CN107892472B - Composition for glass, and preparation method and application thereof - Google Patents
Composition for glass, and preparation method and application thereof Download PDFInfo
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- CN107892472B CN107892472B CN201711187456.3A CN201711187456A CN107892472B CN 107892472 B CN107892472 B CN 107892472B CN 201711187456 A CN201711187456 A CN 201711187456A CN 107892472 B CN107892472 B CN 107892472B
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- 239000011521 glass Substances 0.000 title claims abstract description 153
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 22
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000005728 strengthening Methods 0.000 claims abstract description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 22
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 29
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000035882 stress Effects 0.000 description 34
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-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
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910001414 potassium ion Chemical group 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- FEPMHVLSLDOMQC-UHFFFAOYSA-N virginiamycin-S1 Natural products CC1OC(=O)C(C=2C=CC=CC=2)NC(=O)C2CC(=O)CCN2C(=O)C(CC=2C=CC=CC=2)N(C)C(=O)C2CCCN2C(=O)C(CC)NC(=O)C1NC(=O)C1=NC=CC=C1O FEPMHVLSLDOMQC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0416—Control or interface arrangements specially adapted for digitisers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Theoretical Computer Science (AREA)
- Ceramic Engineering (AREA)
- Human Computer Interaction (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the field of glass materials, and discloses a composition for glass, a preparation method and application thereof. The glass composition of the present invention contains 45 to 66% by weight of SiO based on the total weight of the glass composition210-23% by weight of Al2O30.01-10 wt% of B2O30.01 to 12 wt% of P2O510-19% by weight of Na2O, 0.01-5 wt.% of K2O, 0.01-5 wt% of Li2O, 0.01-5 wt% CaO and 0.01-3 wt% TiO2. The components in the glass composition provided by the invention have synergistic effects, so that the stress relaxation of the prepared glass is effectively improved, and the glass composition has the advantages of enhanced compressive stress, deep strengthening depth, high impact strength and the like. The protective cover plate is suitable for protecting display devices, and is particularly suitable for protecting cover plates of display devices, such as touch screen cover plates.
Description
Technical Field
The invention relates to the field of glass materials, in particular to a composition for glass, a preparation method and application thereof.
Background
In recent years, rapid development of display technology has brought about the successive development of high-tech electronic display products such as liquid crystal display (TFT-LCD), low-temperature polysilicon display technology, OLED display technology, and the like. Displays are widely used as electronic display devices in public places such as high-definition wall-mounted televisions, notebook computers, monitors, communication equipment, home appliance designs, the internet, and stadiums.
Organic materials have been used for the protective cover sheet for the above display devices, but have not been widely used due to defects of the materials themselves (easy aging, poor transmittance). Glass is always an indispensable material in the development of display technology, and the strength of the glass can be improved by changing the composition of the surface of the glass through chemical tempering, so that the glass has great use in the protection of display devices. In the using process, the touch screen cover plate glass is easy to contact and rub, and the generated scratch directly causes the surface roughness and the smoothness reduction of the touch screen, thereby influencing the using effect and more possibly causing the screen to break; but more informative shows that 80% of the display devices are damaged due to damage to the display screen caused by inadvertent dropping.
In the prior art, the glass composition for protecting the display device is difficult to obtain glass with excellent comprehensive properties such as improved stress relaxation and enhanced compressive stress, deep strengthening depth, good impact strength and the like after chemical strengthening.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a glass composition, glass, a preparation method and application thereof, wherein the glass composition and the glass have the advantages of improved stress relaxation, enhanced strengthening compressive stress, deep strengthening depth, good impact strength and other excellent comprehensive properties.
In order to achieve the above object, the present invention provides, in a first aspect, a composition for glass containing 45 to 66% by weight of SiO based on the total weight of the composition for glass210-23% by weight of Al2O30.01-10 wt% of B2O30.01 to 12 wt% of P2O510-19% by weight of Na2O, 0.01-5 wt.% of K2O, 0.01-5 wt% of Li2O, 0.01-5 wt% CaO and 0.01-3 wt% TiO2Wherein, the weight percent of the SiO is less than or equal to 58 percent2+Al2O3+P2O5)-B2O3Less than or equal to 83 weight percent and less than or equal to 8 weight percent of Na2O-(K2O+Li2O) is less than or equal to 15 weight percent, and CaO and TiO are less than or equal to 1 weight percent2Less than or equal to 6 percent by weight.
Preferably, the composition for glass contains 47 to 63 wt% of SiO based on the total weight of the composition for glass212-22% by weight of Al2O31.5-8% by weight of B2O32-10% by weight of P2O511-16% by weight of Na2O, 0.5-4 wt.% of K2O, 0.5-4 wt% Li2O, CaO in an amount of 0.2 to 3 wt% and TiO in an amount of 0.5 to 2 wt%2Wherein, the weight percent of the SiO is less than or equal to 60 percent2+Al2O3+P2O5)-B2O3Not more than 80 wt%, not more than 10 wt% Na2O-(K2O+Li2O) is less than or equal to 14 weight percent, and CaO + TiO2 is less than or equal to 1.2 weight percent and less than or equal to 4 weight percent.
More preferably, the composition for glass contains 50 to 62% by weight of SiO based on the total weight of the composition for glass214-20% by weight of Al2O32-6% by weight of B2O33-8% by weight of P2O512-14% by weight of Na2O, 0.5-3 wt.% of K2O, 0.5-2 wt% Li2O, CaO in an amount of 0.5 to 1.5% by weight, and TiO in an amount of 0.5 to 1.5% by weight2Wherein, the weight percent of the SiO is less than or equal to 60 percent2+Al2O3+P2O5)-B2O3Not more than 77 wt%, and not more than 11 wt% Na2O-(K2O+Li2O) is less than or equal to 13 weight percent, and CaO and TiO are less than or equal to 1.4 weight percent2Less than or equal to 3 percent by weight.
In a second aspect, the present invention provides a method of making glass, the method comprising: the composition for glass is sequentially subjected to mixing, melting, homogenizing, cast molding and annealing.
Preferably, the method further comprises performing chemical strengthening treatment after annealing.
More preferably, the chemical strengthening treatment method includes: the strengthening liquid is pure KNO3The temperature of the melt is 380-450 ℃, and the time is 2-10 h.
More preferably, in the chemical strengthening treatment method, the temperature is 410-450 ℃, and the time is 4-8 h.
In a third aspect, the invention provides glass made by the above method.
The glass prepared by the invention can have the glass density of 2.38-2.48g/cm3Coefficient of expansion 54 × 10-7-83×10-7The Young modulus is 60-81Gpa, the compressive stress is 800-.
Preferably, the glass has a density of 2.41 to 2.45g/cm3Coefficient of expansion 60X 10-7-76×10-7The Young modulus is 62-73GPa, the compressive stress is 900-.
In a fourth aspect, the present invention provides the use of the above-described composition for glass and glass for the protection of display devices, in particular for the protection of cover plates for display devices, such as touch screen cover plates.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the components in the composition for glass provided by the invention interact with each other to generate influence, and the proper composition and content of the composition for glass are obtained after a plurality of tests. The glass of the invention has excellent comprehensive properties and benefits from SiO in the glass component2、Al2O3、B2O3、P2O5、Na2O、K2O、Li2O、CaO、TiO2In combination therewith, wherein: SiO in glass2Substituted by aluminium phosphate (consisting of tetrahedrally coordinated aluminium and phosphorus), the boron atoms being present in three coordination, the network structure of the glass being modified; ② because the glass component of the invention contains Na2O、K2O、Li2O, the special glass structure is suitable for chemical strengthening; ③ glass component Al in chemical strengthening of glass2O3With TiO2The cooperation of the glass reinforcing agent and the glass reinforcing agent can improve the problem of glass fragment caused by too high reinforcing speed, improve the reinforcing effect of the glass and improve the qualified rate of glass reinforcement; CaO and TiO in the glass component2The glass can inhibit glass crystallization, improve glass stability, improve glass impact resistance, and improve stressRelaxation, which helps to increase the compressive stress. Furthermore, the composition for glass of the present invention has a composition of not more than 58% by weight (SiO)2+Al2O3+P2O5)-B2O3Less than or equal to 83 weight percent and less than or equal to 8 weight percent of Na2O-(K2O+Li2O) is less than or equal to 15 weight percent, and CaO and TiO are less than or equal to 1 weight percent2Less than or equal to 6 weight percent can effectively improve the stress relaxation of the glass, enhance the compressive stress, and have deep strengthening depth, high impact strength and the like. The protective cover plate is suitable for protecting display devices, and is particularly suitable for protecting cover plates of display devices, such as touch screen cover plates.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a composition for glass comprising 45 to 66% by weight of SiO based on the total weight of the composition for glass210-23% by weight of Al2O30.01-10 wt% of B2O30.01 to 12 wt% of P2O510-19% by weight of Na2O, 0.01-5 wt.% of K2O, 0.01-5 wt% of Li2O, 0.01-5 wt% CaO and 0.01-3 wt% TiO2Wherein, the weight percent of the SiO is less than or equal to 58 percent2+Al2O3+P2O5)-B2O3Less than or equal to 83 weight percent and less than or equal to 8 weight percent of Na2O-(K2O+Li2O) is less than or equal to 15 weight percent, and CaO and TiO are less than or equal to 1 weight percent2Less than or equal to 6 percent by weight.
In the composition for glass of the present invention, SiO2Is a component constituting the glass skeleton, SiO2At higher contents, the chemical resistance and mechanical strength increase, and the high-temperature viscosity of the glass increases, if SiO is present2Too much glass, SiO, is difficult to obtain with long material properties2When the content is low, glass is not easily formed, the strain point is reduced, the expansion coefficient is increased, and the acid resistance and the alkali resistance are reduced. Therefore, SiO suitable in the present invention is SiO suitable in consideration of the properties of the glass such as melting temperature, upper limit temperature of devitrification, expansion coefficient, mechanical strength, and material properties2The content is 45-66 wt%.
The composition for glass of the present invention contains Al2O3The non-bridging oxygen and Al form an aluminum-oxygen tetrahedron, and the volume of the tetrahedron is larger than that of a silicon-oxygen tetrahedron, so that larger gaps are generated in a glass structure, ion exchange is facilitated, the chemical strengthening effect of the glass is better, and the scratch resistance and the falling resistance of the glass are improved. However, Al2O3Too high content to be melted, and Al2O3If the content is too low, the glass is liable to devitrify, and the mechanical strength is low, which is not favorable for molding, so that Al suitable for the present invention2O3The content is 10-23 wt%.
The composition for glass of the present invention contains B2O3Can reduce glass viscosity, low dielectric loss and vibration loss, and improve glass brittleness, toughness and light transmittance. B is2O3A suitable structure in glass after melting is [ BO ]4]Tetrahedron and [ BO3]Two structures of triangle, B under high temperature melting condition2O3Difficult to form [ BO4]The viscosity at high temperatures can be reduced, and the amount of free oxygen at low temperatures determines the preferential formation of tetrahedra or trigones. Further, in borosilicate glass, [ BO4]The tetrahedron may be reacted with [ SiO ]4]Tetrahedra form a unified continuous three-dimensional network, and [ BO3]The triangle bodies are connected by a rotatable boron ring, and slide is generated after stress to cause plastic rheology, so that the plastic rheology is lowBrittleness and higher fracture toughness. Suitable compounds B in the invention2O3The content is 0.01-10 wt%.
P is introduced into the composition for glass of the present invention2O5The ion exchange rate during subsequent glass strengthening can be increased, and the damage resistance of the glass can be improved. But P is2O5Too high a content may decrease the chemical stability of the glass, and thus, P is suitable in the present invention2O5The content is 0.01-12 wt%.
Li incorporated in the composition for glass of the present invention2O、Na2O、K2O is the main exchange ion during the chemical strengthening treatment. Wherein Li+The ionic radius is more than that of Na+Smaller, containing Li+The ion exchange speed of the glass is higher, so that the glass can obtain a thicker strengthening layer in a short time, namely Li+Ions and Na in the melt+Ion exchange and velocity ratio Na+And K+Ion exchange rate is fast, but Li2When the content of O is high, the corrosion of the refractory is severe. Na (Na)2O、K2Higher O content reduces the mechanical properties of the glass and affects the rate of chemical strengthening. Therefore, the present invention incorporates Na in an amount of 10 to 19% by weight in consideration of the overall properties of the glass2O, 0.01-5 wt.% of K2O, 0.01-5 wt% of Li2O。
The CaO is introduced into the composition for glass, so that the melting temperature of the glass can be reduced, the strain point of the glass can be improved, and the stability of the glass can be improved, wherein the CaO content is 0.01-5 wt%.
The composition for glass of the present invention contains TiO2The glass has improved elastic modulus, bending strength, strain point, etc. TiO in chemical strengthening process2The synergistic effect of the glass and CaO can improve stress relaxation, contribute to enhancing compressive stress and improving the impact resistance of glass, and the glass has better strengthening effect, and in addition, TiO2The alkali resistance and strength of the glass can be increased. However, TiO2At higher contents, the glass tends to be colored and the tendency of the glass to devitrify increases. Thus, the high alkali glass of the present invention is consideredCombination of glass System, TiO suitable in the present invention2The content is 0.1-3 wt%.
In order to further improve the effects of stress relaxation improvement, strengthening compressive stress, deep strengthening and high impact strength of the glass, the glass composition preferably contains 47 to 63 wt% of SiO based on the total weight of the glass composition212-22% by weight of Al2O31.5-8% by weight of B2O32-10% by weight of P2O511-16% by weight of Na2O, 0.5-4 wt.% of K2O, 0.5-4 wt% Li2O, CaO in an amount of 0.2 to 3 wt% and TiO in an amount of 0.5 to 2 wt%2Wherein, the weight percent of the SiO is less than or equal to 60 percent2+Al2O3+P2O5)-B2O3Not more than 80 wt%, not more than 10 wt% Na2O-(K2O+Li2O) is less than or equal to 14 weight percent, and CaO and TiO are less than or equal to 1.2 weight percent2Less than or equal to 4 wt%.
More preferably, the composition for glass contains 50 to 62% by weight of SiO based on the total weight of the composition for glass214-20% by weight of Al2O32-6% by weight of B2O33-8% by weight of P2O512-14% by weight of Na2O, 0.5-3 wt.% of K2O, 0.5-2 wt% Li2O, CaO in an amount of 0.5 to 1.5% by weight, and TiO in an amount of 0.5 to 1.5% by weight2Wherein, the weight percent of the SiO is less than or equal to 60 percent2+Al2O3+P2O5)-B2O3Not more than 77 wt%, and not more than 11 wt% Na2O-(K2O+Li2O) is less than or equal to 13 weight percent, and CaO and TiO are less than or equal to 1.4 weight percent2Less than or equal to 3 percent by weight.
In a second aspect, the present invention provides a method of making glass, the method comprising: the composition for glass is sequentially subjected to mixing, melting, homogenizing, cast molding and annealing.
In the method of the present invention, the melting may be carried out in a platinum rhodium crucible, and preferably, the melting conditions include: the temperature is 1450-1630 ℃, and the time is 6-12 h. The specific melting temperature and melting time can be determined by those skilled in the art according to practical situations, which are well known to those skilled in the art and will not be described herein.
In the method of the present invention, the casting molding is a conventional casting molding manner in the art, for example, it may be performed in a stainless steel mold, and the specific steps and condition parameters are well known in the art and will not be described herein again.
In the method of the present invention, the annealing conditions preferably include: the temperature is 500 ℃ and 800 ℃, and the time is 1-7 h. The specific annealing temperature and annealing time can be determined by those skilled in the art according to practical situations, which are well known to those skilled in the art and will not be described herein.
In the method of the present invention, the method may further include: and cooling the annealed glass to room temperature and then carrying out processing treatment.
The processing treatment in the method of the present invention is not particularly limited, and various mechanical processing methods which are generally used in the art may be used, and for example, the product obtained by the annealing treatment may be sliced, polished, chemically strengthened, or the like.
In the method of the present invention, the chemical strengthening method is various methods known in the art, for example, the chemical strengthening method may include: the strengthening liquid is pure KNO3The temperature of the melt is 380-450 ℃, the time is 2-10h, and the mechanical property of the glass can be improved by chemical strengthening.
Preferably, in order to obtain a glass with further improved mechanical properties, the method of chemical strengthening comprises: the strengthening liquid is pure KNO3The temperature of the melt is 410-450 ℃, and the time is 4-8 h.
In a third aspect, the invention provides glass made by the above method.
The glass prepared by the invention can have the glass density of 2.38-2.48g/cm3Coefficient of expansion 54 × 10-7-83×10-7The Young modulus is 60-81GPa, the compressive stress is 800-.
Preferably, the glass has a density of 2.41 to 2.45g/cm3Coefficient of expansion 60X 10-7-76×10-7The Young modulus is 62-73GPa, the compressive stress is 900-.
In a fourth aspect, the present invention provides the use of the above-described composition for glass and glass for the protection of display devices, in particular for the protection of cover plates for display devices, such as touch screen cover plates.
Examples
The present invention will be described in detail below by way of examples and comparative examples. In the following examples and comparative examples, the materials used are all commercially available unless otherwise specified, and the methods used are conventional in the art unless otherwise specified.
In the present invention, the density of the glass composition is described without going to the contrary with reference to GB/T7962.15-2010 colorless optical glass test method part 20: density "was measured using the Archimedes method.
In the present invention, the coefficient of thermal expansion of the glass composition is determined in accordance with ASTM E228-1985, test method for measuring linear thermal expansion of solid materials by means of a transparent quartz dilatometer, unless otherwise specified.
In the present invention, the Young's modulus of the glass composition is measured with reference to ASTM C-623, unless otherwise specified.
In the present invention, the compressive stress and the strengthening depth of the glass composition are measured by using a FSM-6000LE surface stress meter manufactured by Luceo Co., Ltd. (Tokyo, Japan), unless otherwise specified.
In the present invention, stress relaxation can be stabilized by relaxing the coefficient S without being described to the contrary0Characterization (expressed as the ratio of compressive stress at 7 hours to 3 hours for glass strengthening).
In the present invention, the impact resistance test of the glass composition is carried out by referring to the test of national standard GB15763.2-2005 without going into the contrary, except that 120g of steel ball is used, and the falling height of the steel ball is the falling height of the steel ball when the sample is destroyed.
In the present invention, the Vickers hardness of the glass composition is obtained by reference to the GB/T4340.2-2012 test without going to the contrary.
Examples 1 to 18
The components were weighed and mixed as shown in tables 1 to 3, the mixture was poured into a platinum-rhodium crucible, and then heated at 1620 ℃ for 9 hours, the molten glass was cast into a predetermined block-shaped glass article, and then the glass article was annealed at 640 ℃ for 3 hours in an annealing furnace. Placing the glass product in pure KNO3And in the molten strengthening liquid, chemically strengthening to obtain the finished glass product. The various properties of each finished glass were measured and the results are shown in tables 1-3.
Comparative examples 1 to 5
Finished glass products were obtained in accordance with the procedures of the examples except that the glass components of comparative examples 1 to 5 and the results of measuring the properties of the obtained products were shown in Table 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As can be seen from the results in tables 1, 2 and 3, the glass prepared from the composition for glass of the embodiment of the invention has moderate density, good expansion coefficient and excellent Young modulus, and after chemical strengthening, the stress relaxation is effectively improved, the compressive stress strength is high, the strengthening depth is deep, and the impact resistance height is high.
TABLE 4 comparison with tables 1, 2 and 3, Na in comparative example 12O-(K2O+Li2O) < 8, CaO + TiO in comparative example 22< 1, the glass obtained from the composition for glass of comparative example 1, after being chemically strengthened, has a coefficient of stability S of compressive stress relaxation00.93, the amount of change in the compressive stress strength over a long period of time was small, but comparative example 1 was small in the compressive stress strength, shallow in the depth of reinforcement, and much lower in the impact resistance than the examples in tables 1, 2 and 3. Glass compression stress relaxation stability factor S of comparative example 200.81, large change in compressive stress strength over time, and lower reinforcement depth and impact height than in the examples of tables 1, 2 and 3.
As can be seen, SiO is contained in an appropriate amount in the composition for glass of the present invention2、Al2O3、B2O3、P2O5、Na2O、K2O、Li2O、CaO、TiO2Cooperate with each other, and when the weight percentage of the mixture is less than or equal to 58 percent (SiO)2+Al2O3+P2O5)-B2O3Less than or equal to 83 weight percent and less than or equal to 8 weight percent of Na2O-(K2O+Li2O) is less than or equal to 15 weight percent, and CaO and TiO are less than or equal to 1 weight percent2When the weight percent is less than or equal to 6 percent, the density of the prepared glass is 2.38-2.48g/cm3Coefficient of expansion 54 × 10-7-83×10-7The Young modulus is 60-81Gpa, the compressive stress is 800-. The composition for glass and glass having the above excellent characteristics are suitably used for protecting display devices, particularly for protecting cover plates for display devices, such as touch panel cover plates.
It is worth noting that in the present invention the stress relaxation stabilizes the coefficient S by relaxing0Characterization (in the present invention, the ratio of compressive stress of 7 hours to 3 hours for glass strengthening) is adopted, generally speaking, in the prior art, the aluminosilicate glass is strengthened for about 2 to 5 hours, the surface compressive stress value of the glass reaches the maximum value, the strengthening time is prolonged to about 6 to 10 hours, the surface compressive stress value of the glass is reduced, and therefore the relaxation stability coefficient of the obtained glass is S0< 0.855, by tables 1, 2, 3The result shows that the relaxation stability coefficient of the glass is obviously improved after the chemical strengthening, the stress relaxation of the glass can be effectively improved, and the retention of mechanical properties such as compressive stress of the glass and the like in the strengthening process is facilitated.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. A composition for glass, characterized by containing 50 to 62% by weight of SiO based on the total weight of the composition for glass214-20% by weight of Al2O32-6% by weight of B2O33-8% by weight of P2O512-14% by weight of Na2O, 0.5-3 wt.% of K2O, 0.5-2 wt% Li2O, CaO in an amount of 0.5 to 1.5% by weight, and TiO in an amount of 0.5 to 1.5% by weight2Wherein, 66 weight percent is less than or equal to (SiO)2+Al2O3+P2O5)-B2O3Not more than 77 wt%, and not more than 11 wt% Na2O-(K2O+Li2O) is less than or equal to 13 weight percent, and CaO and TiO are less than or equal to 1.4 weight percent2Less than or equal to 3 percent by weight.
2. A method of making glass, comprising: the composition for glass of claim 1 is subjected to mixing, melting, homogenizing, casting, and annealing in this order.
3. The method of claim 2, further comprising annealing followed by a chemical strengthening treatment.
4. The method of claim 3, wherein the chemically amplified treatment comprises: strengthening liquidIs pure KNO3The temperature of the melt is 380-450 ℃, and the time is 2-10 h.
5. The method as claimed in claim 4, wherein the temperature is 410-450 ℃ and the time is 4-8 h.
6. Glass produced according to the method of any one of claims 2 to 5.
7. The glass made by the method of claim 6, wherein the glass has a density of 2.38 to 2.48g/cm3Coefficient of expansion 54 × 10-7-83×10-7The Young modulus is 60-81Gpa, the compressive stress is 800-.
8. The glass made by the method of claim 7, wherein the glass has a density of 2.41 to 2.45g/cm3Coefficient of expansion 60X 10-7-76×10-7The Young modulus is 62-73GPa, the compressive stress is 900-.
9. Use of the composition for glass of claim 1 or the glass of claim 6 for protecting a display device.
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