CN112452687A - Bendable light and thin toughened glass and preparation method thereof - Google Patents
Bendable light and thin toughened glass and preparation method thereof Download PDFInfo
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- CN112452687A CN112452687A CN202011293769.9A CN202011293769A CN112452687A CN 112452687 A CN112452687 A CN 112452687A CN 202011293769 A CN202011293769 A CN 202011293769A CN 112452687 A CN112452687 A CN 112452687A
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- glass
- thin
- resin film
- bendable light
- transparent flexible
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Links
- 239000005341 toughened glass Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 151
- 229920005989 resin Polymers 0.000 claims abstract description 88
- 239000011347 resin Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000005507 spraying Methods 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229920002050 silicone resin Polymers 0.000 claims abstract description 10
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 60
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007921 spray Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 17
- 229920003257 polycarbosilane Polymers 0.000 claims description 16
- 238000001723 curing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 230000001965 increasing effect Effects 0.000 claims description 10
- 150000003573 thiols Chemical class 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000004017 vitrification Methods 0.000 claims description 9
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 6
- 238000012650 click reaction Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- AKQHUJRZKBYZLC-UHFFFAOYSA-N tri(propan-2-yl)-prop-2-enylsilane Chemical compound CC(C)[Si](C(C)C)(C(C)C)CC=C AKQHUJRZKBYZLC-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 125000005372 silanol group Chemical group 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000010309 melting process Methods 0.000 abstract description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 7
- 239000011734 sodium Substances 0.000 description 5
- 239000006184 cosolvent Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0272—After-treatment with ovens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses bendable light and thin toughened glass and a preparation method thereof. The invention (1) utilizes silanol groups and nano Al2O3Hydrogen bonding force between the Al and the Al2O3The transparent flexible resin film is embedded in a fine network structure formed by crosslinking of the sulfur-containing hyperbranched polysilane and the thiol silicone resin to obtain a transparent flexible resin film, and the transparent flexible resin film is used as a substrate to effectively absorb impact and prevent glass cracks; (2) the fusible glass is designed and prepared, and the adhesive force between the resin film and the fusible glass is effectively enhanced by utilizing the hot melting process, so that the generation and the diffusion of cracks are inhibited; releasing nano Al2O3Entering the glass to fill the gap and enhance the strength of the glass; the chemical exchange of sodium ions and potassium ions is promoted on the surface of the glass, the toughening effect is enhanced, and the wear resistance of the glass is improved. (3) By means of the spraying method, the exchange process of potassium ions and sodium ions is homogenized, the problem of uneven stress is avoided, and the performance of bendable light and thin toughened glass is improved.
Description
Technical Field
The invention relates to the technical field of toughened glass, in particular to bendable light and thin toughened glass and a preparation method thereof.
Background
The tempered glass is glass with compressive stress on the surface, and is tempered by adopting thermal strengthening, physical strengthening and chemical strengthening modes generally, so that the strength of the glass is enhanced, and the brittleness of the glass is compensated. However, the high temperature heat treatment and the physical strengthening are not suitable for light and thin glass, and the chemical strengthening is not related to the size and the thickness, so that the glass is suitable for light and thin toughened glass.
Generally, the thinner the glass, the better its bendability. In the existing bending light and thin tempering preparation process, glass is generally prepared by etching and other methods, and is used as a substrate, and polymer is coated to increase other properties. At present, the method of coating glass material and firing together to form glass by using polymer as a substrate is not seen, and the mechanism of releasing nano particles in the polymer and increasing the strength of the glass by utilizing the co-melting process of the polymer and the glass material is also not seen, so that the research is needed to expand the research direction of toughened glass.
Disclosure of Invention
The invention aims to provide bendable light and thin toughened glass and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the utility model provides a bendable frivolous toughened glass, toughened glass includes transparent flexible resin film I, transparent flexible resin film II to and the fusible glass of intermediate setting.
Preferably, the meltable glass raw material comprises the following components: by weight, Pb3O450-60 parts of B2O315 to 20 portions of Na210-15 parts of O and SiO28 to 16 parts of K3PO45-8 parts.
Preferably, the transparent flexible resin film is prepared from sulfur-containing hyperbranched polysilane, thiol silicone resin and nano Al2O3And (4) forming.
Preferably, the nano Al2O3The particle size is 5 to 100 nm.
Preferably, the preparation method of the bendable light and thin toughened glass comprises the following steps:
s1, preparing a glass material;
s2, preparing a resin material;
and S3, preparing bendable light and thin toughened glass.
Preferably, the method comprises the following steps: the operation environment is an inert gas atmosphere;
s1, preparing a glass material:
weighing Pb3O4、B2O3、SiO2Ultrasonically dispersing in deionized water to obtain a suspension without dust; transferring the mixture into a vacuum box, drying the mixture for 3 hours at the set temperature of 80-100 ℃, removing free water to obtain an agglomerated block, performing ball milling, and sieving the agglomerated block by using a 200-400-mesh sieve; placing the obtained powder in an atmosphere furnace, drying for 30 minutes at the set temperature of 300-400 ℃, and removing capillary water and crystal water; taking out, adding K3PO4Uniformly mixing, filling the mixture into a carbon film, stirring and melting the mixture by using a tungsten rod, and setting the reaction temperature to 750 ℃ for reaction for 30 minutes; cooling to 400-410 ℃ at a cooling rate of 15 ℃/min, and then slowly cooling to room temperature at a cooling rate of 2 ℃/min; crushing the obtained glass into powder with the particle size of less than 100 microns, adding a dispersion medium methanol-ethanol mixed solution, grinding and dispersing by using mixed ZrO balls, setting the rotating speed to be 240-260 rmp, carrying out ball milling for 16 hours, sieving by using a 400-mesh nylon screen to obtain a glass material, and sealing for later use;
s2 preparation of resin material:
(1) stirring and dispersing the weighed magnesium powder and iodine in 3/8 ethyl ether in sequence; keeping the temperature at 0-5 ℃, adding 3-bromopropylene and 5/16 diethyl ether into the mixed solution, and reacting for 120 minutes; adding 3- (trimethyloxysilyl) -1-propyl mercaptan and 5/16 diethyl ether solvent, stirring at room temperature for 16-22 hours, adding methanol to terminate the reaction, filtering, and drying in vacuum to obtain a crude product of allyl triisopropyl silane; setting the reaction temperature to be 120-150 ℃ under the pressure of 2.67kPa, and carrying out vacuum distillation to obtain purified colorless transparent liquid; initiating mercaptan-alkene click reaction under the conditions that the laser wavelength is 365nm and the power is 1000W, wherein the reaction time is 30 seconds, and obtaining sulfur-containing hyperbranched polycarbosilane for later use;
(2) weighing thiol silicone resin and nano Al2O3Mixing the hyperbranched polycarbosilane with the prepared hyperbranched polycarbosilane at a set rotating speed of 800-1000 rmp at a high speed to obtain a resin material, and sealing for later use;
s3, preparing bendable light and thin toughened glass:
(1) placing the carbon film on a rotating disc, rotating at the rotating speed of 3000rmp, and spraying the resin material on the carbon film in a criss-cross mode, wherein the size of a spray gun is 80-100 mu m; setting the laser wavelength to 365nm, the laser power to 1000W, the distance between a light source and the carbon film to be 20cm, and performing ultraviolet curing to form a transparent flexible resin film I;
(2) rotating the transparent flexible resin film I serving as a substrate at a rotating speed of 4000rmp, and spraying the glass material in the step S1 on the transparent flexible resin film I in a criss-cross manner, wherein the size of a spray gun is 80-100 mu m; spraying a resin material on the glass material in the mode in the step (1), and performing ultraviolet curing to form a transparent flexible resin film II to obtain a composite glass substrate;
(3) placing the composite glass substrate in an atmosphere furnace, drying for 2 hours at the set temperature of 80 ℃, heating to 250 ℃ at the speed of 5 ℃/min, reacting for 30 minutes, completely removing the dispersion medium, and continuously heating to 410-480 ℃ for vitrification to obtain bendable light and thin glass;
(4) the rigidity of the glass is increased by a chemical strengthening method, and 21.5 percent KNO is sprayed on the surface of the bendable light and thin glass3The size of the spray gun is 10-50 mu m, the temperature of the bendable light and thin glass is kept at 130 ℃ in the spraying process, and the spraying is carried out for 3 times in a circulating way; and transferring the glass to an atmosphere furnace, setting the heat treatment temperature, and treating for 0.5-3 hours to obtain the bendable light and thin toughened glass.
Preferably, in step S1, the mixed ZrO balls are obtained by mixing three different sizes of ZrO balls of 3mm, 5mm and 8mm at a ratio of 6:3: 1.
Preferably, in step S3, the thickness of the transparent flexible resin film i and the thickness of the transparent flexible resin film ii are both 0.05-0.08 mm.
Preferably, in step S3, the thickness of the glass material is 0.75-0.95 mm.
Preferably, in step S3, the heat treatment temperature is 350-400 ℃.
In the technical scheme, in a three-step walking mode, the first step is as follows: uniformly spraying a glass material prepared in advance between two resin films by taking an ultraviolet-cured transparent flexible resin film as a substrate to obtain a composite glass substrate; the second step is that: performing hot melting vitrification on the glass to prepare bendable light and thin glass; the third step: spraying 21.5% KNO3And chemically toughening the solution to obtain the bendable light and thin toughened glass.
First, because the heat resistance of the polymer may be lower than that of inorganic materials and metals. People can use glass as a substrate and apply polymer paint on the surface, so that the polymer and glass materials cannot be fired into glass together. In the scheme, different from the conventional mode, the method designs that the inorganic layer is prepared by melting glass, takes a transparent flexible resin film as a substrate, sprays glass materials on the two resin films, and then burns the two resin films together to synthesize the bendable light and thin glass.
We are based on the fact that the silanol groups which dissociate can react with Al2O3Hydroxylation reaction and cross-linking reaction of sulfur-containing hyperbranched polysilane and thiol silicone resin are carried out, and the transparent flexible resin film (hereinafter referred to as resin film) is designed into nano Al2O3A mosaic fine mesh structure. And the substrate can effectively absorb impact and is beneficial to preventing cracks from generating. Meanwhile, the polycondensation effect generated in the process of preparing the bendable light and thin glass through melting is utilized, so that the adhesive force between the resin film and the meltable glass is effectively enhanced, and the generation and the diffusion of cracks are effectively inhibited. By using the polycondensation or decomposition process, nano Al is obtained2O3And releasing, wherein one part of the mixture enters the glass to fill the gap and enhance the strength of the glass, and the other part of the mixture is left on the surface of the glass to promote the chemical exchange of sodium ions and potassium ions, enhance the toughening effect and increase the wear resistance of the glass.
In addition, an ultraviolet curing method is adopted, energy consumption is low, rapid curing is carried out at ambient temperature, time is short, no photoinitiator is introduced, the prepared resin film is a transparent flexible substance, the transparency is more than 95%, and the influence on the light transmittance and the flexibility of the glass can be effectively avoided.
Secondly, unlike the prior art of preparing light and thin glass by etching after preparing glass, the method utilizes K3PO4The method is characterized in that meltable glass is designed and prepared as a cosolvent, high-temperature crystallization is carried out firstly, the meltable glass is crushed to form a glass material with small particles, and then vitrification is carried out to directly prepare bendable light and thin glass. K3PO4The glass has the advantages of effectively improving the thermal deformation, having good fluidity, reducing the glass transition temperature, not needing high-temperature treatment and rapid cooling, and reducing the spontaneous explosion probability of the light and thin glass. Meanwhile, before spraying, a dispersion medium methanol-ethanol mixed solvent is added for the uniformity of the glass, and in order to avoid the probability of bubble generation in the glass, multi-step drying is carried out to remove various water one by one.
Finally, we sprayed 21.5% KNO3The solution chemically toughens the bendable light and thin glass, and utilizes the difference of atomic radiuses of potassium ions and sodium ions to cause the matrix to be sprayed and stretched, so that the rigidity is increased. The specific process comprises the following steps: the spraying method is used for uniform exchange, concentration of potassium ions is prevented, reverse diffusion is formed, and stress is not uniform. At the same time, to KNO3Flowing outwards, we take advantage of the nano-Al released in the resin film2O3Induce promotion of ion exchange because potassium ions will follow nano-Al2O3Surface movement, and due to the nano Al in the preparation process of the bendable glass2O3The inward diffusion increases the depth of the potassium ion exchange, increasing the strength of the glass.
Compared with the prior art, the invention has the following beneficial effects: (1) by using silanol group and nano Al2O3Hydrogen bonding force between the Al and the Al2O3The transparent flexible resin film is embedded in a fine network structure formed by crosslinking of sulfur-containing hyperbranched polysilane and thiol silicone resin, is obtained by ultraviolet curing, and can effectively absorb impact and prevent cracks from generating by taking the transparent flexible resin film as a substrate; (2) with K3PO4For cosolvent, preparing fusible glass by thermal fusionThe preparation process comprises the steps of firstly, effectively enhancing the adhesive force between the resin film and the meltable glass, and inhibiting the generation and the diffusion of cracks; the second release of nano Al2O3One part of the glass enters the glass to fill the gap and enhance the strength of the glass; one part of the water is left on the surface of the glass to promote the chemical exchange of sodium ions and potassium ions, strengthen the toughening effect and increase the wear resistance of the glass. (3) By means of a spraying method, the exchange process of potassium ions and sodium ions is homogenized, the problems of reverse diffusion, uneven stress and the like caused by concentration of potassium ions at a certain point are avoided, and the quality of bendable light and thin toughened glass is improved; with the aid of internal nano Al2O3The exchange depth is increased, and the compressive strength is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
s1, preparing a glass material:
weighing Pb3O4、B2O3、SiO2Ultrasonically dispersing in deionized water to obtain a suspension without dust; transferring to a vacuum box, drying at 80 deg.C for 3h, removing free water to obtain agglomerated block, ball milling, and sieving with 200 mesh sieve; placing the obtained powder in an atmosphere furnace, drying for 30 minutes at the set temperature of 300 ℃, and removing capillary water and crystal water; taking out, adding K3PO4Uniformly mixing, filling the mixture into a carbon film, stirring and melting the mixture by using a tungsten rod, and setting the reaction temperature to 750 ℃ for reaction for 30 minutes; cooling to 400 ℃ at a cooling rate of 15 ℃/min, and then slowly cooling to room temperature at a cooling rate of 2 ℃/min; pulverizing the obtained glass into powder smaller than 100 μm, adding dispersion medium methanol-ethanol mixed solution, grinding and dispersing with mixed ZrO balls at rotation speed of 240rmp for 16 hr, and sieving with 400 mesh nylon sieveSieving with a screen to obtain a glass material, and sealing for later use;
s2 preparation of resin material:
(1) stirring and dispersing 0.75mol of weighed magnesium powder and one particle of iodine in 300mL of diethyl ether in sequence; keeping the temperature at 0 ℃, adding 0.63mol of 3-bromopropylene and 270mL of diethyl ether into the mixed solution, and reacting for 120 minutes; adding 0.145mol of 3- (trimethyloxysilyl) -1-propyl mercaptan and 250mL of ether solvent, stirring at room temperature for 16 hours, adding methanol to terminate the reaction, filtering, and drying in vacuum to obtain a crude product of allyl triisopropyl silane; setting the reaction temperature at 120 ℃ under the pressure of 2.67kPa, and carrying out vacuum distillation to obtain purified colorless transparent liquid; initiating mercaptan-alkene click reaction under the conditions that the laser wavelength is 365nm and the power is 1000W, wherein the reaction time is 30 seconds, and obtaining sulfur-containing hyperbranched polycarbosilane for later use;
(2) weighing thiol silicone resin and nano Al2O3Mixing the hyperbranched polycarbosilane with the prepared hyperbranched polycarbosilane at a set rotating speed of 800-1000 rmp at a high speed to obtain a resin material, and sealing for later use;
s3, preparing bendable light and thin toughened glass:
(1) placing the carbon film on a rotating disc, rotating at 3000rmp, and spraying resin material on the carbon film in a criss-cross manner, wherein the size of a spray gun is 80 μm; setting the laser wavelength to 365nm, the laser power to 1000W, the distance between a light source and the carbon film to be 20cm, and performing ultraviolet curing to form a transparent flexible resin film I;
(2) rotating the transparent flexible resin film I serving as a substrate at the rotating speed of 4000rmp, and spraying the glass material in the step S1 on the transparent flexible resin film I in a criss-cross manner, wherein the size of a spray gun is 80 mu m; spraying a resin material on the glass material in the mode in the step (1), and performing ultraviolet curing to form a transparent flexible resin film II to obtain a composite glass substrate;
(3) placing the composite glass substrate in an atmosphere furnace, drying for 2 hours at the set temperature of 80 ℃, heating to 250 ℃ at the speed of 5 ℃/min, reacting for 30 minutes, completely removing the dispersion medium, and continuously heating to 410 ℃ for vitrification to obtain bendable light and thin glass;
(4) increased by chemical strengtheningThe glass is rigid, and 21.5 percent KNO is sprayed on the surface of the bendable light and thin glass3The size of the spray gun is 10 mu m, the temperature of the bendable light and thin glass is kept at 130 ℃ in the spraying process, and the spraying is carried out for 3 times in a circulating way; transferring the glass to an atmosphere furnace, setting the heat treatment temperature and treating for 0.5 hour to obtain the bendable light and thin toughened glass.
In this example, the meltable glass feedstock comprises the following ingredients: by weight, Pb3O450 parts of B2O315 portions of Na2O10 parts, SiO28 parts of, K3PO45 parts of a mixture; nano Al2O3The grain diameter is 5 nm; the thickness of the transparent flexible resin film I and the thickness of the transparent flexible resin film II are both 0.05 mm; the heat treatment temperature is 350 ℃; the thickness of the glass material was 0.75 mm.
Example 2:
s1, preparing a glass material:
weighing Pb3O4、B2O3、SiO2Ultrasonically dispersing in deionized water to obtain a suspension without dust; transferring to a vacuum box, drying at 100 deg.C for 3h, removing free water to obtain agglomerated block, ball milling, and sieving with 400 mesh sieve; placing the obtained powder in an atmosphere furnace, drying for 30 minutes at the set temperature of 400 ℃, and removing capillary water and crystal water; taking out, adding K3PO4Uniformly mixing, filling the mixture into a carbon film, stirring and melting the mixture by using a tungsten rod, and setting the reaction temperature to 750 ℃ for reaction for 30 minutes; cooling to 410 deg.C at a rate of 15 deg.C/min, and slowly cooling to room temperature at a rate of 2 deg.C/min; crushing the obtained glass into powder with the particle size of less than 100 microns, adding a dispersion medium methanol-ethanol mixed solution, grinding and dispersing by using mixed ZrO balls, setting the rotating speed to be 260rmp, carrying out ball milling for 16 hours, sieving by using a 400-mesh nylon screen to obtain a glass material, and sealing for later use;
s2 preparation of resin material:
(1) stirring and dispersing 0.75mol of weighed magnesium powder and one particle of iodine in 300mL of diethyl ether in sequence; keeping the temperature at 5 ℃, adding 0.63mol of 3-bromopropylene and 270mL of diethyl ether into the mixed solution, and reacting for 120 minutes; adding 0.145mol of 3- (trimethyloxysilyl) -1-propyl mercaptan and 250mL of diethyl ether solvent, stirring at room temperature for 22 hours, adding methanol to terminate the reaction, filtering, and drying in vacuum to obtain a crude product of allyl triisopropyl silane; setting the reaction temperature at 150 ℃ under the pressure of 2.67kPa, and carrying out vacuum distillation to obtain purified colorless transparent liquid; initiating mercaptan-alkene click reaction under the conditions that the laser wavelength is 365nm and the power is 1000W, wherein the reaction time is 30 seconds, and obtaining sulfur-containing hyperbranched polycarbosilane for later use;
(2) weighing thiol silicone resin and nano Al2O3Mixing the resin with the prepared hyperbranched polycarbosilane at a set rotating speed of 1000rmp at a high speed to obtain a resin material, and sealing for later use;
s3, preparing bendable light and thin toughened glass:
(1) placing the carbon film on a rotating disc, rotating at 3000rmp, and spraying resin material on the carbon film in a criss-cross manner, wherein the size of a spray gun is 100 mu m; setting the laser wavelength to 365nm, the laser power to 1000W, the distance between a light source and the carbon film to be 20cm, and performing ultraviolet curing to form a transparent flexible resin film I;
(2) rotating the transparent flexible resin film I serving as a substrate at the rotating speed of 4000rmp, and spraying the glass material in the step S1 on the transparent flexible resin film I in a criss-cross manner, wherein the size of a spray gun is 100 mu m; spraying a resin material on the glass material in the mode in the step (1), and performing ultraviolet curing to form a transparent flexible resin film II to obtain a composite glass substrate;
(3) placing the composite glass substrate in an atmosphere furnace, drying for 2 hours at the set temperature of 80 ℃, heating to 250 ℃ at the speed of 5 ℃/min, reacting for 30 minutes, completely removing the dispersion medium, and continuously heating to 480 ℃ for vitrification to obtain bendable light and thin glass;
(4) the rigidity of the glass is increased by a chemical strengthening method, and 21.5 percent KNO is sprayed on the surface of the bendable light and thin glass3The size of the spray gun is 50 mu m, the temperature of the bendable light and thin glass is kept at 130 ℃ in the spraying process, and the spraying is carried out for 3 times in a circulating way; transferring the glass to an atmosphere furnace, setting the heat treatment temperature and treating for 1.5 hours to obtain the bendable light and thin toughened glass.
This exampleWherein the meltable glass feedstock comprises the following ingredients: by weight, Pb3O460 portions of B2O320 portions of Na2O15 parts, SiO216 parts of, K3PO48 parts of a mixture; nano Al2O3The grain diameter is 100 nm; the thickness of the transparent flexible resin film I and the thickness of the transparent flexible resin film II are both 0.08 mm; the heat treatment temperature is 400 ℃; the thickness of the glass material was 0.95 mm.
Example 3:
s1, preparing a glass material:
weighing Pb3O4、B2O3、SiO2Ultrasonically dispersing in deionized water to obtain a suspension without dust; transferring to a vacuum box, drying at 90 deg.C for 3h, removing free water to obtain agglomerated block, ball milling, and sieving with 300 mesh sieve; placing the obtained powder in an atmosphere furnace, drying for 30 minutes at the set temperature of 350 ℃, and removing capillary water and crystal water; taking out, adding K3PO4Uniformly mixing, filling the mixture into a carbon film, stirring and melting the mixture by using a tungsten rod, and setting the reaction temperature to 750 ℃ for reaction for 30 minutes; cooling to 405 deg.C at a rate of 15 deg.C/min, and slowly cooling to room temperature at a rate of 2 deg.C/min; crushing the obtained glass into powder with the particle size of less than 100 microns, adding a dispersion medium methanol-ethanol mixed solution, grinding and dispersing by using mixed ZrO balls, setting the rotating speed to be 250rmp, carrying out ball milling for 16 hours, sieving by using a 400-mesh nylon screen to obtain a glass material, and sealing for later use;
s2 preparation of resin material:
(1) stirring and dispersing 0.75mol of weighed magnesium powder and one particle of iodine in 300mL of diethyl ether in sequence; keeping the temperature at 0-5 ℃, adding 0.63mol of 3-bromopropylene and 270mL of diethyl ether into the mixed solution, and reacting for 120 minutes; adding 0.145mol of 3- (trimethyloxysilyl) -1-propyl mercaptan and 250mL of diethyl ether solvent, stirring at room temperature for 27 hours, adding methanol to terminate the reaction, filtering, and drying in vacuum to obtain a crude product of allyl triisopropyl silane; setting the reaction temperature at 135 ℃ under the pressure of 2.67kPa, and carrying out vacuum distillation to obtain purified colorless transparent liquid; initiating mercaptan-alkene click reaction under the conditions that the laser wavelength is 365nm and the power is 1000W, wherein the reaction time is 30 seconds, and obtaining sulfur-containing hyperbranched polycarbosilane for later use;
(2) weighing thiol silicone resin and nano Al2O3Mixing the resin with the prepared hyperbranched polycarbosilane at a set rotating speed of 900rmp at a high speed to obtain a resin material, and sealing for later use;
s3, preparing bendable light and thin toughened glass:
(1) placing the carbon film on a rotating disc, rotating at 3000rmp, and spraying resin material on the carbon film in a criss-cross manner, wherein the size of a spray gun is 90 μm; setting the laser wavelength to 365nm, the laser power to 1000W, the distance between a light source and the carbon film to be 20cm, and performing ultraviolet curing to form a transparent flexible resin film I;
(2) rotating the transparent flexible resin film I serving as a substrate at the rotating speed of 4000rmp, and spraying the glass material in the step S1 on the transparent flexible resin film I in a criss-cross manner, wherein the size of a spray gun is 90 mu m; spraying a resin material on the glass material in the mode in the step (1), and performing ultraviolet curing to form a transparent flexible resin film II to obtain a composite glass substrate;
(3) placing the composite glass substrate in an atmosphere furnace, drying for 2 hours at the set temperature of 80 ℃, heating to 250 ℃ at the speed of 5 ℃/min, reacting for 30 minutes, completely removing the dispersion medium, and continuously heating to 450 ℃ for vitrification to obtain bendable light and thin glass;
(4) the rigidity of the glass is increased by a chemical strengthening method, and 21.5 percent KNO is sprayed on the surface of the bendable light and thin glass3The size of the spray gun is 30 mu m, the temperature of the bendable light and thin glass is kept at 130 ℃ in the spraying process, and the spraying is carried out for 3 times in a circulating way; transferring the glass to an atmosphere furnace, setting the heat treatment temperature and treating for 3 hours to obtain the bendable light and thin toughened glass.
In this example, the meltable glass feedstock comprises the following ingredients: by weight, Pb3O455 parts of B2O318 portions of Na2O18 parts, SiO212 parts of, K3PO46 parts of (1); nano Al2O3The grain diameter is 50 nm; the thicknesses of the transparent flexible resin film I and the transparent flexible resin film II are both0.07 mm; the heat treatment temperature is 375 ℃; the thickness of the glass material is 0.85 mm.
Example 4:
s1 preparation of resin material:
(1) stirring and dispersing 0.75mol of weighed magnesium powder and one particle of iodine in 300mL of diethyl ether in sequence; keeping the temperature at 5 ℃, adding 0.63mol of 3-bromopropylene and 270mL of diethyl ether into the mixed solution, and reacting for 120 minutes; adding 0.145mol of 3- (trimethyloxysilyl) -1-propyl mercaptan and 250mL of diethyl ether solvent, stirring at room temperature for 22 hours, adding methanol to terminate the reaction, filtering, and drying in vacuum to obtain a crude product of allyl triisopropyl silane; setting the reaction temperature at 150 ℃ under the pressure of 2.67kPa, and carrying out vacuum distillation to obtain purified colorless transparent liquid; initiating mercaptan-alkene click reaction under the conditions that the laser wavelength is 365nm and the power is 1000W, wherein the reaction time is 30 seconds, and obtaining sulfur-containing hyperbranched polycarbosilane for later use;
(2) weighing thiol silicone resin and nano Al2O3Mixing the hyperbranched polycarbosilane with the prepared hyperbranched polycarbosilane at a set rotating speed of 800-1000 rmp at a high speed to obtain a resin material, and sealing for later use;
s2, preparing a glass material:
weighing Pb3O4、B2O3、SiO2Ultrasonically dispersing in deionized water to obtain a suspension without dust; transferring to a vacuum box, drying at 100 deg.C for 3h, removing free water to obtain agglomerated block, ball milling, and sieving with 400 mesh sieve; placing the obtained powder in an atmosphere furnace, drying for 30 minutes at the set temperature of 400 ℃, and removing capillary water and crystal water; taking out, adding K3PO4Uniformly mixing, filling the mixture into a carbon film, stirring and melting the mixture by using a tungsten rod, and setting the reaction temperature to 750 ℃ for reaction for 30 minutes; cooling to 410 deg.C at a rate of 15 deg.C/min, and slowly cooling to room temperature at a rate of 2 deg.C/min; obtaining a glass substrate;
s3, preparing bendable light and thin toughened glass:
(1) etching a glass substrate by using a strong alkaline solution, placing the glass substrate on a rotating disc, rotating at the rotating speed of 3000rmp, and spraying a resin material on the surface of the glass substrate in a criss-cross manner, wherein the size of a spray gun is 100 mu m; setting the laser wavelength to 365nm, the laser power to 1000W, the distance between a light source and the carbon film to be 20cm, and performing ultraviolet curing on the surface of the carbon film to form a transparent flexible resin film I and a transparent flexible resin film II to obtain a composite glass substrate;
(2) the rigidity of the glass is increased by a chemical strengthening method, and 21.5 percent KNO is sprayed on the surface of the composite glass substrate3The size of the spray gun is 50 mu m, the temperature of the bendable light and thin glass is kept at 130 ℃ in the spraying process, and the spraying is carried out for 3 times in a circulating way; transferring the glass to an atmosphere furnace, setting the heat treatment temperature and treating for 1.5 hours to obtain the bendable light and thin toughened glass.
In this example, glass was used as a substrate, and chemical etching was performed to thin the glass and then a transparent flexible resin film was applied. The meltable glass raw material comprises the following components: by weight, Pb3O460 portions of B2O320 portions of Na2O15 parts, SiO216 parts of, K3PO48 parts of a mixture; nano Al2O3The grain diameter is 100 nm; the thickness of the transparent flexible resin film I and the thickness of the transparent flexible resin film II are both 0.08 mm; the heat treatment temperature is 400 ℃; the thickness of the glass material was 0.95 mm.
Example 5: same as example 2, without adding nano Al2O3。
Example 6: same as example 2, without addition of cosolvent K3PO4。
Experiment: according to the bendable light and thin toughened glass prepared in the embodiments 1-6, the compressive strength of the glass is represented by referring to a GB/T6552-2005 standard method; referring to patent document CN201710555148.5, the flexibility index of glass is characterized by the ratio of tensile strength to vickers microhardness, and the larger the flexibility index is, the better the flexibility is, and the better the bendability of the glass is. The results were averaged 3 times and are shown in table 1:
table 1:
and (4) conclusion: from examples 1 to 3, it can be found that the compressive strength of all three bendable light and thin toughened glass is above 90MPa, and the flexibility index is above 0.24, indicating that: the prepared bendable light and thin toughened glass has excellent performance. Among them, the data of example 2 is most excellent in relation to the heat treatment temperature and time, and thus, it can be seen that the heat treatment temperature is preferably 400 ℃ and the time is preferably 1.5 hours.
Example 4 comparison of the data, which shows that the compressive strength is greatly reduced by using a chemical etching method to prepare glass first and then spraying a resin film for protection, because the glass prepared by the method lacks nano Al2O3The release mechanism reduces the strength enhancement of the glass interior and the mechanism of subsequent induction and promotion of potassium-sodium ion exchange strengthening of the glass.
Example 5 addition of no Al2O3The flexural light and thin toughened glass has reduced compressive strength and flexibility index, but is slightly better than that of comparative example 4 because of the lack of nano Al2O3The release mechanism is slightly better because the resin film is used as a substrate, condensation polymerization and decomposition reaction are carried out in the vitrification process, impact can be effectively absorbed, cracks are prevented from being generated, and the film is directly fired thin glass and has slightly stronger flexibility than that prepared by etching.
Example 6 without addition of Co-solvent K3PO4The bendable light and thin toughened glass has low compressive strength and flexibility index because the mobility is poor in the melting process, the vitrification temperature is close to but not reached, the toughened glass is in a semi-molten state, and gaps exist even if nano Al exists2O3Filling up the gap, the performance is still poor.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a frivolous toughened glass of flexible which characterized in that: the toughened glass comprises a transparent flexible resin film I, a transparent flexible resin film II and meltable glass arranged in the middle.
2. The bendable light and thin tempered glass according to claim 1, wherein: the meltable glass raw material comprises the following components: by weight, Pb3O450-60 parts of B2O315 to 20 portions of Na210-15 parts of O and SiO28 to 16 parts of K3PO45-8 parts.
3. The bendable light and thin tempered glass according to claim 1, wherein: the transparent flexible resin film is prepared from sulfur-containing hyperbranched polysilane, thiol silicon resin and nano Al2O3And (4) forming.
4. The bendable light and thin tempered glass according to claim 3, wherein: the nano Al2O3The particle size is 5 to 100 nm.
5. A preparation method of bendable light and thin toughened glass is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a glass material;
s2, preparing a resin material;
and S3, preparing bendable light and thin toughened glass.
6. The method for preparing bendable light and thin tempered glass according to claim 5, wherein the method comprises the following steps: the method comprises the following steps: the operation environment is an inert gas atmosphere;
s1, preparing a glass material:
weighing Pb3O4、B2O3、SiO2Ultrasonically dispersing in deionized water to obtain a suspension without dust; transferring the mixture into a vacuum box, drying the mixture for 3 hours at the set temperature of 80-100 ℃, removing free water to obtain an agglomerated block, performing ball milling, and sieving the agglomerated block by using a 200-400-mesh sieve; placing the obtained powder in an atmosphere furnace, drying for 30 minutes at the set temperature of 300-400 ℃, and removing capillary water and crystal water; taking out, adding K3PO4Uniformly mixing, filling the mixture into a carbon film, stirring and melting the mixture by using a tungsten rod, and setting the reaction temperature to 750 ℃ for reaction for 30 minutes; cooling to 400-410 ℃ at a cooling rate of 15 ℃/min, and then slowly cooling to room temperature at a cooling rate of 2 ℃/min; crushing the obtained glass into powder with the particle size of less than 100 microns, adding a dispersion medium methanol-ethanol mixed solution, grinding and dispersing by using mixed ZrO balls, setting the rotating speed to be 240-260 rmp, carrying out ball milling for 16 hours, sieving by using a 400-mesh nylon screen to obtain a glass material, and sealing for later use;
s2 preparation of resin material:
(1) stirring and dispersing the weighed magnesium powder and iodine in 3/8 ethyl ether in sequence; keeping the temperature at 0-5 ℃, adding 3-bromopropylene and 5/16 diethyl ether into the mixed solution, and reacting for 120 minutes; adding 3- (trimethyloxysilyl) -1-propyl mercaptan and 5/16 diethyl ether solvent, stirring at room temperature for 16-22 hours, adding methanol to terminate the reaction, filtering, and drying in vacuum to obtain a crude product of allyl triisopropyl silane; setting the reaction temperature to be 120-150 ℃ under the pressure of 2.67kPa, and carrying out vacuum distillation to obtain purified colorless transparent liquid; initiating mercaptan-alkene click reaction under the conditions that the laser wavelength is 365nm and the power is 1000W, wherein the reaction time is 30 seconds, and obtaining sulfur-containing hyperbranched polycarbosilane for later use;
(2) weighing thiol silicone resin and nano Al2O3Mixing the hyperbranched polycarbosilane with the prepared hyperbranched polycarbosilane at a set rotating speed of 800-1000 rmp at a high speed to obtain a resin material, and sealing for later use;
s3, preparing bendable light and thin toughened glass:
(1) placing the carbon film on a rotating disc, rotating at the rotating speed of 3000rmp, and spraying the resin material on the carbon film in a criss-cross mode, wherein the size of a spray gun is 80-100 mu m; setting the laser wavelength to 365nm, the laser power to 1000W, the distance between a light source and the carbon film to be 20cm, and performing ultraviolet curing to form a transparent flexible resin film I;
(2) rotating the transparent flexible resin film I serving as a substrate at a rotating speed of 4000rmp, and spraying the glass material in the step S1 on the transparent flexible resin film I in a criss-cross manner, wherein the size of a spray gun is 80-100 mu m; spraying a resin material on the glass material in the mode in the step (1), and performing ultraviolet curing to form a transparent flexible resin film II to obtain a composite glass substrate;
(3) placing the composite glass substrate in an atmosphere furnace, drying for 2 hours at the set temperature of 80 ℃, heating to 250 ℃ at the speed of 5 ℃/min, reacting for 30 minutes, completely removing the dispersion medium, and continuously heating to 410-480 ℃ for vitrification to obtain bendable light and thin glass;
(4) the rigidity of the glass is increased by a chemical strengthening method, and 21.5 percent KNO is sprayed on the surface of the bendable light and thin glass3The size of the spray gun is 10-50 mu m, the temperature of the bendable light and thin glass is kept at 130 ℃ in the spraying process, and the spraying is carried out for 3 times in a circulating way; and transferring the glass to an atmosphere furnace, setting the heat treatment temperature, and treating for 0.5-3 hours to obtain the bendable light and thin toughened glass.
7. The method for preparing bendable light and thin tempered glass according to claim 6, wherein the method comprises the following steps: in step S1, the mixed ZrO balls were obtained by mixing three different sizes of ZrO balls of 3mm, 5mm and 8mm at a ratio of 6:3: 1.
8. The method for preparing bendable light and thin tempered glass according to claim 6, wherein the method comprises the following steps: in step S3, the thickness of the transparent flexible resin film I and the thickness of the transparent flexible resin film II are both 0.05-0.08 mm.
9. The method for preparing bendable light and thin tempered glass according to claim 6, wherein the method comprises the following steps: in step S3, the thickness of the glass material is 0.75-0.95 mm.
10. The method for preparing bendable light and thin tempered glass according to claim 6, wherein the method comprises the following steps: in step S3, the heat treatment temperature is 350-400 ℃.
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| CN112452687B (en) | 2022-12-30 |
| CN115124242A (en) | 2022-09-30 |
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