CN114075044B - Tempered glass with safe stress state and processing method thereof - Google Patents
Tempered glass with safe stress state and processing method thereof Download PDFInfo
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- CN114075044B CN114075044B CN202010833255.1A CN202010833255A CN114075044B CN 114075044 B CN114075044 B CN 114075044B CN 202010833255 A CN202010833255 A CN 202010833255A CN 114075044 B CN114075044 B CN 114075044B
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- 239000005341 toughened glass Substances 0.000 title claims abstract description 64
- 238000003672 processing method Methods 0.000 title claims abstract description 10
- 239000006058 strengthened glass Substances 0.000 claims abstract description 107
- 239000011521 glass Substances 0.000 claims abstract description 104
- 238000005342 ion exchange Methods 0.000 claims abstract description 72
- 150000003839 salts Chemical class 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 8
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 8
- 239000006064 precursor glass Substances 0.000 claims description 48
- 239000011734 sodium Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 12
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 10
- 238000005728 strengthening Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006124 Pilkington process Methods 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical group O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 238000005266 casting Methods 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000005345 chemically strengthened glass Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
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
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a strengthened glass with a safe stress state and a processing method thereof, wherein the numerical values of the surface compressive stress and the thickness of the strengthened glass meet the mathematical relational expression, and the stress state of the strengthened glass obtained after chemical strengthening is intuitively understood through representing the stress state. Furthermore, in the ion exchange process, the concentration of sodium nitrate in the salt bath and the scaling ratio of the tempered glass are controlled, so that the ion exchange reaction degree is controlled, the surface of the obtained tempered glass has high compressive stress compared with the surface of common glass, and the shock resistance of the tempered glass is ensured; meanwhile, when the compressive stress of the tempered glass is improved, the tensile stress in the tempered glass is controlled within a safe range, so that the tempered glass reaches an optimal stress state, and the characteristics of the tempered glass can be better exerted.
Description
Technical Field
The invention relates to the technical field of tempered glass, in particular to tempered glass with a safe stress state and a processing method thereof.
Background
With the progress of science and technology and the improvement of living standard of people, small-sized electromechanical products, especially portable electronic products, are greatly applied to daily lives, including mobile phones, digital cameras, notebook computers and the like. The product is damaged when a consumer accidentally drops the product while carrying or using the product due to the portability of the product. Because the transfer of the momentum of the object in the falling impact is carried out in a very short time, compared with other types of impact, the falling impact of the product is the strongest, and is the main reason for losing the appearance, the internal working performance and even the use function of the small electronic product. In addition, as a precise high-value product, such electronic products are often expensive, and the invisible loss caused by the damage of the electronic products exceeds the value of the product, for example, an important data is lost, a business opportunity is lost, and a personal safety problem may be caused. Therefore, consumers prefer products with good crashworthiness to purchase such products while satisfying the basic functions, and crashworthiness of the products when falling down becomes an important characteristic of product quality and core competitiveness of the products.
At present, the glass used in such electronic products is mainly chemically strengthened glass after chemical strengthening. The chemically strengthened glass is prepared through ion exchange process, and features that the alkali metal ions with relatively large ionic radius in salt bath replace the alkali metal ions with relatively small ionic radius in glass to generate exchange plasma product difference, resulting in high-to-low tensile stress on certain surface of glass to block and delay the expansion of microcrack in glass and raise the mechanical strength of glass. The strengthened glass treated by the ion exchange process generates a corresponding tensile stress in the strengthened glass while generating a compressive stress on the surface. The chemical strengthened glass is a stress balance body, if the compressive stress is lower, the strength of the obtained strengthened glass is not high, and the requirement of customers on high drop resistance of the product when the product drops can not be met; if the compressive stress is too high, although the strengthened glass with high strength can be obtained, high tensile stress can be formed in the strengthened glass, so that the strengthened glass has potential safety hazards, explosive cracking can occur under slight impact, even an auto-explosion phenomenon can be generated, the reliability of a product is seriously influenced, and even the personal safety of a client is also seriously influenced.
However, although the common high-alumina-silica glass and lithium-alumina-silica glass commonly used in the existing cover plate glass industry can be subjected to chemical ion exchange, reinforcement and toughening, the glass is limited in that the intrinsic structural strength of a glass network is insufficient, the bifurcation threshold value of the glass has a limit and cannot support high tensile stress linear density, when the tensile stress linear density greatly exceeds the bifurcation threshold value, the glass can be bifurcated into fragments smaller than 1mm, and can splash around during crushing to cause potential safety hazards, and if a display screen of an electronic product is crushed into fragments smaller than 1mm, the display screen is difficult to continue to use.
Therefore, how to make the compressive stress of the strengthened glass meet the requirement of high drop resistance and maintain the internal tensile stress within a safe range, and how to obtain the strengthened glass are technical problems which need to be solved urgently by those skilled in the art at present.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a strengthened glass with a safe stress state, so as to solve the problem that the strengthened glass in the prior art is difficult to obtain sufficient compressive stress on the surface thereof, so that the strengthened glass has high drop resistance, and the internal tensile stress thereof is maintained within a safe range.
The invention also provides a processing method of the strengthened glass with the safe stress state, and aims to solve the problem that the existing processing method cannot give consideration to both high-pressure stress and high intrinsic strength.
In order to solve the technical problems, the invention adopts the following technical scheme:
a strengthened glass with a safe stress state, wherein the numerical values of the surface compressive stress and the thickness of the strengthened glass meet the following conditions:
wherein CS 50 Is the compressive stress at a distance of 50 microns below the glass surface in MPa; a is-486.23; b is 0.449;217-20T ≦ c ≦ 217+20/T; t is the thickness of the tempered glass in mm.
The invention also provides a processing method of the strengthened glass with the safe stress state, which comprises the following steps:
s1: carrying out preheating treatment on the precursor glass;
s2: putting the precursor glass subjected to the preheating treatment in the step S1 into a salt bath, and heating to perform an ion exchange reaction to obtain the strengthened glass;
wherein the salt bath is a potassium nitrate and sodium nitrate mixed salt bath, and the mass fraction of the sodium nitrate is less than that of Na in the precursor glass component 2 O/(Li 2 O+Na 2 O+K 2 O) and is greater than Na in the precursor glass component 2 The percentage by mole of O, the scaling ratio of the strengthened glass is controlled between 1.5 per mill and 2 per mill.
Compared with the prior art, the invention has the following beneficial effects:
1. when the stress state of the tempered glass is researched, the tempered glass obtained by the preparation method disclosed by the invention can have a sufficiently high compressive stress on the surface of the tempered glass, so that the tempered glass has excellent anti-falling performance, and the mathematical relational expression disclosed by the invention can be used for accurately representing and judging whether the tempered glass after the tempering treatment is in a safe stress state, namely, when the tempered glass meets the mathematical relational expression disclosed by the invention, the fact that the tensile stress of the tempered glass obtained by the treatment is controlled within a safe range is shown, explosive cracking caused by slight impact is avoided, and a self-explosion phenomenon is avoided.
2. When the invention is researched to the ion exchange reaction, the ion exchange reaction degree can be controlled by controlling the concentration of sodium nitrate in the salt bath and the scaling ratio of the strengthened glass in the ion exchange process, so that the strengthened glass with a safe stress state is obtained, and compared with the common glass, the surface of the strengthened glass has high pressure stress, thereby ensuring the shock resistance of the strengthened glass; meanwhile, when the compressive stress of the tempered glass is improved, the tensile stress in the tempered glass is controlled within a safe range, so that the tempered glass reaches an optimal stress state, and the characteristics of the tempered glass can be better exerted.
3. When the precursor glass is subjected to ion exchange reaction, the scaling ratio of the strengthened glass obtained after the reaction is detected in real time, so that the time of the ion exchange reaction is controlled, and the strengthened glass obtained after the reaction reaches the optimal stress state; at the same time, the degree to which the ion exchange reaction proceeds is controlled by scaling the ratio. Compared with the prior art that the ion exchange reaction degree is controlled by a series of parameters of temperature, dipping time and the times of dipping the glass into one or more salt baths, the method can more accurately and efficiently control the ion exchange reaction, so that the obtained strengthened glass reaches the optimal stress state.
Drawings
FIG. 1 is a schematic view of the particles of fragments produced by breakage of the tempered glass of example 1 after it has fallen from a height of 1.7 m.
Fig. 2 is a schematic front view of a consumer electronic device according to the present invention.
Fig. 3 is a schematic rear view of a consumer electronic device according to the present invention.
Detailed Description
The invention will be further explained by the accompanying drawings and examples.
The following is an explanation of the relevant nomenclature and the relevant measurement methods involved in the present invention:
precursor glass: is a glass base material which is not strengthened and does not contain crystals.
Strengthening glass: is chemically strengthened glass treated by a high-temperature ion exchange process. The alkali metal ions with large ionic radius in the high-temperature salt bath replace the alkali metal ions with small ionic radius in the glass so as to generate exchange plasma accumulation difference, and high-to-low pressure stress is generated in the surface layer of the precursor glass, so that the expansion of glass microcracks is hindered and delayed, and the purpose of improving the mechanical strength of the glass is achieved.
Surface compressive stress CS: after the glass is chemically strengthened, alkali metal ions with smaller radius on the surface are replaced by alkali metal ions with larger radius, and the surface of the glass generates compressive stress due to the squeezing effect of the alkali metal ions with larger radius.
Surface compressive stress CS 50 : compressive stress 50 microns below the glass surface.
Depth of compressive stress layer DOL 0 : refers to the depth at which the compressive stress generated from the strengthening process reaches zero within the strengthened glass.
A bifurcation threshold value: when the glass is impacted by adopting a tensile stress release test method, the crack of the glass is just branched by the stress of the glass when the glass is cracked, and the density value of the tensile stress line at the moment is the branching threshold value of the glass.
Scratch threshold: when the glass is impacted by adopting a tensile stress releasing experiment method, the glass generates a trace zone just by self stress when the glass is cracked, and the linear density value of the tensile stress at the moment is the trace zone threshold value of the glass.
Tensile stress release test: the strengthened glass adopts a Vickers diamond drill bit and adopts a guide rail to fix so as to ensure that the drill bit vertically impacts the surface of the glass, the impact adopts air pressure conduction, the air pressure is adjusted and the impact force is controlled by combining a pressure sensor, and the height of the guide rail is adjusted according to the thickness of the glass so as to control the invasion depth of the drill bit, so that a damage point only extends two cracks instead of generating star burst, the influence of external force on a damage state is avoided to the maximum extent, and finally, the tensile stress safety of the glass is judged by observing the damage state of the glass.
And (3) tensile stress linear density CT-LD: the ratio of tensile stress integral to thickness of the glass under the thickness section is obtained according to SLP stress instrument test. The stress of the chemically strengthened glass is in a balanced equal relationship with the tensile stress, and the SLP-1000 stress meter tests the tensile stress area of the glass more accurately, so that the stress contained in the glass under the unit thickness is represented by the ratio of the tensile stress integral to the thickness, and the stress degree of the chemically strengthened glass is represented.
And (3) complete machine drop test: a method for testing the strength of strengthened glass includes sticking the strengthened glass piece to the sample of electronic device such as mobile phone, dropping the glass from high position, recording the height of broken glass, and using the height value to reflect the strength of glass.
Single bar static strength: the single-rod static pressure test refers to the acting force of a round-head rod on glass during glass breaking, also called breaking pressure, and here, the single-rod static pressure test refers to: the glass to be measured is made into a round shape with the diameter of 40mm, the round shape is placed on a circular ring with the inner diameter of 30mm, the outer diameter of 50mm and the semicircular cross section, and then a round head rod with the diameter of 10mm is used for downwards pressing the glass placed in the circular ring at the constant speed of 1mm/s until the glass is broken. This strength characterizes the cover glass 'ability to resist deformation, which is very effective for the glass' ability to resist bending and blunt impacts.
In the invention, the stress measurement can be respectively carried out on a surface high-pressure stress region and a deep low-pressure stress region by FSM6000 and SLP1000 produced by Orihara, and a stress curve is fitted by adopting PMC software to obtain corresponding test results. Of course, other stress testers capable of measuring the surface high-pressure stress region and the deep low-pressure stress region can be used.
The invention provides a strengthened glass with a safe stress state, and the surface compressive stress of the strengthened glass meets the following relation:
wherein, CS 50 The compressive stress is 50mm deep from the surface of the tempered glass and has a unit of MPa; a is-486.23; b is 0.449;217-20T ≦ c ≦ 217+20/T; t is the thickness of the tempered glass in mm.
The strengthened glass is obtained after ion exchange reaction of precursor glass. In one or more embodiments, the strengthened glass is obtained by chemical strengthening, and the surface compressive stress CS of the strengthened glass is 500MPa or more, 600MPa or more, 700MPa or more, 800MPa or more, 900MPa or more, 1000MPa or more, and the maximum is 1200MPa, so that the impact resistance of the strengthened glass is ensured.
In one or more embodiments, the depth DOL of the strengthened glass compressive stress layer 0 Up to 16% or more of the thickness of the strengthened glass, which can also be described as DOL 0 Is a fraction of the glass thickness T. In one or more embodiments, the depth DOL of the strengthened glass compressive stress layer 0 May be equal to or greater than 0.16T, equal to or greater than 0.17T, equal to or greater than 0.18T, equal to or greater than 0.19T, equal to or greater than 0.20T, equal to or greater than 0.21T, up to 0.22T. In some embodiments, the depth DOL of the compressive stress layer of the strengthened glass 0 Can be 0.16T to 0.18T, 0.18T to 0.19T, 0.19T to 0.20T, 0.20T to 0.21T, 0.16T to 0.20T, 0.16T to 0.21T, 0.17T to 0.22T, 0.19T to 0.21T, 0.16T to 0.22T, 0.16T to 0.19T, 0.17T to 0.21T, 0.18T to 0.21T, 0.17T to 0.18T or 0.18T to 0.22T, so as to ensure the anti-falling performance of the tempered glass.
In one or more embodiments, the tempered glass has a safe compressive stress state, the safe compressive stress state is that the compressive stress of the tempered glass is high enough that the drop height of the tempered glass is at least more than 1.5m, and the average size of the vertical projection of more than 70% of the broken piece particles generated when the tempered glass is broken by dropping on a two-dimensional drawing is more than 15mm. Compared with the common tempered glass, the tempered glass has safer stress state, and can meet the requirements of users on the anti-falling performance of products and ensure the safety of the products particularly in the application aspect of electronic products. In a complete machine drop test, the drop resistance height of the tempered glass is more than 1.5m, which shows that the tempered glass has excellent drop resistance. And judging the safety range of the tensile stress of the tempered glass through a tensile stress release experiment. In commercial production, the present invention provides strengthened glasses whose stress state can be determined by their CS 50 And its material thicknessThe relation between the two is characterized, and the production personnel can detect the prepared strengthened glass and can pass the CS of the strengthened glass 50 And T, whether the obtained stress of the tempered glass is in a safe state or not is judged by whether the above relational expression is satisfied or not.
The strengthened glass satisfying the above formula conditions has an optimum compressive stress state and passes through the strengthened glass CS 50 The stress state of the tempered glass is represented by the relation between the thickness of the tempered glass and the stress state of the tempered glass, the tempered glass can be used as a cover plate protection material of electronic products such as mobile phones and the like, compared with common tempered glass, the tempered glass has excellent anti-falling performance and safety, the internal stress state of the tempered glass is optimized, the application range of the tempered glass is wide, the tempered glass can be applied to the field of display protection cover plates of electronic products, and the tempered glass has development and application prospects.
The invention also provides a processing method of the strengthened glass with the safe compressive stress state, which comprises the following steps:
s1: carrying out preheating treatment on the precursor glass;
s2: putting the precursor glass subjected to the preheating treatment in the step S1 into a salt bath, and heating to perform an ion exchange reaction to obtain the strengthened glass;
wherein the salt bath is a potassium nitrate and sodium nitrate mixed salt bath, and the mass fraction of the sodium nitrate is less than that of Na in the precursor glass component 2 O/(Li 2 O+Na 2 O+K 2 O) and greater than Na in the precursor glass component 2 The percentage by mole of O, the zoom ratio of the tempered glass is controlled between 1.5 and 2 per mill.
Wherein the salt bath comprises at least one or more sodium-containing salts and one or more potassium-containing salts. Preferably, the salt bath comprises KNO 3 And NaNO 3 And KNO 3 And NaNO 3 The content of (2) is related to the frequency of ion exchange reaction, and the pressure stress state of the tempered glass is adjusted to reach an optimal range by adjusting the salt bath concentration.
The one or more ion exchange processes used to strengthen the precursor glass may include, but are not limited to: immersing it in a single salt bath, or immersing it in a single salt bathNot in multiple salt baths of the same or different composition. In addition, the composition of one or more salt baths may include more than one larger radius ion (e.g., na) + And K + ) Or a single ion of larger radius. Those skilled in the art will appreciate that parameters of the ion exchange process include, but are not limited to: the composition and temperature of the salt bath, the immersion time, the number of immersions of the inner glass layer in one or more salt baths, the use of multiple salt baths, additional steps (such as annealing, washing), in embodiments the composition of the salt bath may also employ nitrates, sulfates and/or chlorides of alkali metal ions with larger ionic radii.
The control of the reaction conditions varies depending on the number of times the ion exchange reaction is carried out. The invention carries out potassium-sodium and/or sodium-lithium ion exchange on precursor glass in a mixed salt bath of potassium salt and sodium salt, and carries out potassium-sodium ion exchange on the surface layer of the precursor glass, so that the strengthened glass obtains enough surface pressure stress; meanwhile, sodium ions with smaller ion radius in the mixed salt bath can exchange ions with lithium ions in the depth of the precursor glass, so that the ion exchange depth is further deepened, a deeper compressive stress layer depth is formed, and the strength of the strengthened glass is further improved.
In some embodiments, when the ion exchange reaction is performed for a single time, the precursor glass to be treated is subjected to a preheating process at 300 ℃ to 400 ℃ for 10min to 30min. Then, the precursor glass is put in a glass containing KNO 3 And NaNO 3 Reacting in salt bath, and controlling the temperature of ion exchange reaction between 390 ℃ and 460 ℃. Wherein, the salt bath components mentioned in the invention are all calculated by wt%. NaNO in the salt bath 3 Has a certain relation with the concentration of alkali metal in the precursor glass component, naNO in the salt bath 3 Is less than Na in the precursor glass component 2 O/(Li 2 O+Na 2 O+K 2 O) and is greater than Na in the precursor glass component 2 The molar ratio of O to the total components. Wherein Na is contained in the precursor glass component 2 The molar ratio of O to the total components is 1-6%, and Na in the precursor glass component 2 O/(Li 2 O+Na 2 O+K 2 O) is 4.76 to 74.07 percent. The salt bath comprises 6 to 74.07 percent of NaNO 3 And all ranges and subranges therebetween, e.g., 6.8% to 10%,9.8% to 10%,15% to 20%,9.4% to 25%,8.5% to 35%,9% to 44%,10% to 59%,25% to 68%,13% to 37%,24% to 46%,6%,10%,15%,25%,36%,47%,57%, or 68%.
Furthermore, the scaling ratio of the precursor glass after the ion exchange reaction needs to be controlled, the volume of the precursor glass after the ion exchange reaction is carried out can be changed, and the scaling ratio is the ratio of the size variation of the finally obtained strengthened glass to the original size. Recording the original size of the tempered glass before the reaction period, detecting the size of the tempered glass in real time during the ion exchange period, adjusting the ion exchange reaction time by controlling the zoom ratio of the tempered glass to control the zoom ratio of the tempered glass to be between 1.5 per mill and 2 per mill, preferably 1.6 to 2 permillage, 1.7 to 2 permillage, 1.8 to 2 permillage, 1.9 to 2 permillage, 1.5 to 1.6 permillage, 1.5 to 1.7 permillage, 1.5 to 1.8 permillage, 1.5 to 1.9 permillage, 1.6 to 1.7 permillage, 1.6 to 1.8 permillage, 1.6 to 1.9 permillage, 1.6 to 2.0 permillage, 1.7 to 1.8 permillage, 1.7 to 1.9 permillage, 1.7 to 2.0 permillage, 1.8 to 1.9 permillage, 1.8 to 2.0 permillage, or 1.9 to 2.0 permillage, etc., to control the final stress of the glass.
In one or more embodiments, whether a single-step process or a multi-step process, multiple batches of precursor glass are chemically strengthened, i.e., multiple batches of precursor glass are strengthened in batches in the same salt bath environment. During the ion exchange reaction, a small amount of impurity ions, mainly lithium ions exchanged from the precursor glass, are generated in the ion exchange salt bath after the chemical strengthening of each batch of precursor glass is completed, and the concentration of the lithium ions in the ion exchange salt bath is increased after the chemical strengthening of multiple batches of precursor glass, so that the concentration of the lithium ions must be controlled because the lithium ions in the ion exchange salt bath become K + -Na + 、Na + -Li + Hindering ions for ion exchange, presence of small amounts of lithium ionsThe ion exchange degree can be greatly reduced, and the strengthened state of the strengthened glass is weakened. The lithium ion concentration in the salt bath is less than 0.25% and all ranges and subranges therebetween, such as 0.02% to 0.2%,0.1% to 0.16%,0.03% to 0.2%,0.04% to 0.18%,0.05% to 0.1%,0.01% to 0.24%,0.1% to 0.25%,0.1% to 0.18%,0.1% to 0.15%,0.1% to 0.12%,0%,0.15%,0.18%,0.2%,0.19%,0.14%,0.16%,0.05%,0.21%,0.08%,0.06%,0.04%,0.03%,0.02%, or 0.01%, based on the molar ratio of total alkali metal ions in the salt bath.
In some embodiments, when the compressive stress of the non-first-batch strengthened glass surface is reduced to 5% -20% of the compressive stress of the first-batch strengthened glass surface, stopping ion exchange, and adding a lithium ion purified substance into the ion exchange salt bath for heating reaction for a period of time. Preferably, 0.1 to 2 mass percent of lithium ion purified product of the mass of the ion exchange salt bath is added into the ion exchange salt bath, the purification temperature is controlled between 360 and 450 ℃, and the reaction time is consistent with the strengthening time of the strengthened glass.
In some embodiments, when the compressive stress of the non-first-batch strengthened glass surface is reduced to 10% -20% of the compressive stress of the first-batch strengthened glass surface, stopping ion exchange, taking out the precursor glass from the ion exchange salt bath, and then adding 1% -5% lithium ion purified matter of which the mass is equal to that of the ion exchange salt bath into the ion exchange salt bath, wherein the purification temperature is controlled to be 360-450 ℃, and the reaction time is consistent with the strengthened glass strengthening time. However, if a plurality of batches of precursor glasses are separately put into separate salt baths for strengthening treatment, no lithium ion purification material is added.
The lithium ion purification material is an ion sieve material which contains the following components in percentage by weight of oxides: 15% -55% of SiO 2 The metal in the functional metal oxide is univalent and/or bivalent metal, the univalent metal is at least one of lithium, sodium, potassium and rubidium, the bivalent metal is at least one of magnesium, calcium, strontium and barium, and the auxiliary material and SiO are mixed 2 Forming polar covalent bond and ionic bond, and the adjuvant is at least one selected from phosphorus oxide, boron oxide, aluminum oxide, zirconium oxide, chromium oxide, iron oxide, zinc oxide, bismuth oxide, and cobalt oxide. The lithium ion purified product adopted by the invention can be purchased from the market and is an RT product produced by Shenzhen Donglike technology Limited. The lithium ion purification product is mainly used for removing Li in an ion exchange salt bath + Control of Li in ion-exchanged salt bath + To reduce its effect on the ion exchange degree of the strengthened glass; meanwhile, other impurity ions cannot be introduced into the ion exchange salt bath, and the used ion sieve cannot pollute the environment. The use of the lithium ion purified product can effectively avoid the deactivation of the ion exchange salt bath, weaken the strengthening effect thereof and recover the activity of the ion exchange salt bath.
The invention also discloses a consumer electronics terminal, comprising: a housing comprising a front surface, a rear surface, and side surfaces; and an electronic assembly partially located within the housing, the electronic assembly including a display located at or adjacent a front surface of the housing; the front surface or/and the back surface or/and the side surfaces comprise the strengthened glass with the safe stress state. The consumer electronic terminal comprises a mobile phone, a tablet computer or other electronic terminals.
The strengthened glass of the present invention can be included in other articles, such as an article having a display (or display article) (e.g., a consumer electronics product including a mobile phone, tablet, computer, navigation system, etc.), an architectural article, a transportation article (e.g., an automobile, train, airplane, marine vehicle, etc.), an appliance article, or any article that requires some transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles comprising any of the glass articles disclosed herein are shown in fig. 2 and 3. In particular, fig. 2 shows a front surface of a consumer electronic device, fig. 3 shows a rear surface of the consumer electronic device, which comprises a housing comprising a front surface 1, a rear surface 2 and side surfaces; and an electronic assembly partially or fully within the housing, and including not only a display, but also a controller, memory, and other electronic components, wherein the display is located at or adjacent to the front face of the housing. The front surface or/and the back surface or/and the side surface of the housing comprises tempered glass according to the invention.
In some embodiments, a cover article 3 may also be included that covers at the front surface of the housing or is positioned over the display, with the cover article 3 and/or a portion of the housing including the strengthened glass of the present invention.
In the present invention, in order to obtain a strengthened glass having a safe compressive stress state, there is also a certain requirement for the formulation of the glass, and specifically, the glass mainly comprises the following components in mol% based on oxides:
SiO 2 :65 to 75mol%, preferably 70 to 75mol%;
Al 2 O 3 ：8mol％～15mol％；
wherein, siO 2 In an amount of SiO 2 And Al 2 O 3 At least 78mol%, preferably 80mol% or more, of the total amount.
In the glass batch of the invention, the glass network component is mainly SiO 2 And Al 2 O 3 The two can improve the strength of the glass network structure, and the high network architecture composition can increase the quantity of glass bridge oxygen, especially improve the content of silicon components, and can improve the network structure strength of the glass. And Al 2 O 3 Contributes to increase in rigidity of the glass network, al 2 O 3 May be present in the glass in four or five coordination, which increases the packing density of the glass network and thus increases the compressive stress created by the chemical strengthening. The high network structure strength plays an important role in ion exchange of the glass, because the glass can perform K step by step or simultaneously during the ion exchange process + -Na + 、Na + -Li + And binary ion exchange to form a composite compressive stress layer. However, in this process, the glass generates a stress relaxation effect due to the exchange of ions with different radii, and the high temperature and the long time in the ion exchange reactionThe reaction time and other factors can weaken the composite pressure stress layer, especially the middle-deep layer, so that the influence of the reasons on the composite pressure stress layer can be effectively overcome by improving the network structure strength of the glass. In some embodiments, the glass can comprise 8mol% to 15mol% Al 2 O 3 And all ranges and subranges therebetween, e.g., 8mol% to 14.5mol%,8mol% to 14mol%,8mol% to 13.5mol%,8mol% to 13mol%,10mol% to 13mol%,8mol% to 12mol%,9mol% to 14.5mol%,9mol% to 14mol%,9mol% to 11.5mol%,10mol% to 13mol%,9mol%,9.5mol%,10mol%,10.5mol%,11mol%,11.2mol%,12.4mol%,12.6mol%,12.8mol%,13mol%,13.2mol%,13.4mol%,13.6mol%,13.8mol%, or 15mol%.
The component of the glass also comprises B 2 O 3 ，B 2 O 3 As a secondary network architecture for glass, B in appropriate amounts 2 O 3 Can promote the high-temperature melting of the glass, reduce the melting difficulty and effectively improve the ion exchange rate in the glass, particularly for K + -Na + The exchange capacity of (A) is improved remarkably, but B is excessive 2 O 3 Resulting in a weakening of the glass network structure, and thus it is necessary to control B 2 O 3 Amount of (A) added, B 2 O 3 Is controlled within a range of not more than 3mol%. In some embodiments, the glass can include not greater than 3mol% B 2 O 3 And all ranges and subranges therebetween, e.g., 0 to 2.9mol%,0 to 2.7mol%,0 to 2.1mol%,0 to 1.7mol%,0 to 1.2mol%,1mol% to 2.6mol%,1mol% to 2.0mol%,1mol% to 1.5mol%,1mol% to 1.3mol%,1mol% to 1.9mol%,0mol%,1.4mol%,1.6mol%,2.3mol%,2.5mol%,2.9mol%,2.7mol%,2.4mol%,2.1mol%,0.4mol%,0.7mol%,0.6mol%,0.5mol%,0.3mol%,0.2mol%, or 3.0mol%.
The components of the glass also comprise Na 2 O and Li 2 And (O). Wherein, na 2 The molar ratio of O is in the range of 1mol% to 6mol%。Na 2 O is the main component of ion exchange, is the key exchange ion for forming high surface pressure stress, and is K in the ion exchange salt bath + Carrying out K + -Na + Exchange, which enables the glass to achieve a sufficiently high compressive stress through ion exchange, and thus, in some embodiments, the glass may include 1mol% to 6mol% Na 2 O and all ranges and subranges therebetween, e.g., 1 to 4mol%,1mol% to 4.6mol%,1mol% to 4mol%,1mol% to 4.7mol%,1mol% to 3mol%,1mol% to 3.5mol%,2mol% to 5.9mol%,2mol% to 4.7mol%,2mol% to 3.8mol%,1.5mol% to 5.6mol%,2.6mol% to 4.9mol%,1.5mol% to 4mol%,3.7mol% to 5.8mol%,1mol%,1.5mol%,2mol%,2.8mol%,2.6mol%,2.5mol%,2.1mol%,3.8mol%,3.6mol%,4mol%,4.4mol%,4.3mol%,3.2mol%, or 5.1mol%.
Li 2 O is also a major component of ion exchange, li 2 The molar ratio of O is in the range of 7mol percent to 12mol percent, na in the ion exchange salt bath + Radius ratio K + Small, enabling it to penetrate more deeply into the glass and Li + Ion exchange is carried out, li in the glass + Is a key exchange ion for forming deep pressure stress and exchanges Na in salt bath with ions + By carrying out Na + -Li + And exchange, so that the glass can form a high-depth compressive stress layer. In some embodiments, the glass may include from 7mol% to 12mol% Li 2 O and all ranges and subranges therebetween, e.g., 7mol% to 11mol%,7.8mol% to 10.7mol%,7.5mol% to 10mol%,8.6mol% to 11.7mol%,8.2mol% to 11.4mol%,9.1mol% to 10.8mol%,9.2mol% to 11.5mol%,10.2mol% to 11.9mol%,8.5mol% to 11.5mol%,9.5mol% to 10mol%,10.6mol% to 11.9mol%,7.7mol% to 9.8mol%,7.5mol%,8mol%, 9.8mol%, 8.6mol%,9.5mol%,10.1mol%,11.8mol%,7.6mol%,10mol%,10.4mol%,11.3mol%,9.2mol%, or 10.1mol%.
Due to Na 2 O and Li 2 O is an alkali metal oxide, both within the glassIn a free state, the excess oxygen ions will break the bridging oxygen, so Na needs to be added 2 O and Li 2 The molar proportion of O is controlled in the range of 7mol% to 13mol%, and in some embodiments, the glass may include 7mol% to 13mol% Na 2 O+Li 2 O and all ranges and subranges therebetween, e.g., 8mol% to 13mol%,7mol% to 12mol%,8mol% to 10.5mol%,7mol% to 10.6mol%,8mol% to 11mol%,7mol% to 10.5mol%,7mol% to 11.5mol%,9mol% to 11mol%,7mol% to 8.9mol%,8.6mol% to 12.8mol%,9mol% to 12.4mol%,7mol% to 9.8mol%,7mol% to 10.4mol%,7mol% to 10.8mol%,9mol%,10mol%,11.2mol%,11.4mol%,11.6mol%,11.8mol%,12mol%,12.1mol%,12.3mol%,12.5mol%, or 13mol%.
The glass also comprises K 2 O，K 2 The molar ratio of O is controlled between 0mol percent and 3mol percent, K 2 O is the main component of ion exchange. In some embodiments, the glass can include 0mol% to 3mol% K 2 O and all ranges and subranges therebetween, e.g., 0.1mol% to 3mol%,0.2mol% to 2.8mol%,0.1mol% to 2.6mol%,0.3mol% to 2mol%,0.4mol% to 1.8mol%,0.5mol% to 1.0mol%,1mol% to 2.5mol%,1mol% to 2.0mol%,1mol% to 1.8mol%,1mol% to 1.5mol%,1mol% to 1.2mol%,0mol%,1.5mol%,1.8mol%,2mol%,2.9mol%,2.8mol%,2.6mol%,2.5mol%,2.1mol%,0.8mol%,0.6mol%,0.5mol%,0.4mol%,0.3mol%,0.2mol%,0.1mol%, or 0mol%.
The components of the glass also comprise MgO, the molar ratio of the MgO is controlled between 2mol percent and 7.5mol percent, and the MgO is used as a glass network structure intermediate and has the function of reducing the high-temperature viscosity of the glass, thereby achieving the function of increasing the Young modulus of the glass. In some embodiments, the glass can include 2mol% to 7.5mol% MgO and all ranges and subranges therebetween, such as 2.5mol% to 2.8mol%,2.5mol% to 2.6mol%,2.6mol% to 3.2mol%,2.4mol% to 3.8mol%,3.5mol% to 4.0mol%,3mol% to 4.5mol%,2.7mol% to 5.8mol%,2.5mol% to 5.0mol%,3.1mol% to 6.5mol%,4mol% to 5mol%,2.5mol%,3.5mol%,3.8mol%,3mol%,5mol%,2.8mol%,2.6mol%,4.5mol%,4.1mol%,4.8mol%,4.6mol%,3.2mol%,3.4mol%,3.3mol%,3.2mol%, or 3.1mol%.
The glass also includes chemical fining agents, including but not limited to SnO 2 And sodium chloride. In some embodiments, the glass can include not greater than 1mol% SnO 2 And sodium chloride and all ranges and subranges therebetween, e.g., 0.1mol% to 0.9mol%,0.1mol% to 0.8mol%,0.1mol% to 0.7mol%,0.1mol% to 0.6mol%,0.1mol% to 0.5mol%,0.1mol% to 0.4mol%,0.5mol% to 1.0mol%,0.05mol% to 1.0mol%,0.03mol% to 1.0mol%,0.02mol% to 1.0mol%,1mol%,0.9mol%,0.8mol%,0.7mol%,0.6mol%,0.5mol%,0.4mol%,0.3mol%,0.2mol%, or 0mol%.
Specifically, the glass contains neither phosphorus nor other alkaline earth metal elements other than magnesium. I.e. no active addition of phosphorus and other alkaline earth elements, but possibly in very small amounts, e.g. below 300ppm or less in the examples, as impurities. Phosphorus pentoxide in the glass can reduce the high-temperature melting temperature of the glass, but the phosphorus pentoxide has phosphorus-oxygen double bonds, so that the structure is unstable, the scratch resistance of the phosphorus pentoxide is poor, the phosphorus-containing structure can cause the bifurcation threshold of the glass to be reduced, and in the float glass, the phosphorus-containing structure can cause the glass to be easy to separate and crystallize, so that the production difficulty is improved. Magnesium alkaline earth metal has better high-temperature melting promotion property and has less influence on the ion exchange rate, but Ca, zn and other alkaline earth metal oxides have larger ion radius than magnesium and have larger influence on the ion exchange rate.
In this embodiment, the components of the glass frit formulation may optionally include tin oxide and sodium chloride as fining agents at a melting temperature of 1630 ℃ to 1700 ℃, e.g., 1630 ℃, 1640 ℃, 1650 ℃, 1680 ℃, 1690 ℃ or 1700 ℃, in a molar ratio of no more than 1%, e.g., 0.1%, 0.2%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%. And according to the high-temperature viscosity and the material property, the precursor glass can be produced by adopting an overflow down-draw method, a float method and a rolling method.
The processing method of the strengthened glass with the safe compressive stress state takes the embodiment 1 as an example:
s1: first, the glass precursor raw materials were weighed accurately in the proportions thereof according to the raw materials of example 1 in table 1, and then, after the raw materials were sufficiently mixed, they were melted by holding at 1630 ℃ for 4 hours, and then, they were molded to obtain a precursor glass plate having a thickness of 0.7 mm.
S2: preheating the precursor glass plate obtained in the step S1 at 350 ℃ for 23min, and placing 15wt% of NaNO into the preheated precursor glass plate 3 And 85wt% of KNO 3 The mixed salt bath is subjected to ion exchange reaction at the reaction temperature of 440 ℃ for 10 hours, the scaling ratio of the precursor glass plate is detected, and when the scaling ratio is 2 per mill, the precursor glass plate is taken out and cleaned after the reaction is finished, so that the strengthened glass plate is obtained.
The invention is illustrated below by means of specific examples and comparative examples, table 1 being the recipes for the precursor glasses and the comparative examples, table 2 being the process parameters for the preparation of strengthened glasses, table 3 being the performance test parameters for the examples and the comparative examples, and table 4 being the test results for samples of example 1 and example 3 with different thicknesses.
TABLE 1
Note: "-" indicates that the precursor glass does not contain the component.
TABLE 2
| Performance index | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Bifurcation threshold (MPa/mm) | 45000 | 48000 | 50000 | 45000 | 33200 |
| Threshold of scar (MPa/mm) | 38000 | 39800 | 42100 | 38000 | 28000 |
| Thickness (mm) | 0.7 | 0.7 | 0.7 | 0.8 | 0.7 |
| Na 2 O (mole percent) | 4 | 3 | 3 | 4 | -- |
| Na 2 O/(Li 2 O+Na 2 O+K 2 O) | 29.63 | 25 | 20 | 29.63 | -- |
TABLE 3
Note: "-" indicates that the strengthened glass was not tested for this parameter.
TABLE 4
Wherein the thickness and CS of the samples of example 1 and example 3 50 The relationship between the above was further verified, and it can be seen from Table 4 that the CS of the ion-exchanged strengthened glass was found to be present at different thicknesses 50 And the thickness thereof satisfies the relation formula of the invention.
In combination with tables 2 and 3, the tempered glass of this example was K-treated in a potassium-sodium mixed salt bath + -Na + Ion exchange is carried out while Na is also carried out + -Li + Ion exchange to form compressive stress, and chemically strengthening the strengthened glass to improve the strength of the strengthened glass. The surface compressive stress of the strengthened glass is more than 500MPa after strengthening, and the shock resistance of the glass is ensured. At the same time, the CS of the obtained strengthened glass is adjusted by controlling the zoom ratio to adjust the strengthening time 50 The thickness of the glass meets the relational expression of the invention, and finally the strengthened glass has high anti-falling performance. While comparative example 1 has no control of the scaling ratio, which also makes it resistantThe drop performance is far less than in the embodiments of the present invention.
And (3) carrying out a complete machine drop experiment on the tempered glass obtained by the preparation method in the embodiment 1, firmly attaching a mobile phone mold to a sample made of the tempered glass in the embodiment 1, horizontally dropping the tempered glass sample downwards onto a marble plate with the surface attached with sand paper, and taking the highest point of the tempered glass sample which is not broken as an anti-drop height. After the test of a complete machine drop test, the drop resistance of the tempered glass in the example 1 is 1.5m, which is much higher than that of the tempered glass in the comparative example 1, and the example 1 has high drop resistance.
In a tensile stress release experiment, referring to the attached drawing 1, the reinforced glass in the embodiment 1 is broken after falling from the height of 1.7m, the average size of vertical projection of more than 70% of broken particles in broken particles on a two-dimensional drawing is more than 15mm, and fragments with too small particles cannot be generated, which shows that the tensile stress of the reinforced glass in the embodiment 1 is in a safe range, and potential safety hazards cannot be caused.
As can be seen from table 3, the compressive stress and the tensile stress of the strengthened glass of the present invention are in the best state, the strengthened glass has high strength of network structure, and obtains high surface compressive stress, so as to effectively improve the drop-resistant height of the strengthened glass, and simultaneously, the tensile stress of the strengthened glass is controlled in a safe range to further improve the limit of the drop-resistant strength, thereby ensuring the safety of the tensile stress of the strengthened glass. Moreover, explosive cracking due to slight impact can not occur, and the phenomenon of spontaneous explosion can not occur.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (22)
1. The strengthened glass with a safe stress state is characterized in that the numerical values of the surface compressive stress and the thickness of the strengthened glass meet the following conditions:
wherein CS 50 Is the compressive stress at a distance of 50 microns below the glass surface in MPa; a is-486.23; b is 0.449;217-20T ≦ c ≦ 217+20/T; t is the thickness of the tempered glass and the unit is mm;
the safety stress state is that the compressive stress of the reinforced glass is high enough to ensure that the falling resistance height of the reinforced glass is at least more than 1.5m, and the average size of the vertical projection of more than 70% of the broken particles generated when the reinforced glass falls and is broken on a two-dimensional drawing is more than 15mm;
and the scaling ratio of the tempered glass is between 1.5 and 2 per thousand.
2. The strengthened glass having a safe stress state according to claim 1, wherein the surface compressive stress CS of the strengthened glass is 500MPa or more.
3. The strengthened glass having a safe stress state of claim 1, wherein the depth of compressive stress layer of the strengthened glass is DOL 0 The thickness of the tempered glass is more than 16%.
4. The strengthened glass having a safe stress state according to claim 1, wherein the strengthened glass has a thickness T of 0.4mm to 2mm.
5. The strengthened glass having a safe stress state according to claim 1, wherein the strengthened glass composition comprises Na 2 O、Li 2 O or K 2 O。
6. The strengthened glass having a safe stress state according to claim 1, wherein the strengthened glass is free of phosphorous.
7. The strengthened glass having a safe stress state according to claim 1, wherein the strengthened glass is free of alkaline earth elements other than magnesium.
8. A method for processing strengthened glass with a safe stress state is characterized by comprising the following steps:
s1: carrying out preheating treatment on the precursor glass;
s2: putting the precursor glass subjected to the preheating treatment in the step S1 into a salt bath, and heating to perform an ion exchange reaction to obtain the strengthened glass according to any one of claims 1 to 7;
wherein the salt bath is a potassium nitrate and sodium nitrate mixed salt bath, and the mass fraction of the sodium nitrate is less than that of Na in the precursor glass component 2 O/(Li 2 O+Na 2 O+K 2 O) and greater than Na in the precursor glass component 2 The percentage by mole of O, the scaling ratio of the strengthened glass is controlled between 1.5 per mill and 2 per mill.
9. The method of claim 8, wherein the precursor glass composition comprises Na 2 O、Li 2 O or K 2 O。
10. The method of processing a strengthened glass having a safe stress state according to claim 8, wherein the salt bath in step S2 contains lithium ions at a concentration of less than 0.25 mol% based on the total alkali metal ions in the salt bath.
11. The method of claim 8, wherein the precursor glass is preheated at 300-400 ℃ for 10-30 min in step S1.
12. The method of claim 8, wherein the ion exchange reaction temperature in step S2 is 350 to 500 ℃.
13. The method of claim 8, wherein the ion exchange reaction temperature in step S2 is 390-460 ℃.
14. The method of claim 8, wherein the precursor glass is formed by any one of a float process, an overflow process, a rolling process, and a casting process.
15. The method of processing a strengthened glass having a safe stress state according to claim 8, wherein when the precursor glass is ion-exchanged in a plurality of batches, when it is detected that the compressive stress CS on the surface of the non-first-batch strengthened glass has decreased to 10% to 20% of the compressive stress on the surface of the first-batch strengthened glass, the ion exchange reaction is stopped, and after the lithium ion purification product is charged into the salt bath, the ion exchange is continued by heating and purifying.
16. The method of processing a strengthened glass having a safe stress state of claim 15, wherein the lithium ion purification material is an ionic sieve material comprising, in wt% on an oxide basis: siO 2 2 15-55 percent of auxiliary material, 5-50 percent of at least one functional metal oxide and 15-48 percent of at least one functional metal oxide; the metal in the functional metal oxide is a monovalent and/or divalent metal.
17. The method of claim 16, wherein the lithium ion purification material is an ion sieve material, the monovalent metal is at least one of lithium, sodium, potassium, rubidium, and the divalent metal is at least one of magnesium, calcium, strontium, and barium; the auxiliary material and SiO 2 Forming polar covalent bond and ionic bond, wherein the adjuvant is selected from phosphorus oxide, boron oxide, aluminum oxide, zirconium oxide, chromium oxide, iron oxide, zinc oxide, and zinc oxideAt least one of bismuth and cobalt oxide.
18. The method of claim 15, wherein the heating to refine the glass is at a temperature of 300 ℃ to 500 ℃ and the reaction time is substantially the same as the strengthening time of the strengthened glass.
19. The method for processing a strengthened glass having a safe stress state according to claim 15, wherein the amount of the lithium ion purification material added is 1% to 5% by mass of the ion-exchange salt bath.
20. A consumer electronics terminal, comprising:
a housing comprising a front surface, a rear surface, and side surfaces;
and an electronic assembly partially located within the housing, the electronic assembly including a display located at or adjacent a front surface of the housing;
the front surface or/and the back surface or/and the side surface comprises the strengthened glass with the safe stress state as defined in any one of claims 1 to 7 and/or the strengthened glass with the safe stress state prepared by the processing method as defined in any one of claims 8 to 19.
21. The consumer electronic terminal according to claim 20, further comprising a cover article covering the front surface of the housing or on the display, the cover article comprising the strengthened glass having a safe stress state according to any one of claims 1 to 7 and/or the strengthened glass having a safe stress state produced by the process according to any one of claims 8 to 19.
22. The consumer electronic terminal according to claim 20 or 21, wherein the consumer electronic terminal comprises a mobile phone, a tablet computer, or other electronic terminal.
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| CN202010833255.1A CN114075044B (en) | 2020-08-18 | 2020-08-18 | Tempered glass with safe stress state and processing method thereof |
| PCT/CN2021/106369 WO2022037333A1 (en) | 2020-08-18 | 2021-07-15 | Tempered glass having safe stress state and processing method therefor |
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| CN106000287A (en) * | 2016-06-16 | 2016-10-12 | 深圳市东丽华科技有限公司 | Ion sieve material and preparing and using methods thereof |
| CN108147657A (en) * | 2017-12-29 | 2018-06-12 | 深圳市东丽华科技有限公司 | A kind of element glass, strengthened glass and preparation method |
| WO2019054342A1 (en) * | 2017-09-13 | 2019-03-21 | Ａｇｃ株式会社 | Chemically strengthened glass sheet and production method therefor |
| CN110040982A (en) * | 2019-05-14 | 2019-07-23 | 深圳市东丽华科技有限公司 | Chemically reinforced glass and the preparation method and application thereof with combined stress advantage |
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| US8304078B2 (en) * | 2005-09-12 | 2012-11-06 | Saxon Glass Technologies, Inc. | Chemically strengthened lithium aluminosilicate glass having high strength effective to resist fracture upon flexing |
| KR102205919B1 (en) * | 2016-01-21 | 2021-01-21 | 에이지씨 가부시키가이샤 | Chemically strengthened glass and method for manufacturing chemically strengthened glass |
| CN110240419B (en) * | 2019-06-06 | 2021-11-05 | 重庆鑫景特种玻璃有限公司 | Lithium aluminum silicon glass, lithium aluminum silicon chemically strengthened glass, and preparation method and application thereof |
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| CN106000287A (en) * | 2016-06-16 | 2016-10-12 | 深圳市东丽华科技有限公司 | Ion sieve material and preparing and using methods thereof |
| WO2019054342A1 (en) * | 2017-09-13 | 2019-03-21 | Ａｇｃ株式会社 | Chemically strengthened glass sheet and production method therefor |
| CN108147657A (en) * | 2017-12-29 | 2018-06-12 | 深圳市东丽华科技有限公司 | A kind of element glass, strengthened glass and preparation method |
| CN111302654A (en) * | 2018-12-11 | 2020-06-19 | 深圳市东丽华科技有限公司 | Single-side dominant compressive stress glass and preparation method and application thereof |
| CN110040982A (en) * | 2019-05-14 | 2019-07-23 | 深圳市东丽华科技有限公司 | Chemically reinforced glass and the preparation method and application thereof with combined stress advantage |
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| CN114075044A (en) | 2022-02-22 |
| WO2022037333A1 (en) | 2022-02-24 |
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