CN117658474A - Microcrystalline glass cover plate, preparation method, repairing and anti-fingerprint method and electronic equipment - Google Patents
Microcrystalline glass cover plate, preparation method, repairing and anti-fingerprint method and electronic equipment Download PDFInfo
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- CN117658474A CN117658474A CN202311394260.7A CN202311394260A CN117658474A CN 117658474 A CN117658474 A CN 117658474A CN 202311394260 A CN202311394260 A CN 202311394260A CN 117658474 A CN117658474 A CN 117658474A
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- 239000011521 glass Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000003666 anti-fingerprint Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 136
- 238000005342 ion exchange Methods 0.000 claims abstract description 61
- 238000005728 strengthening Methods 0.000 claims abstract description 60
- 239000013078 crystal Substances 0.000 claims abstract description 58
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 229910013553 LiNO Inorganic materials 0.000 claims abstract description 29
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000010453 quartz Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000013003 hot bending Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 21
- 238000005498 polishing Methods 0.000 claims description 20
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052670 petalite Inorganic materials 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000004579 marble Substances 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 230000003746 surface roughness Effects 0.000 claims description 5
- 238000001771 vacuum deposition Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- 239000006059 cover glass Substances 0.000 claims 3
- 230000003287 optical effect Effects 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 239000004575 stone Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 19
- 238000005520 cutting process Methods 0.000 description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000006116 anti-fingerprint coating Substances 0.000 description 5
- 238000005034 decoration Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000037452 priming Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 238000007649 pad printing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010023 transfer printing 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- 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
- C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Abstract
The application provides a microcrystalline glass cover plate which is obtained by subjecting microcrystalline glass sheets to chemical ion exchange strengthening treatment. The molten salt used for strengthening treatment contains LiNO 3 The stability of the surface state can be ensured while the surface stress is enhanced and the strength is improved. The glass ceramic cover plate comprises: glass phase, volume ratio is 10% -70%; quartz crystal, the volume ratio is 10% -55%; lithium disilicate crystals having a volume ratio of 10% -40%; lithium penetration lengthThe volume ratio of the stone crystal is 10-40%. The application also provides a preparation method of the glass ceramic cover plate, electronic equipment applying the glass ceramic cover plate, a repairing method of the glass ceramic cover plate and an anti-fingerprint method of the glass ceramic cover plate. The glass ceramic cover plate has high strength, excellent anti-drop performance, transparency and optical performance, and meets the screen use requirements of electronic equipment such as mobile phones.
Description
Technical Field
The application relates to a glass ceramic cover plate and a preparation method thereof, a repairing method of the glass ceramic cover plate, an anti-fingerprint method of the glass ceramic cover plate and electronic equipment using the glass ceramic cover plate.
Background
Compared with the rear cover/shell made of metal and plastic, the transparent glass is used as the rear cover/shell of various electronic devices such as mobile phones, and has better appearance grade, better touch feeling, stronger decorativeness and higher technological sense. In addition, the glass material has a smaller shielding against electromagnetic waves than the metal material, and this is also an advantage of the glass material with the advent of the 5G age. However, glass is a brittle material and is easily broken when used in electronic devices.
Disclosure of Invention
The first aspect of the embodiment of the application provides a glass-ceramic cover plate, which is obtained by strengthening treatment of glass-ceramic sheet material through chemical ion exchange, wherein molten salt used in the strengthening treatment contains LiNO 3 ；
The glass ceramic cover plate comprises:
15-70% of glass phase by volume;
quartz crystal, the volume ratio is 10% -55%;
lithium disilicate, the crystal volume ratio is 10% -40%;
the volume ratio of the petalite to the crystal is 10-40%.
The strengthening process of the glass ceramic cover plate comprises two times of ion exchange, and LiNO is added in the water proportion of the strengthening furnace 3 The components can enhance the surface stress and improve the strength, and can ensure the stability of the surface state, so that the microcrystalline glass cover plate with high strength and excellent anti-drop performance and optical performance meeting the use requirement of a display screen can be obtained. Increasing LiNO 3 The reason for (2) is: compared with the conventional glass, the microcrystalline glass contains a certain proportion of crystal phase, and the characteristic of the microcrystalline glass is that the microcrystalline glassWhen the chemical strengthening is carried out, besides the ion exchange of the glass phase, part of ions in the crystal phase of the surface layer also participate, so that the crystal phase of the surface layer is damaged, loose holes are formed in the surface layer, the exchanged Na ions and K ions are enriched in the holes, and under the high-temperature and high-humidity environment, the part of ions and water vapor form white Na salts and K salts which are attached to the surface of the glass, so that the cleanliness and the display effect of the material are affected. Increasing LiNO 3 On one hand, the damage to the surface crystal in the strengthening process can be restrained; on the other hand, na ions and K ions enriched on the surface can be reduced, so that the material can keep stable surface performance in a high-temperature and high-humidity environment.
In this embodiment, the formula of the glass ceramic cover plate is as follows:
SiO 2 65 to 85 percent of the weight ratio,
Al 2 O 3 5 to 12 percent of the weight ratio,
Na 2 o weight ratio is 0.5-6%,
Li 2 4 to 9 percent of O by weight,
P 2 O 5 0.05 to 3 percent of the weight ratio,
K 2 o weight ratio is 0.5-3%,
MgO in 0.5-8 wt%,
TiO 2 0.5 to 3 percent of the weight ratio,
ZrO 2 0.1 to 3 percent by weight.
In the embodiment of the application, the microcrystalline glass cover plate is obtained by performing hot bending forming and chemical ion exchange strengthening treatment on microcrystalline glass sheets.
During 3D hot bending, the formation of lithium disilicate crystals and petalite crystals is promoted, so that the lithium disilicate crystals and the petalite crystals in the microcrystalline glass sheet are increased, and the optimization of optical performance and the improvement of strength are brought. As can be seen from the raman spectrum test results before and after the hot bending, during the hot bending, along with the rupture of Si-O non-bridging oxygen bonds, silicon oxygen combines with Li, al and the like to form lithium disilicate crystals and petalite crystals.
In the embodiment of the application, the strengthening partThe process includes two ion exchanges; first ion exchange: KNO with molten salt composition of 0mol% to 50mol% 3 50mol% to 100mol% NaNO 3 0mol% to 5mol% LiNO 3 The temperature of molten salt is 400-480 ℃; second ion exchange: the molten salt has a composition KNO 3 And the weight is KNO 3 0.05% -5% by weight of LiNO 3 The temperature of the molten salt is 350-420 ℃.
In this embodiment, after the strengthening treatment, the surface layer of the glass-ceramic sheet is transformed to form a strengthening layer, the thickness of the strengthening layer is greater than or equal to 90 micrometers, the surface compressive stress of the strengthening layer is greater than or equal to 160MPa, and the compressive stress at a position with a depth of 50 micrometers from the outer surface is greater than or equal to 65MPa.
In an embodiment of the present application, the crystal sizes of the quartz crystal, the lithium disilicate crystal and the petalite crystal are all smaller than 80nm, preferably smaller than 50nm.
In the embodiment of the application, the average transmittance of the microcrystalline glass cover plate to light with the wavelength ranging from 450nm to 1000nm is more than or equal to 88%.
In the embodiment of the application, the haze of the glass ceramic cover plate is less than or equal to 0.2%, and preferably the haze is less than or equal to 0.15%.
In the embodiment of the application, the color difference b value of the microcrystalline glass cover plate meets the value of |b| to be less than or equal to 1.2, and is preferably |b| to be less than or equal to 0.8.
In the embodiment of the application, the four-bar bending strength B10 of the microcrystalline glass cover plate is greater than 550Mpa, and the average value is greater than 800Mpa.
In the embodiment of the application, the monomer falling energy which can be born by the microcrystalline glass cover plate is larger than 0.2J.
In the embodiment of the application, the microcrystalline glass cover plate is assembled on a complete machine with the weight of 180g and has the complete machine sand paper falling and marble falling strength of more than 1.5 m.
The second aspect of the embodiment of the application provides an electronic device, which comprises a transparent screen display cover plate and a shell, wherein at least one of the screen display cover plate and the shell is the glass ceramic cover plate in the first aspect of the application.
The microcrystalline glass cover plate has high strength and excellent anti-drop performance, and can effectively prolong the service life of the electronic equipment.
A third aspect of the embodiments of the present application provides a method for preparing a glass ceramic cover plate, including:
the glass stock solution is prepared by smelting the following raw materials at the temperature of 1300-1700 ℃:
SiO 2 65 to 85 percent of the weight ratio,
Al 2 O 3 5 to 12 percent of the weight ratio,
Na 2 o weight ratio is 0.5-6%,
Li 2 4 to 9 percent of O by weight,
P 2 0.05 to 3 percent of O5 by weight,
K 2 o weight ratio is 0.5-3%,
MgO in 0.5-8 wt%,
TiO 2 0.5 to 3 percent of the weight ratio,
ZrO 2 0.1 to 3 percent by weight.
Forming the glass stock solution into a glass body;
carrying out heat treatment on the glass body at the temperature of 500-650 ℃ for 0.5-10 h to nucleate, and carrying out heat treatment at the temperature of 650-800 ℃ for 0.5-10 h to crystallize after nucleating to obtain microcrystalline glass;
cutting and grinding the microcrystalline glass to obtain a sheet of microcrystalline glass;
and performing chemical ion exchange strengthening treatment on the microcrystalline glass sheet.
In an embodiment of the present application, the strengthening treatment comprises two ion exchanges; first ion exchange: KNO with molten salt composition of 0mol% to 50mol% 3 50mol% to 100mol% NaNO 3 0mol% to 5mol% LiNO 3 The temperature of molten salt is 400-480 ℃; second ion exchange: the molten salt has a composition KNO 3 And the weight is KNO 3 0% -5% by weight of LiNO 3 The temperature of the molten salt is 350-420 ℃.
In an embodiment of the present application, the preparation method further includes performing a hot bending forming process on the glass-ceramic sheet at a temperature of 650-800 ℃ and a forming pressure of 0.3MPa-0.8MPa before the strengthening process is performed.
A fourth aspect of the embodiments of the present application provides a repair method for a glass ceramic cover board scratch according to the first aspect of the present application, including:
polishing two opposite surfaces of the glass ceramic cover plate;
ion exchange treatment is carried out on the polished microcrystalline glass cover plate, and the process and parameters of the ion exchange treatment are as follows:
the molten salt has a composition KNO 3 And the weight is KNO 3 0% -5% LiNO 3 The temperature of the molten salt is 350-420 ℃, and the ion exchange time is 0.5-2h; or,
KNO with molten salt composition of 0mol% to 50mol% 3 50mol% to 100mol% NaNO 3 0mol% to 3mol% LiNO 3 The temperature of the molten salt is 400-480 ℃ and the ion exchange time is 0.5-2h.
According to the repairing method, the processing yield of the glass ceramic cover plate is remarkably improved through the reinforced scheme of ion exchange after regrinding.
In this embodiment, two opposite surfaces of glass apron are concave surface and convex surface respectively, adopt the polishing dish of sponge material, the polishing time of concave surface is 900s-2500s, the polishing time of convex surface is 500s-1500s.
A fifth aspect of the embodiments of the present application provides a method for improving fingerprint resistance of a glass ceramic cover plate according to the first aspect of the present application, including:
cleaning a glass ceramic cover plate by adopting an alkaline solution, wherein the pH value of the alkaline solution is less than 12, and the surface roughness Ra of the glass ceramic cover plate is less than 1.5nm after cleaning;
and plating an anti-fingerprint film on the microcrystalline glass cover plate in a vacuum coating mode.
By controlling the cleaning process in the processing process, the water drop angle is more than 105 degrees after the anti-fingerprint coating film resists rubber friction 2500 times, and the water drop angle is more than 102 degrees after the anti-steel wool friction 2500 times. In general, glass ceramics are difficult to achieve with conventional coating processes.
In this embodiment, after the cleaning, the change value of the b value of the glass ceramic cover plate before and after the cleaning is less than 0.3.
Drawings
FIG. 1 is a Raman spectrum of a glass-ceramic sheet before and after hot bending.
Fig. 2 is a graph of light transmittance of a glass-ceramic sheet and a glass-ceramic cover plate.
FIG. 3 is a haze distribution diagram of a glass-ceramic cover plate.
FIG. 4 is a graph showing the b-value distribution of a glass ceramic cover plate.
FIG. 5 is a graph showing the distribution of the single-body ball-drop cracking ability of a glass-ceramic cover plate.
FIG. 6 is a graph showing the probability distribution of the four-bar bending strength B10 of the glass-ceramic cover plate.
FIG. 7 is a graph showing a glass-ceramic cover plate assembly 180g mobile phone drop fracture height distribution.
FIG. 8 is a graph of probability distribution of a glass-ceramic cover plate assembly 180g mobile phone drop fracture height B20.
Fig. 9 is an atomic force microscope image of a glass-ceramic cover plate.
Fig. 10 is a schematic flow chart of a method for preparing a glass ceramic cover plate according to an embodiment of the present application.
Fig. 11 is a schematic diagram of an electronic device according to an embodiment of the present application.
Description of the main reference signs
Electronic device 100
Screen display cover board 10
Housing 30
Detailed Description
Embodiments of the present application are described below with reference to the accompanying drawings in the embodiments of the present application.
The data range values recited in this application shall include the end values unless otherwise specified.
The cover plate made of transparent glass is used as a rear cover/shell of various electronic devices such as mobile phones, and has better appearance grade, better touch feeling, stronger decorative property and higher technological sense. However, glass is a brittle material, and when used as a rear cover or a case of an electronic device, the glass is liable to be broken.
The glass ceramic cover plate can be used as a rear cover/shell or a transparent screen cover plate of various electronic equipment such as a mobile phone. The microcrystalline glass cover plate has high strength and excellent anti-falling performance, the falling height of the whole machine on sand paper and marble is more than or equal to 1.5m, and meanwhile, the transparency and the optical performance meet the screen use requirements of electronic equipment such as mobile phones and the like.
The formula of the microcrystalline glass cover plate in the embodiment of the application is as follows:
SiO 2 65 to 85 percent of the weight ratio,
Al 2 O 3 5 to 12 percent of the weight ratio,
Na 2 o weight ratio is 0.5-6%,
Li 2 4 to 9 percent of O by weight,
P 2 O 5 0.05 to 3 percent of the weight ratio,
K 2 o weight ratio is 0.5-3%,
MgO in 0.5-8 wt%,
TiO 2 0.5 to 3 percent of the weight ratio,
ZrO 2 0.1 to 3 percent by weight.
The microcrystalline glass cover plate is prepared from the raw materials in the proportion.
The microcrystalline glass cover plate is obtained by strengthening treatment of chemical ion exchange of microcrystalline glass sheets prepared from the raw materials in the proportion. Compared with the conventional glass strengthening treatment, the molten salt used in the strengthening treatment increases LiNO 3 The surface stress of the microcrystalline glass cover plate is enhanced by strengthening treatment, and the stability of the surface state can be ensured while the strength is improved. After the strengthening treatment, the surface layer of the microcrystalline glass sheet with a certain thickness (depth) is transformed into a strengthening layer, wherein the thickness of the strengthening layer is more than or equal to 90 micrometers, the surface compressive stress of the strengthening layer is more than or equal to 160MPa, and the depth from the outer surface is 5The compressive stress at 0 micrometers is more than or equal to 65MPa.
Increasing LiNO 3 The reason for (2) is: the microcrystalline glass is different from conventional glass in that the microcrystalline glass contains a certain proportion of crystal phase, and the characteristic ensures that when the microcrystalline glass is subjected to chemical strengthening, besides the ion exchange of the glass phase, part of ions in the crystal phase of the surface layer also participate, so that the crystal phase of the surface layer is destroyed, loose holes are formed in the surface layer, the exchanged Na ions and K ions are enriched in the holes, and under the high-temperature and high-humidity environment, the part of ions and water vapor form white Na salt and K salt which are adhered to the surface of the glass, so that the cleanliness and the display effect of the material are affected. Increasing LiNO 3 On one hand, the damage to the surface crystal in the strengthening process can be restrained; on the other hand, na ions and K ions enriched on the surface can be reduced, so that the material can keep stable surface performance in a high-temperature and high-humidity environment. The glass-ceramic cover plate comprises a glass phase, quartz (SiO) 2 ) Crystalline, lithium disilicate (Li) 2 Si 2 O 5 ) Crystals and petalite (Li [ ALSi ] 4 O 10 ]) And (5) a crystal. The glass phase is an amorphous substance formed by a series of physical and chemical reactions of each constituent substance and impurities during high-temperature sintering, and is mainly used for bonding dispersed crystalline phases together. In the microcrystalline glass cover plate, the glass phase volume accounts for 15% -70%, the quartz crystal volume accounts for 10% -55%, the lithium disilicate crystal volume accounts for 10% -40%, and the petalite crystal volume accounts for 10% -40%. The crystal sizes of the quartz crystal, the lithium disilicate crystal, and the petalite crystal are less than 80nm, preferably less than 50nm.
In some embodiments, the glass-ceramic cover plate is obtained by performing hot bending forming and chemical ion exchange strengthening treatment on glass-ceramic sheets. That is, the hot bend forming may be performed selectively or not. When the microcrystalline glass sheet is subjected to hot bending treatment, the formation of lithium disilicate crystals and petalite crystals is promoted, so that the lithium disilicate crystals and the petalite crystals are increased, and the optimization of optical performance and the improvement of strength are brought. The main forming mechanism is that lithium disilicate crystals and petalite crystals are formed by combining with Li, al and the like along with the rupture of Si-O non-bridging oxygen bonds in the hot bending process.
The shape of the glass ceramic cover plate comprises a two-dimensional flat plate structure (2D), a two-dimensional flat plate structure (2.5D) with a certain radian and a three-dimensional structure (3D) with bending. The hot bending forming can be selectively performed, and the hot bending forming treatment can not be performed on the 2D/2.5D glass ceramic cover plate.
Referring to FIG. 1, a Raman spectrum of a glass-ceramic sheet and a glass-ceramic sheet after being subjected to hot bending molding at 750 ℃; wherein the abscissa is 950-1050cm -1 Corresponding Si-O non-bridging oxygen bond; horizontal coordinate 400-700cm -1 Represents bridging oxygens. As can be seen from fig. 1: corresponding abscissa 950-1050cm of microcrystalline glass sheet after hot bending forming -1 The peak strength at the point is obviously reduced, which indicates that Si-O non-bridging oxygen bonds are broken and reduced.
Referring to FIG. 2, the average transmittance of the microcrystalline glass sheet for light with the wavelength ranging from 450nm to 1000nm is more than or equal to 85%; the microcrystalline glass cover plate obtained by hot bending forming and strengthening treatment of the microcrystalline glass sheet has the average transmittance of more than or equal to 88 percent for light with the wavelength ranging from 450nm to 1000 nm. This demonstrates that the hot bend forming and strengthening process can significantly improve the light transmittance of the glass.
The haze of the microcrystalline glass sheet is 1.0-1.35%, and the value b of the color difference value b is 1.5-2.8. The haze of the glass ceramic cover plate is less than or equal to 0.2%, and preferably less than or equal to 0.15%. Haze of the glass-ceramic cover sheet obtained by hot bending (optionally) and strengthening the glass-ceramic sheet is less than or equal to 0.2%, as shown in FIG. 3, wherein each point of FIG. 3 represents one test data and the ordinate represents the haze value. The color difference b value of the glass ceramic cover plate is smaller than or equal to |b| and smaller than or equal to 1.2, and is preferably smaller than or equal to 0.8. As shown in FIG. 4, the color difference value b value b.ltoreq.1.2, where each point in FIG. 4 represents data from a test, and the ordinate represents the color difference value b value.
As shown in FIG. 5, the monomer falling energy of the microcrystalline glass cover plate is more than 0.2J. The test of the single body falling ball energy is to place a test sample on a test table, freely fall a steel ball with a specified weight on the sample from a specified falling height, impact the sample until the sample is broken, and calculate the impact energy value through the falling height and the weight of the steel ball.
As shown in FIG. 6, the four-bar bending strength (Wei Bo distribution B10) of the glass-ceramic cover plate is greater than 550Mpa, and the average value is greater than 800Mpa. The four-bar bending strength is a conventional test in the field of mobile phones, and the specific test method comprises the following steps: the lower two support rods support the two opposite ends of the sample, the upper two cylindrical press rods are pressed downwards from the middle position of the sample, and some stress values and displacement amounts of the test sample during fracture are converted to obtain bending strength.
The glass-ceramic cover plate was assembled on a complete machine, which included a glass-ceramic cover plate with a weight of 180g, and dropped on sandpaper and marble with a drop height of 1.5m or more, as shown in fig. 7. As shown in fig. 8, the drop height (Wei Bo distribution B20) is greater than 1.65m.
Referring to fig. 9, an afm of the glass-ceramic cover plate can be seen from fig. 9: the grain diameter of the glass ceramic cover plate is about 50nm, and the surface roughness is about 1.5nm.
Referring to fig. 10 in combination, the preparation method of the glass ceramic cover plate comprises the following steps:
(1) The glass stock solution is prepared by smelting the following raw material formulation at 1300-1700 ℃:
SiO 2 65 to 85 percent of the weight ratio,
Al 2 O 3 5 to 12 percent of the weight ratio,
Na 2 o weight ratio is 0.5-6%,
Li 2 4 to 9 percent of O by weight,
P 2 O 5 0.05 to 3 percent of the weight ratio,
K 2 o weight ratio is 0.5-3%,
MgO in 0.5-8 wt%,
TiO 2 0.5 to 3 percent of the weight ratio,
ZrO 2 0.1 to 3 percent by weight.
(2) Forming the glass stock solution into a transparent glass body;
(3) Carrying out heat treatment on the glass body at the temperature of 500-600 ℃ for 0.5-10 h to nucleate, and carrying out heat treatment at the temperature of 650-800 ℃ for 0.5-10 h to crystallize after nucleating to obtain a microcrystalline glass sheet;
(4) Performing hot bending forming treatment on the microcrystalline glass sheet;
(5) And strengthening the glass ceramic sheet after hot bending molding by a chemical ion exchange process.
The step (2) of forming the glass body from the glass stock solution comprises the following steps: the glass body is formed by one of a rolling method, a melt casting method, a float method, an overflow method, and a sintering method, and then the glass body is cooled to room temperature at a uniform speed, and the cooling process is called rough annealing. The method further comprises the step of removing bubbles in the glass stock solution before forming the glass body.
As shown in fig. 10, the preparation method further includes: prior to step (4) of performing a hot-bending forming process on the glass-ceramic sheet, cutting, polishing, and computer numerically controlled machining (Computerized Numerical Control, CNC) of the glass-ceramic sheet. The cutting may be performed by a numerically controlled machine tool, for example, assuming that a glass-ceramic product having a thickness d is to be finally produced, the thickness of the glass-ceramic sheet obtained by cutting is 0.1 to 0.25mm greater than the thickness d. Since the glass is also polished after cutting, the thickness may be reduced. The thickness of the glass cover plate of a mobile phone is generally 0.3mm-1.2mm. The slices of the glass ceramic sheet obtained after cutting are polished to make the surface flat and smooth, and can be roughly and finely ground by adopting polishing leather, a hairbrush, a sponge polishing disk and the like in combination with polishing powder.
It will be appreciated that step (4) of the hot-bending process may also be omitted. The step (4) of performing the hot bending forming treatment on the glass-ceramic sheet is specifically performed by selectively performing the hot bending forming treatment on the glass-ceramic sheet: performing hot bending forming at 650-800 deg.c and forming pressure of 0.3-0.8 MPa. The purpose of the hot-bending molding is to obtain a glass cover plate of a desired 3D shape. The step (5) of strengthening the glass-ceramic sheet comprises two ion exchange strengthening steps. Strong strengthThe melting treatment is performed in a strengthening furnace in which an alkali metal salt (molten salt, also referred to as strengthening furnace water) in a molten state is provided, and the glass ceramic is immersed in the molten salt for ion exchange and then cooled. First ion exchange: KNO with molten salt composition of 0mol% to 50mol% 3 50mol% to 100mol% NaNO 3 0mol% to 5mol% LiNO 3 The temperature of the molten salt is 400-480 ℃ and the ion exchange time is 6-15 h. Second ion exchange: the molten salt has a composition KNO 3 And the weight is KNO 3 0.05% -5% by weight of LiNO 3 The temperature of the molten salt is 350-420 ℃, and the ion exchange time is 0.5-2h. The principle of the chemical ion exchange is that a compressive stress strengthening layer is formed on the surface of glass by ion exchange of alkali metal ions (K ions, na ions) with larger radius and alkali metal ions (Na ions, li ions) with smaller radius in strengthening furnace water, wherein the first ion exchange mainly carries out sodium ions in molten salt to replace lithium ions in the microcrystalline glass sheet, and the second ion exchange mainly carries out potassium ions in molten salt to replace sodium ions in the microcrystalline glass sheet. The stress strengthening layer formed on the surface of the glass ceramics after the twice chemical ion exchange strengthening can effectively improve the anti-falling strength of the glass ceramics.
As shown in fig. 10, the glass-ceramic obtained by the strengthening treatment may be subjected to a surface decoration treatment, for example, a surface decoration treatment by a screen printing, pad printing, coating or film lamination process, so as to obtain a glass-ceramic cover plate with a final effect.
The microcrystalline glass sheet is subjected to hot bending forming and chemical ion exchange strengthening treatment, wherein the strengthening process comprises two ion exchanges, and LiNO is added in strengthening furnace water 3 The component can enhance the surface stress and improve the strength and ensure the stability of the surface state.
When the glass ceramic cover plate is subjected to high-temperature 3D hot bending forming, lithium disilicate crystals and petalite crystals in the glass ceramic sheet are increased, optimization of optical performance and improvement of strength are brought, and then the glass ceramic cover plate with high strength and excellent anti-drop performance, wherein the optical performance meets the use requirement of a display screen, is obtained. The microcrystalline glass sheet mainly comprises quartz crystals, lithium disilicate crystals and petalite crystals; the microcrystalline glass sheet can promote the formation of lithium disilicate crystals and petalite crystals during hot bending treatment. As can be seen from the raman spectrum test results before and after the hot bending, during the hot bending, along with the rupture of Si-O non-bridging oxygen bonds, silicon oxygen combines with Li, al and the like to form lithium disilicate crystals and petalite crystals. The glass phase volume in the microcrystalline glass cover plate accounts for 15% -70%, the quartz crystal volume accounts for 10% -55%, the lithium disilicate crystal volume accounts for 10% -40%, and the petalite crystal volume accounts for 10% -40%.
The average transmittance of the microcrystalline glass sheet to light with the wavelength ranging from 450nm to 1000nm is more than or equal to 85 percent; the glass ceramic cover plate obtained through hot bending forming (selective carrying out) and strengthening treatment has the average transmittance of more than or equal to 88 percent for light with the wavelength ranging from 450nm to 1000 nm.
The haze of the microcrystalline glass sheet is 1.0-1.35%, and the value b of the color difference value is 1.5-2.8; the haze of the microcrystalline glass cover plate obtained through hot bending forming (selective carrying out) and strengthening treatment is less than or equal to 0.2%, and the color difference value b is less than or equal to 1.2.
Referring to fig. 11, the present application further provides an electronic device 100, which includes a transparent screen display cover 10 and a housing 30, wherein the screen display cover 10 and the housing 30 cooperate to accommodate a functional module (not shown) of the electronic device 100, such as a touch panel, a battery, a circuit board, a chip, and the like. At least one of the screen display cover 10 and the housing 30 is the glass ceramic cover described above. In this embodiment, the electronic device 100 is a mobile phone, but is not limited to a mobile phone, and may be other electronic devices, such as a tablet computer.
The glass ceramic cover plate has high strength and excellent anti-falling performance, and meanwhile, the transparency and the optical performance meet the screen use requirements of electronic equipment such as mobile phones, so that the service life of the electronic equipment 100 can be effectively prolonged.
The application also provides a method for repairing the surface scratch and other appearance defects of the glass ceramic cover plate. The method can effectively improve the processing yield of the glass ceramic cover plate.
The method comprises the following steps: (1) Polishing two opposite surfaces of the microcrystalline glass cover plate; (2) And placing the polished microcrystalline glass cover plate into a strengthening furnace for ion exchange treatment.
The two opposite surfaces of the glass cover plate are distributed into concave surfaces and convex surfaces, a polishing disk made of sponge materials is adopted, the polishing time of the concave surfaces is 900s-2500s, and the polishing time of the convex surfaces is 500s-1500s.
Ion exchange is carried out on the glass ceramic cover plate after polishing in a strengthening furnace, and the molten salt component is KNO 3 And the weight is KNO 3 0% -5% LiNO 3 The temperature of the molten salt is 350-420 ℃, and the ion exchange time is 0.5-2h.
Alternatively, the ion exchanged molten salt composition is KNO of 0mol% to 50mol% 3 50mol% to 100mol% NaNO 3 0mol% to 3mol% LiNO 3 The temperature of the molten salt is 400-480 ℃ and the ion exchange time is 0.5-2h.
And through the strengthening treatment of ion exchange, the compressive stress (CS_50) of the microcrystalline glass cover plate with the depth of 50 microns from the outer surface is more than or equal to 65MPa, the strengthening Depth (DOL) is more than or equal to 90 microns, and the surface stress (CT) is more than or equal to 160MPa. The single-body strength four-bar bending strength B10 of the microcrystalline glass cover plate is more than 550Mpa, and the single-body falling energy is more than 0.2J.
The application also provides an anti-fingerprint method of the glass ceramic cover plate. The method comprises the following steps: (1) Cleaning the glass ceramic cover plate by adopting an alkaline solution; (2) And plating an anti-fingerprint film on the microcrystalline glass cover plate in a vacuum coating mode.
And cleaning the glass-ceramic cover plate by adopting an alkaline solution, wherein the pH value of the alkaline solution is less than 12, the surface roughness Ra of the glass-ceramic cover plate is less than 1.5nm after cleaning, and the change value of the b value of the glass-ceramic cover plate is less than 0.3 after cleaning.
And plating an anti-fingerprint film on the microcrystalline glass cover plate in a vacuum coating mode. Before the anti-fingerprint film is plated, a priming layer is formed on the microcrystalline glass cover plate in advance, wherein the priming layer can be SiO with the thickness of 3nm-15nm 2 The layer can be coated by vacuum sputtering or evaporationIs obtained by way of example. Then forming an anti-fingerprint film with low surface energy and thickness of 10nm-50nm on the priming layer, wherein the component can be chain substances such as perfluoropolyether, and the like, and the anti-fingerprint film is mainly obtained by an evaporation coating mode. The vacuum degree of the coating machine is preferably 5 x 10 -5 torr above. In some embodiments, the vacuum coating is divided into 3 operation steps: plasma treatment of glass surface, siO plating 2 A priming layer and an anti-fingerprint film layer plated with organic materials. Plasma treatment time is 50-300s; plating SiO 2 The rotation speed of the priming layer is 0.5-2rpm, the time is 200-600s, the voltage is 2-5v, and the current is 150mA-300mA; the rotation speed of the anti-fingerprint film plating layer is 1.0-2rpm, the time is 300-700s, the voltage is 2-5v, and the current is 150mA-300mA.
The microcrystalline glass cover plate plated with the fingerprint-resistant film layer has a rubber friction resistance of 3500 times and a water drop angle of more than 105 degrees. As shown in the following table one, the water drop angle of the microcrystalline glass cover plate plated with the anti-fingerprint film layer is larger than 109 degrees after 3500 times of rubber friction resistance.
List one
The water drop angle of the microcrystalline glass cover plate plated with the anti-fingerprint film layer is larger than 102 degrees after 2500 times of steel wool friction resistance. As shown in table two below, the drop angle was greater than 103 °.
Watch II
The embodiments of the present application are further described below by way of specific examples.
Example 1
Mixing 70% of SiO by mass 2 ，11％ Al 2 O 3 ，1％ Na 2 O，8％ Li 2 O，3％ P 2 O 5 ，1％ K 2 O，3％ MgO，2％TiO 2 ，1％ZrO 2 Is melted at 1650 ℃ and shaped into blocks. Cutting the block into blocks with thickness of 0.7-0.9m by cutting processm, then carrying out crystallization treatment on the sheet, carrying out heat treatment for 6 hours at 550 ℃, then heating to 720 ℃ at 30 ℃/h, preserving heat for 5 hours, and finally cooling to room temperature in a furnace to obtain the transparent microcrystalline glass.
The crystallized sheet was polished to a 0.55-0.75mm transparent sheet by profile CNC machining and polishing. And then forming the flat glass-ceramic into the glass-ceramic with the 3D curved surface under the hot bending forming condition of 730 ℃ and 0.65 MPa.
Carrying out ion exchange strengthening on the formed 3D microcrystalline glass, wherein the strengthening conditions are as follows: for the first ion exchange, the molten salt component is 7.8mol% KNO 3 ，92mol％NaNO 3 ，0.2mol％LiNO 3 The temperature of the molten salt is 450 ℃, and the ion exchange time is 11h; the second ion exchange, the molten salt composition is 99.8wt% KNO 3 ，0.2wt％LiNO 3 The molten salt temperature is 390 ℃ and the ion exchange time is 1h.
And finally, carrying out appearance decoration treatment on the processed 3D glass ceramics by using pad printing ink and anti-fingerprint coating to obtain the glass ceramics cover plate with the 3D curved surface.
The average light transmittance of the prepared curved glass ceramic cover plate is more than or equal to 88%, preferably more than or equal to 91.5%, the value of b is less than or equal to 1.2%, the value of b is preferably less than or equal to 0.8, the haze is less than or equal to 0.2%, and the haze is preferably less than or equal to 0.15% in the wavelength range of 450-1000 nm.
The prepared glass ceramic cover plate is assembled on a 180g mobile phone, and can fall through marble of 1.5m and 180-mesh sand paper ground.
Example two
Mixing 68% of SiO by mass 2 ，10％ Al 2 O 3 ，3％ Na 2 O，7％ Li 2 O，5％ P 2 O 5 ，1％ K 2 O，3％ MgO，2％TiO 2 ，1％ZrO 2 Is melted at 1650 ℃ and shaped into blocks. Cutting the block material into sheets with the thickness of 0.7-0.9mm through a cutting process, crystallizing the sheets, performing heat treatment at 550 ℃ for 7.5 hours, heating to 720 ℃ at 40 ℃/h, preserving heat for 6 hours, and finally cooling the furnace to room temperature to obtain the transparent microcrystalline glass.
The crystallized sheet was polished to a 0.55-0.75mm transparent sheet by profile CNC machining and polishing. And then forming the flat glass-ceramic into the 3D curved glass-ceramic under the hot bending forming condition of 720 ℃ and 0.75 MPa.
Carrying out ion exchange strengthening on the formed 3D microcrystalline glass, wherein the strengthening conditions are as follows: first ion exchange, the molten salt composition is 9.8mol% KNO 3 ，90mol％NaNO 3 ，0.2mol％LiNO 3 The temperature of the molten salt is 450 ℃, and the ion exchange time is 10 hours; the second ion exchange, the molten salt composition is 99.8wt% KNO 3 ，0.2wt％LiNO 3 The temperature of the molten salt is 380 ℃ and the ion exchange time is 1.5h.
And finally, carrying out appearance decoration treatment on the processed curved glass ceramics by using pad printing ink and anti-fingerprint coating to obtain the glass ceramics cover plate with the 3D curved surface.
In the processing process, long-time alkali treatment is avoided, and when a flat plate and an ultrasonic tank are adopted for cleaning, the pH value of cleaning liquid is less than 12, the temperature is less than 65 ℃, and the single cleaning time is less than 60 minutes.
Before anti-fingerprint coating, the change value of b value before and after cleaning is less than 0.3 and the surface roughness Ra is less than 1.5nm by controlling cleaning in the process.
The water drop angle of the prepared curved glass ceramic cover plate is larger than 105 degrees after 2500 times of rubber friction can be achieved, and the water drop angle is larger than 100 degrees after 2500 times of steel wool friction resistance.
The prepared glass ceramic cover plate is assembled on a 180g mobile phone, and can fall through marble of 1.5m and 180-mesh sand paper ground.
Example III
Mixing the materials with 69% of SiO by mass 2 ，10％ Al 2 O 3 ，2％ Na 2 O，7％ Li 2 O，3％ P 2 O 5 ，1％ K 2 O，5％ MgO，2％TiO 2 ，1％ZrO 2 Is melted at 1650 ℃ and shaped into blocks. Cutting the block material into sheets with the thickness of 0.7-0.9mm through a cutting process, crystallizing the sheets, performing heat treatment at the temperature of 580 ℃ for 6 hours, heating to 720 ℃ at the speed of 30 ℃/h, preserving heat for 6 hours, and finally cooling the furnace to room temperature to obtain the transparent glass ceramics.
The crystallized sheet was polished to a 0.55-0.75mm transparent sheet by profile CNC machining and polishing. And then forming the flat glass-ceramic into the glass-ceramic with the 3D curved surface under the hot bending forming condition of 730 ℃ and 0.65 MPa.
Carrying out ion exchange reinforcement on the formed 3D glass ceramic cover plate, wherein the reinforcement conditions are as follows: first ion exchange, fused salt to 21.8mol% KNO 3 ，78mol％NaNO 3 ，0.2mol％LiNO 3 The temperature of the molten salt is 450 ℃, and the ion exchange time is 11h; the second ion exchange, the molten salt composition is 99.5wt% KNO 3 ，0.5wt％LiNO 3 The molten salt temperature is 390 ℃ and the ion exchange time is 45min.
And finally, carrying out appearance decoration treatment on the processed curved glass ceramics by using pad printing ink and anti-fingerprint coating to obtain the glass ceramics cover plate with the 3D curved surface.
The surface scratch of the strengthened glass cover plate or the defect in the transfer printing ink process can be treated by reworking a defective sample, and the reworking process is as follows: and (5) carrying out back grinding on the defective products for 1200s in a concave surface sweeping and grinding mode and 700s in a convex surface sweeping and grinding mode. Strengthening the sample in a strengthening furnace after grinding, wherein the molten salt component is 99.8wt% KNO 3 ，0.2wt％LiNO 3 The molten salt temperature is 390 ℃ and the ion exchange time is 1h.
The prepared glass ceramic cover plate can repair scratch defects and printing ink defects after strengthening reworking, wherein after reworking, a glass ceramic sample CS_50 is more than or equal to 80MPa, DOL is more than or equal to 100 mu m, and CT is less than or equal to 125MPa.
The prepared glass ceramic cover plate is assembled on a 180g mobile phone, and can fall through marble of 1.5m and 180-mesh sand paper ground.
It should be noted that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the present application, and the changes or substitutions should be covered in the scope of the present application; in the case of no conflict, the embodiments of the present application and features of the embodiments may be combined with one another. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (16)
1. A glass-ceramic cover plate is characterized in that the glass-ceramic cover plate is obtained by strengthening treatment of glass-ceramic sheet through chemical ion exchange, and molten salt used in the strengthening treatment contains LiNO 3 ；
The glass ceramic cover plate comprises:
15-70% of glass phase by volume;
quartz crystal, the volume ratio is 10% -55%;
lithium disilicate crystals having a volume ratio of 10% -40%;
the volume ratio of the petalite crystal is 10-40%, and the crystal sizes of the quartz crystal, the lithium disilicate crystal and the petalite crystal are smaller than 80nm.
2. The glass-ceramic cover plate according to claim 1, wherein the glass-ceramic cover plate has a formula of:
SiO 2 65 to 85 percent of the weight ratio,
Al 2 O 3 5 to 12 percent of the weight ratio,
Na 2 o weight ratio is 0.5-6%,
Li 2 4 to 9 percent of O by weight,
P 2 O 5 0.05 to 3 percent of the weight ratio,
K 2 o weight ratio is 0.5-3%,
MgO in 0.5-8 wt%,
TiO 2 0.5 to 3 percent of the weight ratio,
ZrO 2 0.1 to 3 percent by weight.
3. The glass-ceramic cover plate according to claim 1 or 2, wherein the glass-ceramic cover plate is obtained by subjecting glass-ceramic sheet to hot bending forming and chemical ion exchange strengthening treatment.
4. A glass-ceramic cover sheet according to any one of claims 1 to 3, wherein the glass-ceramic cover sheet has a four-bar bending strength B10 of greater than 550MPa and an average value of greater than 800MPa.
5. The glass-ceramic cover sheet according to any one of claims 1 to 4, wherein an average transmittance of the glass-ceramic cover sheet to light in a wavelength range of 450nm to 1000nm is 88% or more.
6. The glass-ceramic cover sheet according to any one of claims 1 to 5, wherein the depth of the strengthening layer of the glass-ceramic cover sheet is 90 μm or more, the surface compressive stress of the strengthening layer is 160MPa or more, and the compressive stress at a depth of 50 μm from the outer surface is 65MPa or more.
7. The glass-ceramic cover sheet according to any one of claims 1 to 6, wherein,
the color difference b value of the glass ceramic cover plate is smaller than or equal to |b| and smaller than or equal to 1.2.
8. The glass-ceramic cover sheet of any one of claims 1 to 7, wherein the glass-ceramic cover sheet has a haze of 0.2% or less.
9. The glass-ceramic cover sheet of any one of claims 1 to 8, wherein the glass-ceramic cover sheet can withstand a monomer ball drop energy of greater than 0.2J.
10. The cover glass according to any one of claims 1 to 9, wherein the cover glass is mounted on a complete machine comprising the cover glass having a weight of 180g, and has a complete machine sandpaper drop and marble drop strength of 1.5m or more.
11. The glass-ceramic cover sheet of any one of claims 1 to 10, further comprising an anti-fingerprint film, wherein the glass-ceramic cover sheet has a drop angle greater than 105 ° after 3500 rubber rubs.
12. An electronic device comprising a transparent screen display cover and a housing, wherein at least one of the screen display cover and the housing is the glass-ceramic cover of any one of claims 1 to 11.
13. The repair method of the glass ceramic cover plate scratch is characterized by comprising the following steps:
polishing two opposite surfaces of the glass ceramic cover plate;
ion exchange treatment is carried out on the polished microcrystalline glass cover plate, and the process and parameters of the ion exchange treatment are as follows:
the molten salt has a composition KNO 3 And the weight is KNO 3 0% -5% LiNO 3 The temperature of the molten salt is 350-420 ℃, and the ion exchange time is 0.5-2h; or,
KNO with molten salt composition of 0mol% to 50mol% 3 50mol% to 100mol% NaNO 3 0mol% to 3mol% LiNO 3 The temperature of the molten salt is 400-480 ℃ and the ion exchange time is 0.5-2h.
14. The repairing method according to claim 13, wherein the opposite surfaces of the glass cover plate are respectively a concave surface and a convex surface, a polishing disk made of sponge material is adopted, the polishing time of the concave surface is 900s-2500s, and the polishing time of the convex surface is 500s-1500s.
15. The fingerprint resistance method of the glass ceramic cover plate is characterized by comprising the following steps of:
cleaning a glass ceramic cover plate by adopting an alkaline solution, wherein the pH value of the alkaline solution is less than 12, and the surface roughness Ra of the glass ceramic cover plate is less than 1.5nm after cleaning;
and plating an anti-fingerprint film on the microcrystalline glass cover plate in a vacuum coating mode, so that the microcrystalline glass cover plate plated with the anti-fingerprint film layer has a rubber friction resistance 3500 times and a water drop angle greater than 105 degrees.
16. The method of claim 15, wherein the glass-ceramic cover plate has a b-value variation value of < 0.3 before and after cleaning.
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| WO2019191358A1 (en) * | 2018-03-29 | 2019-10-03 | Corning Incorporated | Ion exchanged glass-ceramic articles |
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| Publication number | Publication date |
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| CN117658473A (en) | 2024-03-08 |
| CN115477473B (en) | 2023-09-22 |
| CN115477473A (en) | 2022-12-16 |
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