in electronic devices, and it is desirable that the glass materials be made lighter and thinner, while also being stiffer and stronger.
Some people strengthen microcrystalline glass containing a large amount of crystals in an ion exchange mode, and the microcrystalline glass strengthened by the ion exchange has more excellent comprehensive mechanical properties. However, the glass-ceramic production process generally comprises two steps of nucleation and crystallization, which increases the energy consumption of production and thus increases the production cost of glass-ceramic. Second, since glass ceramics contain a large number of crystals, it makes grinding and polishing during deep processing extremely difficult.
Sodium aluminosilicate glass strengthened by ion exchange is currently commonly used as a glass material in electronic devices. However, the existing ion exchange reinforced sodium aluminosilicate glass has insufficient hardness and low transmittance.
Disclosure of Invention
The invention aims to solve the technical problems that: how to improve the hardness of the glass without reducing the transmittance of the glass.
In order to solve the technical problems, the embodiment of the invention provides reinforced glass and a preparation method and application thereof; the oxide content and proportion of different cations are controlled, and the split-phase glass is obtained after heat treatment and then has high transmittance and hardness through strengthening.
The embodiment of the invention also provides a preparation method of the reinforced glass;
the embodiment of the invention also provides an application of the reinforced glass.
In some embodiments, the tempered glass comprises the following components in mass percent: 45-55% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 17-20% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3-8% MgO; 4-8% TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 2 to 5 percent of K 2 O; 11-18% of Na 2 O;0.5 to 2 percent of CaO and 0 to 6 percent of ZnO.
The invention obtains split-phase glass after heat treatment by controlling the oxide content and proportion of different cations, and the main components are as follows:
SiO 2 : the network forming body of the base glass can be independently formed into glass, belongs to one of the essential components, mainly forms a netlike main structure of the base glass, and endows the base glass and the microcrystalline glass with better chemical stability, mechanical property and forming property. SiO (SiO) 2 The content is at least 45%; but too high SiO 2 At the same time, the glass melting temperature is increased, clarification and melting are difficult, and SiO 2 The content is 50% at most. SiO (SiO) 2 The content is 45-50%.
Al 2 O 3 : the volume of aluminum oxide tetrahedron formed in the glass is larger than that of silicon oxide tetrahedron, and the volume of the glass is expanded, so that the density of the glass is reduced, a strengthening channel is provided for the glass in the ion strengthening process, the ion strengthening of the base glass and the microcrystalline glass is promoted, and the Al in the base glass is promoted 2 O 3 The content is at least 17%; but Al is 2 O 3 Belongs to extremely refractory oxide, can rapidly improve the high-temperature viscosity of glass, so that the difficulty of glass clarification and homogenization is increased, and the defect concentration of bubbles in the glass is greatly increased; thus on the basis ofAl in glass 2 O 3 The content is up to 20%. Al (Al) 2 O 3 The content is 17-20%
Na 2 O: one of essential components of the base glass, namely the network external oxide, can obviously reduce the viscosity of the base glass and promote the melting and clarification of the base glass; but to promote the crystallization of glass with K in the potassium nitrate molten salt + The ions strengthen to generate high compressive stress on the surface of the glass to improve the strength of the glass, and the glass must have enough Na + Exists, therefore, na in the present invention 2 The O content is 11-18%
K 2 O: one of the essential components of the base glass, the network external oxide, can obviously reduce the viscosity of the base glass and promote the melting and clarification of the base glass. At the same time, the ion potential of potassium ion is less than 1, the devitrification phenomenon generated by the phase separation of glass is inhibited, and the content is 2 to 5 percent
MgO: is an important component of reinforced glass, the ionic potential of the reinforced glass is more than 1.4, and the reinforced glass is easy to form larger ionic potential difference with other metal cations, thereby being beneficial to glass phase separation, and the MgO can enhance the mechanical strength and chemical stability of the glass; however, an excessively high content results in a high heat treatment temperature required for phase separation, and thus, the mass fraction of MgO is 3% to 8%.
CaO: the transmittance of the tempered glass is improved, but the excess CaO increases the viscosity of the glass and makes it difficult to clarify, so that the content thereof is 0.5 to 2%.
TiO 2 : is a nucleating agent for promoting precipitation of nanocrystals and increasing uniformity of tempered glass, but TiO 2 Too high a content may lead to glass microcrystallization, thereby reducing transmittance and even devitrification, and thus, tiO 2 The mass fraction of (2) should be controlled between 4% -8%.
ZnO: the ZnO is used for forming the base glass into high-strength stable strengthened glass, and ZnO can further increase the mechanical strength and chemical stability of the strengthened glass.
In some embodiments, the strengthened glass comprises 0.1.ltoreq.K by mass percent 2 O/Na 2 O≤0.4；
0.1≤K 2 O/(MgO+CaO+TiO 2 +ZnO)≤0.38；
And/or, na is more than or equal to 0.7 2 O/(MgO+CaO+TiO 2 +ZnO)≤1.3。
In some embodiments, the strengthened glass further comprises 0 to 2 percent by mass of Li 2 O; zrO 0-2% 2 The method comprises the steps of carrying out a first treatment on the surface of the 0-5% SrO;0 to 2 percent of BaO and 0 to 0.2 percent of clarifying agent;
preferably, the fining agent is SnO 2 And/or CeO 2 。
Explaining the reason why the oxide glass melt is immiscible, i.e., phase-separated, from a crystallization chemistry standpoint, it is believed that the liquid phase separation of the melt is caused by cation-to-oxygen ion competition. In silicate melts, the bridging oxygen ions are attracted to themselves in the form of silicon oxygen tetrahedra, so that the extra-network cations always tend to attract non-bridging oxygen ions to themselves and are arranged according to their own structural requirements. The practice proves that the magnitude of the cationic field intensity has a decisive effect on the phase separation of oxide glass. When the cation content with large ion potential is more, the free energy of the system is larger, and a stable and uniform glass phase cannot be formed, so that the reinforced phase-separated glass is obtained by controlling the oxide content and the proportion of different types of cations contained in the base glass. The ion potentials of the different cations are shown in table 1 below:
TABLE 1 ion potentials of different cations
As shown in Table 1, the cations were classified according to ion potentials Z/r < 1, 1 < Z/r < 1.4, and Z/r > 1.4.
More preferably, 0.1.ltoreq.K by mass 2 O/(Na 2 O+Li 2 O+BaO)≤0.4；
0.1≤K 2 O/(MgO+CaO+TiO 2 +ZnO+ZrO 2 +SrO)≤0.38；
And/or, 0.7.ltoreq.Na (Na) 2 O+Li 2 O+BaO)/(MgO+CaO+TiO 2 +ZnO+ZrO 2 +SrO)≤1.3。
In some embodiments, the isolated microbeads within the strengthened glass have a particle size of less than or equal to 100nm;
preferably, the transmittance of the tempered glass of 1mm thickness is more than 87%, and the vickers hardness of the tempered glass is 890kgf/mm 2 The above;
more preferably, the transmittance of the tempered glass having a thickness of 1mm is 87 to 89%, and the vickers hardness of the tempered glass is 890 to 900kgf/mm 2 。
In some embodiments, the method for preparing the strengthened glass comprises preparing a glass substrate and performing a heat treatment process on the glass substrate, wherein the heat treatment process is followed by chemical strengthening, and the chemical strengthening comprises immersing the glass substrate in sodium-potassium mixed salt for ion exchange;
preferably, the mass ratio of sodium to potassium in the sodium-potassium mixed salt is 0.1-10.
In some embodiments, the glass substrate is subjected to a heat treatment process to form a phase-separated glass, and the phase-separated glass is subjected to a pre-heating treatment prior to ion exchange;
the temperature of the preheating treatment is 320-380 ℃, and the time of the preheating treatment is more than 5 minutes;
preferably, the temperature of the ion exchange is 380-470 ℃, and the time of the ion exchange is 0.5-10 hours;
more preferably, the temperature of the ion exchange is 430-460 ℃, and the time of the ion exchange is 4-8 hours.
In some embodiments, the glass substrate is maintained at 20-100 ℃ after annealing during the preparation of the glass substrate.
Specifically, after annealing, the glass substrate is subjected to heat preservation at 20-100 ℃ for 1-4 hours;
preferably, the melt is cooled to an annealing temperature at a rate of 0.5 to 20 ℃/min;
more preferably, the annealing temperature is 480-520 ℃ and the annealing time is 1-3 hours.
In some embodiments, the conditions of the heat treatment process are: the temperature is 720-780 ℃ and the time is 2-4h;
preferably, the conditions of the heat treatment process are: the temperature was 750℃and the time was 3 hours.
And (3) after annealing, in the preparation process of insulating the glass matrix at 20-100 ℃, the melting treatment temperature after raw material mixing is 1500-1600 ℃ and the time is 2-6h.
The tempered glass or the application of the tempered glass prepared by the preparation method takes the tempered glass as a packaging glass or a shell material of intelligent equipment.
Through the technical scheme, the reinforced glass provided by the invention adopts SiO 2 、Al 2 O 3 、MgO、TiO 2 、K 2 O、Na 2 O, caO and ZnO as main components, and is prepared by preparing glass matrix, heat treating, and chemically strengthening, wherein the Vickers hardness of the strengthened glass is equal to or higher than 890kgf/mm 2 Softening point is 700-715 ℃; the haze is 0.2-0.25%, and the transmittance is 87-89%. Therefore, the reinforced glass has higher transmittance and hardness.
The invention obtains the split-phase glass by controlling the oxide content and the proportion of different cations contained, and then strengthens the split-phase glass by a special solution, thereby improving the hardness of the split-phase glass without reducing the transmittance of the glass.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Figure 1 is an XRD profile obtained from the test of example 2 provided by the present invention.
Detailed Description
Embodiments of the present invention are described in further detail below with reference to the accompanying drawings and examples. The following detailed description of embodiments is provided to illustrate the principles of the invention and not to limit the scope of the invention, which may be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein, but rather should be construed to include all technical solutions falling within the scope of the appended claims.
These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It should be noted that: the relative arrangement of parts and steps, the composition of materials, numerical expressions and numerical values set forth in these embodiments should be construed as exemplary only and not limiting unless otherwise specifically stated.
As used herein, the word "comprising" or "comprises" and the like means that elements preceding the word encompass the elements recited after the word, and that no other elements are excluded from the possible coverage as well.
All terms used herein have the same meaning as understood by one of ordinary skill in the art to which the present invention pertains, unless specifically defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques, methods, and apparatus should be considered part of the specification.
In the following examples, each material used was commercially available as not specifically described, and the method used was conventional in the art.
In the following examples and comparative examples, various performance indexes of the tempered glass article or the matrix glass were tested using the following methods:
crystalline phase: analysis by XRD diffractometer showed that 2Theta = 10-80 ° with a step size of 0.02, the equipment used in this example was shimadzu XRD-6000.
Crystallinity: analysis by XRD diffractometer showed that 2Theta = 10-80 ° with a step size of 0.02, the equipment used in this example was shimadzu XRD-6000. According to the ray diffraction pattern, the software JADE is used for searching crystalline phases and calculating the crystallinity.
Particle size: and (3) measuring by using an SEM scanning electron microscope, carrying out surface treatment on the transparent glass ceramics in HF acid, then carrying out metal spraying on the surface of the transparent glass ceramics, carrying out surface scanning under the SEM scanning electron microscope, and determining the size of crystal grains.
Haze: the haze is measured by using a haze tester and using GB2410-80 as a standard, wherein the haze tester is prepared by using a sample with the thickness of less than 1mm
Transmittance: the transmittance is measured by using a haze tester and a sample with the thickness of less than 1mm and GB2410-80 as a standard.
Vickers hardness: the load (N) when a diamond quadrangular pyramid indenter having an included angle of 136 DEG with respect to the surface was pressed into a pyramid-shaped recess on the test surface was divided by the surface area (mm 2) calculated from the length of the recess. The test load was 200 (N) and the holding time was 15 (seconds). The vickers hardness is sometimes referred to simply as hardness in the present invention.
In the present invention, siO 2 Introduced in the form of quartz sand, K 2 O is introduced in the form of potassium carbonate, na 2 O is introduced in the form of sodium carbonate, caO is introduced in the form of calcium carbonate, and the other components are introduced in the form of oxides.
Example 1
The reinforced glass provided in the embodiment uses quartz sand and Al 2 O 3 、MgO、TiO 2 The main raw materials of the composite material comprise the following components in percentage by mass:
SiO 2 (Quartz sand), al 2 O 3 (aluminum oxide), mgO (magnesium oxide), tiO 2 (titanium dioxide), K 2 O (Potassium oxide), na 2 O (sodium oxide), caO (calcium oxide), znO: (zinc oxide); the specific raw materials and proportions are shown in Table 2.
Example 2
The reinforced glass provided in the embodiment uses quartz sand and Al 2 O 3 、MgO、TiO 2 The main raw materials of the composite material comprise the following components in percentage by mass:
SiO 2 (Quartz sand), al 2 O 3 (aluminum oxide), mgO (magnesium oxide), na 2 O (sodium oxide), caO (calcium oxide), K 2 O (potassium oxide), tiO 2 (titanium dioxide), snO 2 (tin oxide); the specific raw materials and proportions are shown in Table 2.
The preparation method of the reinforced glass comprises the following steps:
preparation of base glass: weighing the raw materials, and uniformly mixing to obtain a uniform mixture; then transferring the mixture into a platinum crucible of about 1500ml, placing the platinum crucible into a silicon-molybdenum rod of high Wen Lulu, gradually heating to 1500-1600 ℃, holding the temperature for 2-6 hours, and accelerating the discharge of glass bubbles by stirring. After melting, pouring the molten liquid into a heat-resistant stainless steel mold for molding, taking out the glass block, transferring into a box-type annealing furnace for annealing at 500 ℃ for 2 hours, and naturally cooling to room temperature to obtain the base glass. The glass block was cut and ground to prepare a sample that was consistent with the relevant test.
The heat treatment process comprises the following steps: placing the glass substrate in a precision annealing furnace for heat treatment at 750 ℃ and preserving heat for 3 hours; after heat treatment, phase-separated glass is formed.
Chemical strengthening process: heating the split-phase glass to 350 ℃ and preserving the heat for at least 5 minutes; the split-phase glass is then put into NaNO 3 And KNO 3 In the mixed molten salt (the mass ratio of sodium to potassium in the sodium-potassium mixed salt is 0.1-10), the ion exchange conditions are set as follows: heating to 400 ℃, and keeping the temperature for 3 hours; the surface residues of the chemically strengthened glass were cleaned with hot water and tested. The results were analyzed by XRD diffractometer and are shown in figure 1.
Examples 3 to 6
The preparation methods of examples 3-6 are the same as in example 1, except that: the selection and proportion of the raw materials are different, and are shown in table 2.
Comparative example 1
This comparative example is substantially identical to example 2, with the only difference that: no heat treatment was performed.
Comparative example 2
This comparative example is substantially identical to example 2, with the only difference that: by KNO 3 Solution (instead of NaNO) 3 And KNO 3 Molten salt mixed) ion-exchanged to the split phase glass.
Comparative example 3
This comparative example is substantially identical to example 2, with the only difference that: k (K) 2 O/(Na 2 O+Li 2 O+BaO)≥0.4；
Comparative example 4
This comparative example is substantially identical to example 2, with the only difference that: k (K) 2 O/(MgO+CaO+TiO 2 +ZnO+ZrO 2 +SrO)≥0.38；
Comparative example 5
This comparative example is substantially identical to example 2, with the only difference that: (Na) 2 O+Li 2 O+BaO)/(MgO+CaO+TiO 2 +ZnO+ZrO 2 +SrO)≥1.3。
TABLE 2 comparison of raw materials and Properties for examples 1-6
Comparison of example 2 with comparative examples 1-5 results are shown in Table 3:
TABLE 3 comparison of the raw materials and Properties of example 2 and comparative examples 1 to 5
The above experiment results show that comparative example 1, which was not heat-treated, gave a glass having a Vickers hardness of 650kgf/mm 2 The hardness is lower.
Comparative example 2 uses KNO alone 3 Ion-exchanging the split-phase glass with the solution to obtain glass with the Vickers hardness of 730kgf/mm 2 Hardness is also low.
The comparative examples 3 to 5 were not appropriate in oxide content and ratio, and were in a glassy state, and phase-separated glass could not be formed, resulting in low hardness.
The grain diameter of the isolated microbeads in the reinforced glass is less than or equal to 100nm, and the Vickers hardness of the reinforced glass after the reinforced glass is reinforced by a chemical reinforcing process is more than or equal to 890kgf/mm 2 Softening point is 700-715 ℃; the haze is 0.2-0.25%, and the transmittance of the reinforced glass with the thickness of 1mm is 87-89%. Therefore, the reinforced glass has higher transmittance and hardness.
Experiments show that the reinforced glass provided by the invention adopts SiO 2 、Al 2 O 3 、MgO、TiO 2 、K 2 O、Na 2 O, caO and ZnO are used as main components, oxide content and proportion of different cations are controlled, the split-phase glass is obtained after heat treatment, and then the split-phase glass is strengthened by a special solution, so that the hardness of the split-phase glass is improved, and the transmittance of the glass is not reduced.
In some embodiments, the tempered glass of embodiments 1-6 is used as a packaging glass or housing material for a smart device, such as a smart device protective cover plate.
Thus, various embodiments of the present invention have been described in detail. In order to avoid obscuring the concepts of the invention, some details known in the art have not been described. How to implement the solutions applied herein will be fully apparent to those skilled in the art from the above description.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be understood by those skilled in the art that the foregoing embodiments may be modified and equivalents substituted for elements thereof without departing from the scope and spirit of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict.
Claims (10)
1. The reinforced glass is characterized by comprising the following components in percentage by mass:
45-55% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 17-20% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 3-8% MgO; 4-8% TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 2 to 5 percent of K 2 O; 11-18% of Na 2 O;0.5 to 2 percent of CaO and 0 to 6 percent of ZnO.
2. The tempered glass according to claim 1, wherein 0.1.ltoreq.K by mass% in the tempered glass 2 O/Na 2 O≤0.4；
0.1≤K 2 O/(MgO+CaO+TiO 2 +ZnO)≤0.38；
And/or, na is more than or equal to 0.7 2 O/(MgO+CaO+TiO 2 +ZnO)≤1.3。
3. The tempered glass according to claim 1, further comprising 0 to 2% by mass of Li 2 O; zrO 0-2% 2 The method comprises the steps of carrying out a first treatment on the surface of the 0-5% SrO;0 to 2 percent of BaO and 0 to 0.2 percent of clarifying agent;
preferably, the fining agent is SnO 2 And/or CeO 2 ；
More preferably, 0.1.ltoreq.K by mass 2 O/(Na 2 O+Li 2 O+BaO)≤0.4；
0.1≤K 2 O/(MgO+CaO+TiO 2 +ZnO+ZrO 2 +SrO)≤0.38；
And/or, 0.7.ltoreq.Na (Na) 2 O+Li 2 O+BaO)/(MgO+CaO+TiO 2 +ZnO+ZrO 2 +SrO)≤1.3。
4. A strengthened glass according to any one of claims 1 to 3 wherein the isolated microbeads within the strengthened glass have a particle size of less than or equal to 100nm;
preferably, the transmittance of the tempered glass of 1mm thickness is more than 87%, and the vickers hardness of the tempered glass is 890kgf/mm 2 The above;
more preferably, the transmittance of the tempered glass having a thickness of 1mm is 87 to 89%, and the vickers hardness of the tempered glass is 890 to 900kgf/mm 2 。
5. The method for producing a tempered glass according to any one of claims 1 to 4, comprising a production of a glass substrate and a heat treatment process for the glass substrate, characterized in that a chemical strengthening is performed after the heat treatment process, the chemical strengthening comprising immersing the glass substrate in a sodium-potassium mixed salt for ion exchange;
preferably, the mass ratio of sodium to potassium in the sodium-potassium mixed salt is 0.1-10.
6. The method according to claim 5, wherein the glass substrate is subjected to a heat treatment to form a phase-separated glass, and the phase-separated glass is subjected to a preheating treatment before ion exchange;
the temperature of the preheating treatment is 320-380 ℃, and the time of the preheating treatment is more than 5 minutes;
preferably, the temperature of the ion exchange is 380-470 ℃, and the time of the ion exchange is 0.5-10 hours;
more preferably, the temperature of the ion exchange is 430-460 ℃, and the time of the ion exchange is 4-8 hours.
7. The method according to claim 5 or 6, wherein the heat treatment of the glass substrate is carried out at a rate of 0.5 to 20 ℃/min from the melting temperature to the annealing temperature; then preserving the heat of the glass matrix at the temperature of 20-100 ℃ higher than the glass transition point for 1-4 h;
more preferably, the annealing temperature is 480-520 ℃ and the annealing time is 1-3 hours.
8. The method according to any one of claims 5 to 7, wherein the conditions of the heat treatment process are: the temperature is 720-780 ℃ and the time is 2-4h;
preferably, the conditions of the heat treatment process are: the temperature was 750℃and the time was 3 hours.
9. The method according to any one of claims 5 to 8, wherein the glass substrate is prepared by mixing the raw materials and then melting the raw materials at 1500 to 1600 ℃ for 2 to 6 hours.
10. Use of a tempered glass according to any one of claims 1 to 4 or a tempered glass produced by a method according to any one of claims 5 to 9 as a packaging glass or casing material for an intelligent device.
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