CN116143402A - Aluminosilicate glass, tempered glass and use - Google Patents
Aluminosilicate glass, tempered glass and use Download PDFInfo
- Publication number
- CN116143402A CN116143402A CN202310063589.9A CN202310063589A CN116143402A CN 116143402 A CN116143402 A CN 116143402A CN 202310063589 A CN202310063589 A CN 202310063589A CN 116143402 A CN116143402 A CN 116143402A
- Authority
- CN
- China
- Prior art keywords
- glass
- mass
- percent
- raw materials
- sno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005354 aluminosilicate glass Substances 0.000 title claims abstract description 60
- 239000005341 toughened glass Substances 0.000 title description 7
- 239000011521 glass Substances 0.000 claims abstract description 123
- 239000002994 raw material Substances 0.000 claims abstract description 70
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 35
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 29
- 238000005728 strengthening Methods 0.000 claims abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims description 20
- 239000006058 strengthened glass Substances 0.000 claims description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000011282 treatment Methods 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 description 19
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003190 augmentative effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000013003 hot bending Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 lithium aluminum silicon Chemical compound 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229950000033 proxetil Drugs 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to the technical field of glass, in particular to aluminosilicate glass, reinforced glass and application. The aluminosilicate glass comprises the following raw materials in percentage by mass: 55.4 to 65.4 percent of SiO 2 10.2 to 18.2 percent of Al 2 O 3 10.7 to 16.7 percent of Na 2 O, 2.2-6.6% K 2 O,2.9 to 6.0 percent of MgO,0.1 to 3.0 percent of ZrO 2 0.01 to 2.0 percent of SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the And the content of the raw materials also satisfies the following relationship: zrO (ZrO) 2 With SnO 2 The mass ratio of (2) is 1.0-20.0; siO (SiO) 2 With Al 2 O 3 The sum of the mass percentages of the components is not more than 77.5 percent. The present application is made by adding a quantity of SnO to the feedstock 2 And regulating and controlling the proportion of other components in the raw materials to prepare the aluminosilicate glassThe network structure contains [ SnO ] 4 ]Tetrahedron, because the field intensity of tin atoms is larger, the formed chemical bonds are more stable, so that the intrinsic strength of the product can be improved. In addition, the prepared aluminosilicate glass has better chemical strengthening performance, and a product with better mechanical strength can be obtained through subsequent strengthening treatment.
Description
Technical Field
The application relates to the technical field of glass, in particular to aluminosilicate glass, reinforced glass and application.
Background
With the rapid development of the smart technology industry and the popularization of digital products in recent years, smart phones, tablet computers and the like with touch screens have become an indispensable part in life, and a cover plate protection material arranged on the outermost layer of the touch screen is a 'armor' for protecting the touch screen. The traditional touch screen cover plate is mainly made of high-alumina glass, and has the functions of impact resistance, scratch resistance, oil stain resistance, fingerprint resistance, light transmittance enhancement and the like. The conventional technology develops high-alumina silicate glass and lithium-alumina silicate glass which are resistant to impact, scratch, drop and sweat erosion by means of increasing the alumina content in the glass or adding lithium oxide and the like and combining one or more chemical strengthening treatments. However, electronic products such as mobile phones often fall off the ground due to accidents, and when the traditional mobile phone screen protective glass contacts the ground, the protective glass is broken and invalid due to the impact of sharp objects such as stones, gravel or concrete on the ground, and even serious damage is caused to the electronic products.
In addition, for the automobile glass, during the high-speed running process of the automobile, stones or gravel on the ground are driven by the tire, and the high-speed shooting toward the window glass can also cause glass breakage and failure, so that the safety of personnel in the automobile can be further endangered. Other surfaces such as architectural glass and mechanical protective windows are impacted by foreign objects, breakage and failure of the glass can also occur.
Therefore, how to improve the penetration resistance and strength of glass is a problem to be solved.
Disclosure of Invention
Based on the above, the application provides the aluminosilicate glass, the reinforced glass and the application, wherein the aluminosilicate glass has better chemical reinforcing performance and strength, and the reinforced glass obtained after the reinforcing treatment has better puncture resistance and mechanical strength.
In a first aspect, the present application provides an aluminosilicate glass, the aluminosilicate glass comprising, in mass percent based on the total mass of the raw materials:
and the content of the raw materials also satisfies the following relationship:
ZrO 2 with SnO 2 The mass ratio of (2) is 1.0-20.0;
SiO 2 with Al 2 O 3 The sum of the mass percentages of the components is not more than 77.5 percent.
By adding a certain amount of SnO to the raw materials 2 And regulating and controlling the proportion of other components in the raw materials, so that the network structure of the prepared aluminosilicate glass contains [ SnO ] 4 ]Tetrahedron, because the field intensity of tin atoms is larger, the formed chemical bonds are more stable, so that the intrinsic strength of the product can be improved. In addition, the prepared aluminosilicate glass has better chemical strengthening performance, and a product with better mechanical strength can be obtained through subsequent strengthening treatment.
Further, by controlling SnO 2 The added amount of (2) ensures the transparency of the product and prevents the SnO from being caused 2 Problems of devitrification or phase separation opacification caused by excessive content. By regulating and controlling ZrO in raw materials 2 And SnO 2 The ratio of the two components is such that the two components interact to enhance the intrinsic strength of the product. By controllingSiO in the raw materials 2 And Al 2 O 3 Ensures the melt processing property of the aluminosilicate glass, and can be applied to large-scale industrial production.
In some of these embodiments, al is present in the total mass of the feedstock 2 O 3 The mass percentage of the (C) is 14.3-18.2%.
In some of these embodiments, snO is present in a mass percentage based on the total mass of the feedstock 2 The mass percentage of the (B) is 0.01-1.2%.
In some of these embodiments, zrO 2 With SnO 2 The mass ratio of (2.0-20.0).
In some of these embodiments, siO 2 With Al 2 O 3 The sum of the mass percentages of the components is 71.0 to 76.8 percent.
In some of these embodiments, na is present in a mass percentage based on the total mass of the feedstock 2 The mass percentage of O is 12.2-16.7%.
In some of these embodiments, K is calculated as mass percent based on the total mass of the feedstock 2 The mass percentage of O is 3.0-5.6%.
In some of these embodiments, the MgO is present in an amount of 2.9% to 5.3% by mass based on the total mass of the feedstock.
In some of these embodiments, the starting materials for the aluminosilicate glass further comprise: li (Li) 2 O、B 2 O 3 At least one of ZnO, caO and SrO. Optionally, li is calculated as mass percent of the total mass of the raw materials 2 The mass percentage of O is 0 to 1.0 percent; optionally, B is calculated as mass percent of the total mass of the raw materials 2 O 3 The mass percentage of the (B) is 0-2.0%; optionally, the ZnO accounts for 0 to 2.0 percent of the total mass of the raw materials; optionally, the mass percentage of CaO is 0 to 2.0 percent based on the mass percentage of the total mass of the raw materials; optionally, the mass percentage of SrO is 0-2.0% based on the total mass of the raw materials.
In a second aspect, the present application provides a strengthened glass obtained by strengthening the aluminosilicate glass of the first aspect. Optionally, chemically strengthening the aluminosilicate glass of the first aspect by ion exchange to obtain a strengthened glass. Further alternatively, the exchange melt used for the ion exchange is potassium nitrate melt.
By strengthening the aluminosilicate glass, a compact compressive stress layer can be formed on the surface of the aluminosilicate glass, so that the strengthened glass with the surface stress value of over 815MPa, the stress depth of over 38 mu m and the sharp object penetration resistance of over 850N is obtained, and further the protected object is effectively protected from being damaged by the external environment.
In a third aspect, the present application provides the use of the tempered glass of the second aspect for the preparation of a cover glass.
Detailed Description
In order to make the above objects, features and advantages of the present application more comprehensible, embodiments accompanied with the present application are described in detail below. In the following description, numerous specific details are set forth
The details are provided to facilitate a thorough understanding of the present application. This application is, however, susceptible of embodiment in many other forms than those described herein and similar modifications can be made by those skilled in the art without departing from the spirit of the application, and therefore the application is not to be limited to the specific embodiments disclosed below.
In the description of the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly defined otherwise. As used herein, "at least one" refers to any one, any two, or any two or more of the listed items. As used herein, "above a certain number" should be understood to mean a range of numbers and greater than a certain number.
The term "and/or," "and/or" as used in this application includes any one of two or more of the listed items in relation to each other and also includes any and all combinations of the listed items in relation to each other, including any two or more of the listed items in relation to each other, or all combinations of the listed items in relation to each other.
Where the terms "comprising," "having," "including," and "containing" are used herein, it is intended to cover a non-exclusive inclusion, such that another element may be added, unless a specifically defined term is used, such as "consisting of … … only," etc. Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Traditional automobile glass, mechanical equipment protection windows, building glass and part of low-end industrial control display screens, television display screens, tablet computer display screens and mobile phone display screens are still made of soda lime glass. The strength of the soda-lime glass is improved by a physical strengthening or chemical strengthening means in the traditional technology, but the requirements of properties such as drop resistance, impact resistance, sharp object puncture resistance and the like in a practical application scene are still not met. In addition, most of the protection glass of the mobile phone screen at present adopts aluminosilicate glass or lithium aluminum silicon glass, the content of alumina in the glass is up to 20wt%, the required melting temperature is excessively high, the viscosity and the surface tension of the glass are excessively high, and the problems of difficult glass clarification, difficult bubble removal and impossible mass production are caused. After the traditional aluminosilicate glass and lithium aluminum silicon glass are subjected to primary or secondary strengthening, the strength and puncture resistance are obviously improved. However, in the actual testing and application process, the protection capability of the glass on sharp objects still cannot meet the application requirements, and in the falling process, the breaking failure probability is still high. In addition, with the rapid development of the intelligent science and technology industry and the popularization of digital products, higher and higher requirements are put on the performances such as strength, drop resistance, impact resistance and puncture resistance of glass.
The research of the application finds that the traditional glassThe penetration resistance and strength of the glass are difficult to further improve, mainly because physical strengthening or chemical strengthening treatment is difficult to improve the network structure inside the glass, and the intrinsic strength of the glass product cannot be improved. The application has found that by adding a specific amount of tin dioxide into the raw material for preparing glass and regulating the proportion of other components, the tin dioxide and the other components in the raw material have synergistic effect, so that the tin atoms are converted from hexacoordinated to tetracoordinated, thereby [ SnO ] in the system 6 ]Octahedron transformation to [ SnO 4 ]Tetrahedra. The tetrahedron can participate in the network structure of the glass, so that the intrinsic strength and the chemical strengthening performance of the glass can be improved.
An embodiment of the present application provides an aluminosilicate glass, the raw materials of the aluminosilicate glass including, in mass percent based on the total mass of the raw materials:
and the content of the raw materials also satisfies the following relationship:
ZrO 2 with SnO 2 The mass ratio of (2) is 1.0-20.0;
SiO 2 with Al 2 O 3 The sum of the mass percentages of the components is not more than 77.6 percent.
Aluminosilicate glass in SiO 2 And Al 2 O 3 As a main raw material component, the composite material has better chemical stability, electrical insulation, mechanical strength and lower thermal expansion coefficient. Wherein SiO is 2 Framework for forming glass network structure, al 2 O 3 The stability of the glass network structure is enhanced as an intermediate. The present application adds specific amount of tin dioxide to the raw material based on the traditional aluminosilicate glass to make it in [ SnO ] 4 ]Tetrahedral forms participate in the glass network structure.
SiO 2 Is a framework component forming a glass network structure, and can improve the mechanical strength, chemical stability and heat resistance of glass. SiO (SiO) 2 Content ofWhen too high, the melting and fining temperatures of the glass are raised, and at the same time the melt viscosity of the system is increased, making the glass difficult to shape. SiO (SiO) 2 When the content is too low, crystallization of the glass is accelerated, and the thermal expansion coefficient of the produced glass is high. Thus, siO 2 The amount of (2) affects the overall properties of the glass. Based on the mass percentage of SiO based on the total mass of the raw materials 2 The content (the content is 55.4-65.4% by mass percent based on the total mass of the raw materials, which is not specifically described below). Specifically, siO 2 May be 55.4%, 56.4%, 56.6%, 57.4%, 57.6%, 58.3%, 58.85%, 59.5%, 60.3%, 61.1%, 61.6%, 62.4%, 62.6%, 63.1%, 63.9%, 64.1%, 65.1% or 65.4%.
Al 2 O 3 Is an intermediate of a glass network structure, participates in the formation of the glass network structure, and can enhance the stability of the network structure. And Al is 2 O 3 Can reduce crystallization tendency of glass and improve chemical stability, thermal stability, hardness and mechanical strength of glass. In addition, al 3+ Can form [ AlO ] 4 ]Tetrahedra due to [ AlO ] 4 ]Tetrahedral network structure ratio [ SiO ] 4 ]Tetrahedra are large, facilitating migration and diffusion of free ions, therefore Al 2 O 3 The addition of (3) promotes ion exchange. But Al is 2 O 3 When the content is too high, the viscosity and the melting temperature of the system are increased, so that the problems of difficulty in clarifying glass and difficulty in removing bubbles are caused, and the processability and the post-treatment performance of the glass are affected. Al (Al) 2 O 3 When the content is too low, ion exchange is not facilitated, and the stability and mechanical strength of the obtained glass product are poor, so that the requirements of practical application are difficult to meet. Based on the mass percentage of Al in the total mass of the raw materials 2 O 3 The content of (2) is 10.2-18.2%. Specifically, al 2 O 3 May be 10.2%, 11.0%, 12.2%, 13.1%, 14.2%, 15.2%, 16.2%, 17.0%, 17.7% or 18.2%.
In a specific example, toThe mass percentage of the total mass of the raw materials is calculated as Al 2 O 3 The mass percentage of the (C) is 14.3-18.2%. Specifically, al 2 O 3 May be present in an amount of 14.3%, 14.75%, 15.7%, 16.5%, 17.7%, 18.0% or 18.2%.
In a specific example, siO 2 With Al 2 O 3 The sum of the mass percentages of the components is not more than 77.6 percent. When SiO 2 And Al 2 O 3 Above 77.6% by mass, the melting temperature of the system exceeds 1680 ℃, whereas the melting temperature of conventional glass melters is less than 1680 ℃. Thus when SiO 2 And Al 2 O 3 When the total content of (c) is too high, it is difficult to satisfy the melting requirement of the glass melting furnace in the process of preparing glass, and large-scale production may not be possible. And SiO 2 And Al 2 O 3 The total content of the product is too high, so that bubbles generated in the melting process cannot be discharged in time, and a homogeneous and qualified product is difficult to obtain.
In a specific example, siO 2 With Al 2 O 3 The sum of the mass percentages of the components is 71.0 to 76.8 percent. Specifically, siO 2 And Al 2 O 3 The sum of the mass percentages of (a) is 71.0%, 72.1%, 72.6%, 73.6%, 73.8%, 74.3%, 74.6%, 75.1%, 75.55% or 76.8%.
Na 2 O can provide free oxygen and break Si-O-Si or Si-O-Al bond, thereby lowering the melting temperature of the system and facilitating the clarification and homogenization of glass. Na (Na) 2 When the content of O is too low, the melting and the forming are not facilitated. Na (Na) 2 When the content of O is too high, the thermal expansion coefficient of the product increases, and the thermal shock resistance and thermal stability decrease. In addition, na 2 O is the main component of ion exchange, na 2 The content of O can influence the progress of ion exchange. Based on the mass percentage of Na in the total mass of the raw materials 2 The content of O is 10.7-17.2%. Specifically, na 2 The O content may be 10.7%, 11.2%, 12.7%, 13.7%, 14.7%, 15.3%, 16.0%, 16.7% or 17.2%.
In a specific exampleBased on the mass percentage of the total mass of the raw materials, na 2 The mass percentage of O is 12.2-16.7%. Specifically, na 2 The O content may be 12.2%, 13.2%, 14.0%, 15.0% or 16.7%.
K 2 O can form a "mixed alkali effect" in the system, i.e. with a small amount of K 2 O replaces Na 2 O improves the melting property, ion exchange rate and acid-base resistance of the glass. But K is 2 When the content of O is too high, the rate of ion exchange and weather resistance are affected. Based on the mass percentage of K in the total mass of the raw materials 2 The content of O is 1.9-6.9%. Specifically, K 2 The O content may be 1.9%, 2.2%, 2.3%, 3.0%, 4.2%, 4.6%, 5.0%, 5.6%, 6.6% or 6.9%.
In a specific example, K is calculated as the mass percent of the total mass of the raw materials 2 The mass percentage of O is 3.0-5.6%, specifically K 2 The O content may be 3.0%, 3.6%, 4.3%, 5.3% or 5.6%.
MgO is an exo-oxide of a glass network structure and can be used as a reinforcing agent. And MgO can lower the melting point of glass, improve uniformity, increase hydrolysis resistance, and improve durability. However, the addition of MgO can adversely affect the compressive stress depth of the article. Based on the above, the content of MgO is 2.9-6.0% based on the total mass of the raw materials. Specifically, the MgO content may be 2.9%, 3.4%, 4.0%, 4.5%, 4.8%, 5.3%, 5.9%, or 6.0%.
In a specific example, the mass percentage of MgO is 2.9% -5.3% based on the total mass of the raw materials. Specifically, the MgO content may be 2.9%, 3.0%, 3.5%, 4.4%, 4.9%, 5.2%, or 5.3%.
ZrO 2 Is a common nucleating agent and can be prepared by using [ ZrO 4 ]Tetrahedra and [ ZrO 6 ]The octahedron form participates in the network structure of the glass, so that the strain point, the mechanical strength, the stability and the alkali resistance of the glass are improved. But ZrO 2 Too high a content may lead to glass bleedingCrystallization, difficult melting, and too high molding temperature. Based on the above, zrO is contained in mass percent based on the total mass of the raw materials 2 The content of (2) is 0.1% -3.0%. Specifically, zrO 2 The content of (c) may be 0.1%, 0.5%, 0.6%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.7%, 1.8%, 2.0%, 2.3%, 2.5%, 2.6% or 3.0%.
SnO 2 Is usually used as a fining agent, typically as [ SnO ] 6 ]The formation of octahedra exists and does not enter the network structure of the glass. The glass has the main function of reducing the bubble content in the glass, so as to improve the average visible light transmittance of the glass. However, the present application has accidentally found that SnO in certain situations 2 Can be made of [ SnO ] 4 ]Tetrahedral forms participate in the network structure of the glass and are associated with ZrO 2 Interaction occurs, and the intrinsic strength of the aluminosilicate glass is further enhanced significantly. [ SnO 4 ]Tetrahedra can be characterized by coordination number analysis of the product by XRD and the like, and the specific test method is not limited in this application. Under the raw material formula, free oxygen and/or bridge-cut oxygen in the system are increased, so that tin atoms are converted from hexacoordinated to tetracoordinated to form [ SnO ] 4 ]Tetrahedra. Further, since the field strength of the tin atom is large, the formed Sn-O chemical bond is stable, that is, [ SnO ] 4 ]The tetrahedron has better stability and [ SnO ] 4 ]The tetrahedron can participate in the network structure of the glass, so that the intrinsic strength of the glass can be improved. Note that [ SnO ] 4 ]The mechanism of tetrahedral formation is not limited to the above mechanism. In addition, when the product is impacted by external force, the [ SnO ] therein 4 ]Tetrahedra can be converted to [ SnO ] 6 ]Octahedron is separated out from the network structure, so that the glass is deformed, the toughness of the glass is improved, and macroscopic appearance is improved in puncture resistance and impact resistance. But SnO 2 When the content is too high, problems such as crystallization or phase separation opacification are likely to occur. Based on the mass percentage of SnO in the total mass of the raw materials 2 The content of (2) is 0.01-2.0%. Specifically, snO 2 The content of (C) can be 0.01%, 0.02%, 0.05%,0.11%, 0.15%, 0.65%, 0.71% or 2.0%.
In a specific example, snO is present in a mass percentage based on the total mass of the feedstock 2 The mass percentage of the (B) is 0.1-1.6%. Specifically, snO 2 The content of (c) may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% or 1.6%.
Understandably, due to ZrO 2 And SnO 2 There is an exchange action between them, and thus ZrO 2 With SnO 2 The mass ratio of (c) has an influence on the penetration resistance and mechanical strength of the glass. In addition, in the actual production process, zrO should be determined by combining meltability, fining and mass productivity of the glass 2 With SnO 2 The value range of the mass content ratio of (2). Based on this, zrO 2 With SnO 2 The mass ratio of (2) is 1.0-20.0. When the above ratio is less than 1.0, the improvement of the intrinsic strength of the product is effective, the practical application requirements are difficult to meet, and the reinforcement performance of the product may be also affected. When the above ratio is more than 20.0, the mechanical strength of the strengthened glass obtained by strengthening is lowered. Specifically, zrO 2 With SnO 2 The mass ratio of (c) may be 1.0, 1.1, 1.3, 1.5, 1.6, 2.0, 2.2, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0 or 20.0.
In a specific example, zrO 2 With SnO 2 The mass ratio of (2.0-20.0). Specifically, the above ratio may be 2.5, 2.7, 2.8, 3.3, 3.5, 3.6, 2.4, 4.7, 5.5, 10.9, 15.2 or 20.0.
By adding a certain amount of SnO to the raw materials 2 The network structure of the prepared aluminosilicate glass contains [ SnO ] 4 ]The tetrahedron has high field intensity of tin atoms, so that the formed chemical bond is stable, and the tetrahedron can participate in the network structure of the glass, thereby improving the intrinsic strength of the glass product. When the product is impacted by external force, the [ SnO ] therein 4 ]Tetrahedra can be converted to [ SnO ] 6 ]Octahedra and form a network junctionThe glass is deformed by precipitation in the structure, so that the toughness of the glass is improved, and macroscopic appearance is improved in puncture resistance and impact resistance. In addition, the prepared aluminosilicate glass has better chemical strengthening performance, and a product with better mechanical strength can be obtained through subsequent strengthening treatment.
Further, by controlling SnO 2 The added amount of (2) ensures the transparency of the product and prevents the SnO from being caused 2 Problems of devitrification or phase separation opacification caused by excessive content. By regulating and controlling ZrO in raw materials 2 And SnO 2 The ratio of the two components is such that the two components interact, resulting in a product with a higher intrinsic strength. By regulating and controlling SiO in raw materials 2 And Al 2 O 3 Ensures the melt processing property of the aluminosilicate glass, and can be applied to large-scale industrial production.
In a specific example, the raw materials of the aluminosilicate glass further include, in mass percent of oxides: li (Li) 2 O、B 2 O 3 At least one of ZnO, caO and SrO.
Li 2 Li in O + Has a smaller radius, and thus Li is added 2 O is favorable for ion exchange, and can improve the compression stress depth of the strengthened glass, reduce the thermal expansion coefficient and improve the chemical stability. And Li (lithium) 2 O can be used as a fluxing agent, so that the processability of the system is improved. But Li 2 When the O content is too high, the hardness of the product is lowered. In a specific example, li is contained in mass percent based on the total mass of the raw materials 2 The mass percentage of O is 0-1.0%. Specifically, li 2 The content of O may be 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%.
B 2 O 3 Can be used as fluxing agent, and can reduce the viscosity of glass under high temperature condition. At low temperature, can form [ BO ] 4 ]The tetrahedron makes the structure of the product more compact, and improves the stability of the product. But B is 2 O 3 When the content is too high, the strain point and Young's modulus of the glass are reduced, and the clarification effect of the glass can be influencedAnd (5) fruits. In a specific example, B is calculated as the mass percent of the total mass of the raw materials 2 O 3 0 to 2.5 mass percent, specifically B 2 O 3 The content of (c) may be 0, 0.2%, 0.3%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 2.0% or 2.5%.
ZnO can help the melting of glass, improve the light transmittance of the glass and make the glass difficult to devitrify. And ZnO can form [ ZnO 4 ]The tetrahedron makes the broken network structure reconnected, and further improves the properties of the product such as density, hardness and the like. However, when the content is too high, the compressive stress of the glass is adversely affected. In a specific example, the ZnO is 0 to 2.0% by mass based on the total mass of the raw material, and specifically, the ZnO may be 0, 0.5%, 1.0%, 1.5% or 2.0%.
CaO enables [ SiO ] 4 ]The network structure formed by tetrahedra is more relaxed, improves the melting property of the glass at high temperature, and makes the glass difficult to devitrify. However, when the content is too high, the weather resistance of the glass is impaired, and the progress of ion exchange is hindered. In a specific example, the CaO is 0 to 2.0% by mass based on the total mass of the raw materials. Specifically, the CaO content may be 0, 0.5%, 1.0%, 1.5%, or 2.0%.
SrO is used as a fluxing agent to prevent crystallization of glass, but when the content is too high, the density of the glass is too high, and the quality of the product is too high. In a specific example, the mass percentage of SrO is 0 to 2.0% based on the total mass of the raw material. Specifically the content of SrO may be 0, 0.5%, 1.0%, 1.5% or 2.0%.
In a specific example, the raw materials of the aluminosilicate glass include, in mass percent based on the total mass of the raw materials: 56.4 to 62.95 percent of SiO 2 11.0 to 18.2 percent of Al 2 O 3 12.2 to 16.7 percent of Na 2 3.0 to 5.6 percent of O and K 2 O, mgO 2.9-5.5%, zrO 0.1-2.2% 2 0.1 to 2.0 percent of SnO 2 0 to 1.0 percent of CaO, zrO 2 With SnO 2 The mass ratio of (2) is 1.0-2.7, siO 2 With Al 2 O 3 The sum of the mass percentages of the components is 71.1 to 76.6 percent.
In a specific example, the raw materials of the aluminosilicate glass include, in mass percent based on the total mass of the raw materials: 55.4 to 60.4 percent of SiO 2 13.2 to 18.2 percent of Al 2 O 3 0 to 0.2 percent of Li 2 O, na 13.1-16.7% 2 O, 2.2-5.6% K 2 O,3.0 to 5.9 percent of MgO,2.3 to 2.8 percent of ZrO 2 0.05 to 0.5 percent of SnO 2 0 to 1.0 percent of ZnO, zrO 2 With SnO 2 The mass ratio of (2) is 1.0-13.0, siO 2 With Al 2 O 3 The sum of the mass percentages of the components is 73.6 to 76.8 percent.
In a specific example, the raw materials of the aluminosilicate glass include, in mass percent based on the total mass of the raw materials: 57.4 to 65.4 percent of SiO 2 10.2 to 17.7 percent of Al 2 O 3 0 to 1.0% of Li 2 O, 10.7-16.0% Na 2 O, 2.6-6.6% K 2 O, mgO 2.9-6.0%, zrO 0.1-2.0% 2 0.01 to 1.1 percent of SnO 2 0 to 2.0 percent of ZnO,0 to 2.0 percent of SrO, zrO 2 With SnO 2 The mass ratio of (2) is 1.0-20.0, siO 2 With Al 2 O 3 The sum of the mass percentages of the components is 73.09 to 77.5 percent.
In a specific example, the raw materials of the aluminosilicate glass include, in mass percent based on the total mass of the raw materials: 55.4 to 65.4 percent of SiO 2 14.3 to 18.2 percent of Al 2 O 3 0 to 1.0% of Li 2 O, na accounting for 12.2 percent to 16.7 percent 2 3.0 to 5.6 percent of O and K 2 O,2.9 to 5.3 percent of MgO,0.1 to 3.0 percent of ZrO 2 0.01 to 1.2 percent of SnO 2 0 to 2.0 percent of ZnO,0 to 2.0 percent of CaO,0 to 2.0 percent of SrO and ZrO 2 With SnO 2 The mass ratio of (2.0-20.0), siO 2 With Al 2 O 3 Is contained in mass percentThe sum is 71.0 to 76.8 percent.
The aluminosilicate glass of the present application can be prepared by, but is not limited to, the following method, and specifically comprises the following steps:
s1, melting raw materials to obtain glass liquid;
s2, forming the glass liquid to prepare the aluminosilicate glass.
In one specific example, the melting temperature in S1 is 1500-1650℃for 8 hours. Then the temperature is reduced to 1300-1500 ℃ and the temperature is kept for 2h. S2, preparing glass blocks by casting molten glass into a forming die at 450 ℃. And immediately transferring the glass blocks into an annealing furnace for annealing after the glass blocks are hardened, and preserving heat for 2 hours. And finally, cooling to 140 ℃ within 6 hours, naturally cooling, and taking out for later use.
Another embodiment of the present application also provides a strengthened glass obtained by strengthening any one of the aluminosilicate glasses described above. Optionally, the aluminosilicate glass is chemically strengthened by ion exchange to provide a strengthened glass.
By strengthening the aluminosilicate glass, a compact compressive stress layer can be formed on the surface of the aluminosilicate glass, so that the strengthened glass with the surface stress value of over 815MPa, the stress depth of over 38 mu m and the sharp object penetration resistance of over 850N is obtained, and further the protected object is effectively protected from being damaged by the external environment.
The strengthened glass of the present application can be prepared by, but not limited to, the following methods, which specifically comprise the following steps:
s3, strengthening the aluminosilicate glass.
Wherein, the method further comprises cutting the glass block into glass sheets with preset sizes before the step S3. S3, immersing the glass sheet in 390-430 ℃ potassium nitrate melt, and keeping for 3-8 hours to enable the glass sheet to undergo ion exchange, thereby achieving the purpose of chemical strengthening. The glass according to the present application can be obtained in a conventional sheet glass manufacturing process, and the manufacturing process is not limited to a float forming process, an overflow down-draw process, a draw-up process, a flat draw process, a calendaring process, and the like.
Finally, an embodiment of the present application also provides an application of the tempered glass in preparing the protection glass. The protective glass can be applied to the fields of electronic equipment, windows, semiconductor devices and the like. Electronic devices include, but are not limited to, cell phones, tablet computers, televisions, wearable devices, virtual Reality (VR) terminal devices, and augmented reality (augmented reality, AR) terminal devices. Windows may be used in, but are not limited to, the fields of construction, transportation, mechanical equipment, and the like. Semiconductor devices include, but are not limited to, semiconductor sensors.
In order to make the objects and advantages of the present application more apparent, the present application will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In the different examples and comparative examples, the raw materials for preparing aluminosilicate glass and the strengthening process conditions of the strengthened glass are different, and specific preparation methods are as follows: examples 1 to 56 and comparative examples 1 to 12 were weighed according to the proportions shown in tables 1 to 8, after being thoroughly and uniformly mixed, the materials were melted for 8 hours at 1500 to 1650 ℃ by a platinum crucible, and simultaneously stirred by a platinum stirring paddle, after the stirring paddle was pulled out, the temperature was lowered to 1300 to 1500 ℃, and the temperature was kept for 2 hours, and homogenization was performed. And then casting the glass blocks on an iron mold to form aluminosilicate glass blocks with the size of 80 mm or about 160mm, preheating the glass blocks to 450 ℃ before casting the mold, immediately transferring the glass blocks into an annealing furnace for annealing after hardening, preserving heat for 2 hours, cooling to 140 ℃ within 6 hours, and taking out the glass blocks for later use after natural cooling.
The aluminosilicate glass block is cut into 70 x 140 x 1.1mm aluminosilicate glass sheets by an STX-1203 wire cutting machine of Shenyang crystal, thinned and polished by an HD-640-5L double-sided grinding polisher of Shenzhen Haide, and then subjected to CNC edging. The density of the sample was measured by an AKD-120A solid density volume tester without tin kessel, the thermal expansion coefficient of the sample was measured by a relaxation-resistant thermal expansion tester DIL 402Expedis class, and the softening point of the sample was measured according to national standard G B/T28195-2011, and the measurement results are shown in tables 1 to 8.
The aluminosilicate glass sheets of each example and comparative example were then chemically strengthened to obtain strengthened glass. The time and temperature of the strengthening are shown in tables 1 to 8. It should be noted that tables 1 to 8 only provide one optional strengthening process parameter, and those skilled in the art may select specific strengthening process parameters according to actual requirements. Specifically, an aluminosilicate glass sheet is immersed in a potassium nitrate melt at a preset strengthening temperature, kept for a preset strengthening time, and subjected to ion exchange.
The surface compressive stress CS and the compressive stress depth Dol of the tempered glass were measured by an FSM6000LE stress tester of japan foldback. The limit ball drop energy of the reinforced glass is specifically tested by a 110g steel ball by using a ZJ-9968 ball drop tester of an Zhengjie instrument. The tempered glass was tested for hoop stress using a PT-307A universal tester for proxetil (upper hoop phi=16 mm, lower hoop phi=32 mm). The ST-DT100 pressure-resistant tester using the Sitai instrument uses a tungsten steel pressure head with phi=0.5 mm to squeeze the surface of the glass until the maximum pressure resistance of the glass is broken, namely the sharp object puncture resistance of the reinforced glass, and the test results are shown in tables 1 to 8. ZrO in the following tables 2 /SnO 2 Represents ZrO 2 With SnO 2 Mass ratio of SiO 2 +Al 2 O 3 Representing SiO 2 With Al 2 O 3 The sum of the mass percentages of (3).
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
Referring to tables 1 to 7, examples 1 to 56 had good mechanical strength, falling ball strength could reach more than 1.49J, strength could reach more than 3000N, sharp object puncture strength could reach more than 850N, and the appearance of the samples of examples 1 to 56 were all transparent. In some preferred embodiments, the falling ball strength can reach more than 1.80J, the strength can reach more than 4000N, the sharp object puncture strength can reach more than 1100N, and the damage of the sharp object to the window glass can be effectively prevented, so that personnel in an automobile are protected. When the glass is used as a screen of electronic equipment or applied to semiconductor sensors and other fields, related equipment can be effectively protected. In addition, the samples of examples 1 to 56 form a compact compressive stress layer on the surface, the stress value can reach over 815MPa, and the stress depth exceeds 38 mu m, which shows that the samples of each example have better chemical strengthening performance.
Further, referring to tables 1 to 5, zrO in examples 1 to 45 2 /SnO 2 The values of (a) are sequentially increased, and the mechanical strength of the samples of the examples is increased, indicating that when ZrO 2 /SnO 2 When the number of (a) is within a suitable range (e.g., 2.0 to 20.0), snO 2 Can form a certain amount of [ SnO ] 4 ]Tetrahedra, and can also interact with ZrO 2 Interaction is generated, and the strength of the sample is further improved. The raw material components in each example as a whole have an effect on the formability, the strength and the strength properties of the sample, and therefore, the synergy between the raw material formulation and each raw material component in the whole should be considered in analyzing and comparing the properties of each example. That is, the present application passes a number of experiments and considers the intrinsic strength of aluminosilicate glass comprehensivelyThe raw material formula of the product has better mechanical strength after strengthening.
Referring to Table 7, comparative example 1 contains no SnO 2 Thus, it is impossible to form [ SnO ] participating in the glass network structure 4 ]The tetrahedron glass structure has the inherent characteristics of the traditional brittle material, and the falling ball strength, the ring pressure strength and the sharp object puncture strength are greatly reduced. SnO in comparative example 2 2 More than 2wt%, snO in the case of a large alkali metal/alkaline earth metal content 2 Is made of [ SnO ] 4 ]Tetrahedra and [ SnO ] 6 ]Octahedral forms participate in the glass network and, with SnO 2 Increased content of [ SnO ] 6 ]The octahedral structure occupies the majority. Due to [ SnO ] 6 ]The octahedron cannot participate in the glass network structure, but can only enter the structure gaps, so that the intrinsic strength is reduced. More importantly, due to [ SnO ] 6 ]The octahedron has higher field intensity, is easy to gather, increases crystallization tendency, thereby causing a small amount of phase separation of glass, reducing optical transmittance and appearing semi-transparent.
ZrO in comparative example 3 2 /SnO 2 Less than 1, zrO in comparative example 4 2 /SnO 2 Above 20, the sharp object penetration strength is significantly reduced. And the strengthening stress depth Dol in the comparative example 3 also has obviously reduced ball falling strength and ring compression strength.
The MgO content in comparative example 5 was reduced to 1.5wt%, and its effect of modifying the glass network structure was significantly reduced, resulting in relaxation of the glass structure, and its surface compressive stress value was significantly reduced, directly affecting the strength properties of the tempered glass, particularly the ring crush and sharp object puncture resistance. The MgO component in comparative example 6 increased to 7.8wt% and more MgO was filled in the gaps of the glass structure, and the MgO had a smaller molecular weight, blocking the ion exchange channels, decreasing the ion exchange capacity, and its enhanced stress depth Dol decreased, directly affecting the falling ball, ring pressure and sharp object puncture strength properties of the product.
Referring to Table 8, comparative example 7 shows K 2 The O content is reduced to 2.0wt percent, the channels for K ion exchange are reduced,the K/Na ion exchange efficiency is reduced, the ion exchange capacity is seriously reduced, the reinforced stress depth Dol is reduced, and the falling ball, ring pressure and sharp object puncture strength performance of the reinforced glass are directly affected. K in comparative example 8 2 The O content increased to 8.2wt%, and the thermal expansion coefficient exceeded 115 x 10 due to the excessive total alkali metal content -7 1/°c, exacerbating the problem of cte mismatch during subsequent thermal processing processes (e.g., thermal bowing, physical strengthening, and bonding). In addition, the excessive alkali metal provides excessive free oxygen, so that the bond breaking capability is strong, the network structure of the glass is seriously damaged, and the puncture resistance of the product is obviously reduced.
Al in comparative example 9 2 O 3 The content is reduced to 9 weight percent, the chemical strengthening capability is obviously reduced, the surface compressive stress and the depth of compressive stress Dol are reduced, and the falling ball, ring pressure and sharp object puncture resistance of the strengthened glass are affected. Al in comparative example 10 2 O 3 The content is increased to 19.2wt%, the glass modifier has less components, the melting temperature and the forming difficulty are increased, and even the temperature exceeds the temperature of the conventional glass production process. And the softening point also increased significantly, exceeding 840 ℃. In general, the automobile glass, the mobile phone cover plate glass, part of the building glass and the like need the processes of physical tempering, hot bending and the like, and the common heat treatment temperature is not more than 820 ℃, so that the sample of the comparative example 10 cannot be suitable for the conventional production process and is not suitable for mass production.
Na in comparative example 11 2 The O content is reduced to 9.9wt percent, the glass modifier has less components, the melting temperature is greatly increased, and the temperature exceeds the temperature of the conventional glass production process. And the softening point is increased to 848 ℃, which is also not suitable for the conventional production process and is not suitable for mass production. Na in comparative example 12 2 The O content increased to 17.3% and the thermal expansion coefficient increased to 115.2x10 -7 1/°c, aggravates the problem of mismatch of thermal expansion coefficients and the like caused by subsequent thermal processing processes (such as hot bending, physical strengthening and bonding), and reduces puncture resistance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. The scope of the patent is, therefore, indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (11)
1. An aluminosilicate glass characterized in that the raw materials of the aluminosilicate glass comprise, in mass percent based on the total mass of the raw materials:
and the content of the raw materials also satisfies the following relationship:
the ZrO 2 And the SnO 2 The mass ratio of (2) is 1.0-20.0;
the SiO is 2 With the Al 2 O 3 The sum of the mass percentages of the components is not more than 77.6 percent.
2. The aluminosilicate glass according to claim 1, wherein the Al is in mass percent based on the total mass of the raw materials 2 O 3 The mass percentage of the (C) is 14.3-18.2%.
3. The aluminosilicate glass according to claim 1, wherein the SnO is present in a mass percentage based on the total mass of the raw materials 2 The mass percentage of the (B) is 0.01-1.2%.
4. According toThe aluminosilicate glass of claim 1, wherein the ZrO 2 And the SnO 2 The mass ratio of (2.0-20.0).
5. The aluminosilicate glass of claim 1, wherein the SiO 2 With the Al 2 O 3 The sum of the mass percentages of the components is 71.0 to 76.8 percent.
6. The aluminosilicate glass according to claim 1, wherein the Na is in mass percent based on the total mass of the raw materials 2 The mass percentage of O is 12.2-16.7%.
7. The aluminosilicate glass according to claim 1, wherein the K is based on the mass percentage of the total mass of the raw materials 2 The mass percentage of O is 3.0-5.6%.
8. The aluminosilicate glass according to claim 1, wherein the MgO is present in an amount of 2.9% to 5.3% by mass based on the total mass of the raw materials.
9. The aluminosilicate glass of claim 1, wherein the starting materials for the aluminosilicate glass further comprise Li 2 O、B 2 O 3 At least one of ZnO, caO and SrO;
optionally, the Li is calculated as mass percent of the total mass of the raw materials 2 The mass percentage of O is 0 to 1.0 percent;
optionally, the B is calculated as mass percent of the total mass of the raw materials 2 O 3 The mass percentage of the (B) is 0-2.5%;
optionally, the ZnO accounts for 0 to 2.0 percent of the total mass of the raw materials;
optionally, the CaO accounts for 0 to 2.0 percent of the total mass of the raw materials;
optionally, the mass percentage of the SrO is 0-2.0% based on the total mass of the raw materials.
10. A reinforced glass obtained by reinforcing the aluminosilicate glass according to any one of claims 1 to 9;
optionally, chemically strengthening the aluminosilicate glass of any one of claims 1-9 by ion exchange to obtain the strengthened glass;
further alternatively, the exchange melt used for the ion exchange is potassium nitrate melt.
11. Use of the strengthened glass of claim 10 in the preparation of a protective glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310063589.9A CN116143402A (en) | 2023-01-31 | 2023-01-31 | Aluminosilicate glass, tempered glass and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310063589.9A CN116143402A (en) | 2023-01-31 | 2023-01-31 | Aluminosilicate glass, tempered glass and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116143402A true CN116143402A (en) | 2023-05-23 |
Family
ID=86353837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310063589.9A Pending CN116143402A (en) | 2023-01-31 | 2023-01-31 | Aluminosilicate glass, tempered glass and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116143402A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092940A (en) * | 2009-12-11 | 2011-06-15 | 肖特公开股份有限公司 | Aluminum silicate glass for touch screen |
| CN102557432A (en) * | 2011-12-26 | 2012-07-11 | 海南中航特玻材料有限公司 | High-strength touch screen glass component suitable for chemical tempering |
| CN102985382A (en) * | 2010-07-12 | 2013-03-20 | 日本电气硝子株式会社 | Glass plate |
| CN108503213A (en) * | 2017-02-23 | 2018-09-07 | 中国南玻集团股份有限公司 | Alumina silicate glass and strengthened glass |
| CN109320084A (en) * | 2018-12-03 | 2019-02-12 | 湖南兴龙环境艺术工程有限公司 | A kind of preparation method of surface high-compactness cement sheet material |
-
2023
- 2023-01-31 CN CN202310063589.9A patent/CN116143402A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092940A (en) * | 2009-12-11 | 2011-06-15 | 肖特公开股份有限公司 | Aluminum silicate glass for touch screen |
| CN102985382A (en) * | 2010-07-12 | 2013-03-20 | 日本电气硝子株式会社 | Glass plate |
| CN102557432A (en) * | 2011-12-26 | 2012-07-11 | 海南中航特玻材料有限公司 | High-strength touch screen glass component suitable for chemical tempering |
| CN108503213A (en) * | 2017-02-23 | 2018-09-07 | 中国南玻集团股份有限公司 | Alumina silicate glass and strengthened glass |
| CN109320084A (en) * | 2018-12-03 | 2019-02-12 | 湖南兴龙环境艺术工程有限公司 | A kind of preparation method of surface high-compactness cement sheet material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI491571B (en) | Glass plate for display device, plate glass for display device and production process thereof | |
| CN110615610B (en) | Lithium-zirconium aluminosilicate glass, tempered glass, preparation methods of lithium-zirconium aluminosilicate glass and tempered glass, and display device | |
| CN110316974B (en) | Alkali-containing aluminosilicate glass, product, strengthening method and application thereof | |
| US8691711B2 (en) | Glass for display device and glass plate | |
| TWI439435B (en) | Glass plate for display devices | |
| KR20190022707A (en) | Chemically temperable glass plate | |
| TW201318996A (en) | Glass composition, glass obtained therefrom, and preparation process and use of the glass | |
| JP2009084075A (en) | Reinforced glass substrate and glass, and method for manufacturing reinforced glass substrate | |
| WO2011007785A1 (en) | Glass plate for display device | |
| CN109678341B (en) | Alkali-free glass composition, alkali-free glass and application | |
| CN103992032B (en) | Be suitable for chemical enhanced glass and enhancement method thereof | |
| JPWO2020121888A1 (en) | Chemically tempered glass plate, and cover glass and electronic devices including chemically strengthened glass | |
| WO2021145258A1 (en) | Chemically strengthened glass article and manufacturing method thereof | |
| CN108975688B (en) | Glass and preparation method thereof | |
| JPWO2012077796A1 (en) | Method for producing chemically strengthened glass | |
| CN112723736B (en) | Glass, tempered glass, preparation method of glass and electronic product | |
| CN112479587B (en) | Alkali aluminosilicate glass composition, tempered glass, preparation method and application | |
| WO2016170931A1 (en) | Strengthened glass | |
| CN112456793A (en) | Lithium-aluminum silicate glass for float production | |
| CN115286241A (en) | Ultrathin flexible glass with high fracture toughness and preparation method thereof | |
| CN109020196A (en) | A kind of chemically reinforced glass being easy to ion exchange | |
| CN105884189B (en) | A kind of cover board glass composition and cover-plate glass and its preparation method and application | |
| CN109052934B (en) | Protective glass plate with impact stress resistance | |
| CN116143402A (en) | Aluminosilicate glass, tempered glass and use | |
| CN114195381B (en) | Soda-lime silicate glass, reinforced glass, and preparation methods and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |