CN110937810A - Mildew-proof glass and preparation method thereof - Google Patents
Mildew-proof glass and preparation method thereof Download PDFInfo
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- CN110937810A CN110937810A CN201911361304.XA CN201911361304A CN110937810A CN 110937810 A CN110937810 A CN 110937810A CN 201911361304 A CN201911361304 A CN 201911361304A CN 110937810 A CN110937810 A CN 110937810A
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- glass
- lithium
- mildew
- vanadium pentoxide
- proof
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- 239000011521 glass Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 238000004381 surface treatment Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 229920001992 poloxamer 407 Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000005329 float glass Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 239000006066 glass batch Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229940119177 germanium dioxide Drugs 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- 239000003513 alkali Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses mildew-proof glass and a preparation method thereof. The mildew-proof glass comprises the following components: SiO 2268～77％、CaO 5～12％、MgO 0～5％、Al2O30～3％、Na2O 10～18％、K2O 0～2％、WO30～1％、GeO20.05～2％、ZrO20.01-1% of lithium-containing mesoporous vanadium pentoxide and 1-3.5% of lithium-containing mesoporous vanadium pentoxide, wherein WO3+GeO2+ZrO20.5 to 3 percent. The mildew-proof glass is prepared by adding a certain amount of amphoteric metal oxide and lithium-containing mesoporous vanadium pentoxide into a glass body and adapting to a float glassThe glass production process finally enables the prepared glass to have excellent mildew-proof effect through sulfur dioxide surface treatment, and meets the requirement of high-end glass for realizing the mildew-proof for a super-long time.
Description
Technical Field
The invention belongs to the technical field of glass manufacturing, and particularly relates to mildew-proof glass and a preparation method thereof.
Background
The problem of the float glass mildewing in the processes of storage, transportation and deep processing is always a big problem in the glass industry. Float glass has poor resistance to mildew compared to other types of glass because float glass is a soda-lime-silicate glass in which Na is present2The content of O is about 15 percent. Na in the glass when the surface of the glass is corroded by water to form a static water film+With H in water-Exchange occurs, and the glass surface is gradually enriched to generate NaOH solution. The NaOH solution in turn dissolves and destroys the silicate network structure, so that the surface of the glass is microscopically uneven, and the phenomena of white spots, rainbow, devitrification and the like appear by visual observation, which is called 'glass mildewing'.
At present, the common glass mildew-proof methods at home and abroad mainly comprise the following methods: the method for adding the mildew-proof paper has a certain mildew-proof effect, but the effective mildew-proof period is short, and the acidic mildew-proof paper can generate paper lines and is not easy to clean when being stored for a certain period; secondly, a protective film coating method, wherein acidic mildew-proof materials such as formic acid, salicylic acid, adipic acid and other steam are used for sweeping the surface of the glass to form a protective film; thirdly, the sulfur dioxide fumigation method has the function of delaying the mildew to a certain extent, but has very limited function, can not solve the problem of mildew fundamentally and has short effective mildew-proof period; and fourthly, applying mildew-proof powder, namely forming a layer of isolating layer between the glass by adopting modes of electrostatic powder spraying, gas atomization powder spraying and the like, wherein the method can obtain a better mildew-proof effect only by strictly ensuring the even and sufficient spraying of the mildew-proof powder on the surface of the glass.
Chinese patent application publication No. CN 107162420 a discloses a nano mildewproof glass and a manufacturing method thereof, which inhibit the mildew of glass by adding components such as zinc oxide and copper chloride into a glass body to play a role of sterilization, and the prepared glass has a better mildewproof effect by replacing mildewproof powder with non-powdery mildewproof paint composed of nano titanium dioxide, nano silicon dioxide, nano metal additives and the like. However, the method requires spraying the nano-coating on the surface of the glass, and the process is relatively complex.
Disclosure of Invention
The invention aims to provide mildewproof glass and a preparation method thereof. According to the mildew-proof glass, a certain amount of amphoteric metal oxide and lithium-containing mesoporous vanadium pentoxide are added into a glass body, the production process of float glass is adapted, and finally, the surface treatment is carried out through sulfur dioxide, so that the prepared glass has an excellent mildew-proof effect, and the requirement of high-end glass for realizing the ultra-long-time mildew prevention is met.
The invention is realized by the following technical scheme:
the mildew-proof glass comprises the following components in percentage by weight: SiO 2268～77％、CaO 5～12％、MgO0～5％、Al2O30～3％、Na2O 10～18％、K2O 0～2％、WO30～1％、GeO20.05～2％、ZrO20.01-1% of lithium-containing mesoporous vanadium pentoxide and 1-3.5% of lithium-containing mesoporous vanadium pentoxide, wherein WO3+GeO2+ZrO20.5～3％。
Preferably, the mildew-proof glass comprises the following components in percentage by weight: SiO 2270～75％、CaO 8～10％、MgO 2～4％、Al2O30.5～1.5％、Na2O 10～14％、K2O 0.5～1％、WO30.1～0.5％、GeO20.5～1.5％、ZrO20.1-0.5% of lithium-containing mesoporous vanadium pentoxide and 1.5-3% of lithium-containing mesoporous vanadium pentoxide, wherein WO3+GeO2+ZrO21～2.5％。
Preferably, Li and V in the lithium-containing mesoporous vanadium pentoxide2O5The molar ratio of (A) to (B) is 1-3: 1.
Preferably, Li and V in the lithium-containing mesoporous vanadium pentoxide2O5Is 1: 1.
Preferably, the lithium-containing mesoporous vanadium pentoxide is prepared by the following steps:
(1) dissolving a triblock copolymer Pluronic F127 in an ethanol water solution at 35-40 ℃ to obtain a template solution;
(2) dissolving ammonium metavanadate and lithium nitrate in water, and stirring for dissolving to obtain V, Li-containing precursor solution;
(3) dropwise adding the V, Li-containing precursor solution obtained in the step (2) into the template solution obtained in the step (1), stirring while adding, adding ammonia water to adjust the pH value to 8-9, stirring and reacting at 35-40 ℃ for 12-24 h to obtain a suspension containing flocculent precipitates, then placing the mixed system into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting at 100-120 ℃ for 20-24 h to obtain a crystallized product; and filtering, washing, drying and calcining the crystallized product to obtain the lithium-containing mesoporous vanadium pentoxide.
In the preparation step of the lithium-containing mesoporous vanadium pentoxide, the volume ratio of ethanol to water in the ethanol aqueous solution is 2:1, and the mixing ratio of Pluronic F127 to the ethanol aqueous solution is 1g: 10-12 mL. The mixing molar ratio of the ammonium metavanadate, the lithium nitrate and the water is 2 (1-3) to 425; the dosage of the Pluronic F127 is 2-3 times of the total mass of the ammonium metavanadate and the lithium nitrate.
The calcination is to heat the mixture to 450-550 ℃ at the speed of 2 ℃/min in the air atmosphere, and to calcine the mixture for 4-6 hours at the temperature of 450-550 ℃.
The triblock copolymer Pluronic F127 has the molecular formula of EO106PO70EO106EO is ethylene oxide and PO is propylene oxide; average molecular weight 12600.
The method takes Pluronic F127 as a template agent, completely dissolves the Pluronic F127 in an ethanol water solution by water bath heating (35-40 ℃), and then adds V5+、Li+Stirring the precursor solution to V5+、Li+Uniformly distributing in an ethanol water solution of F127, and adding ammonia water to ensure that V is dissolved5+、Li+Forming a hydroxide; the F127 is rich in hydroxyl, so that the hydroxyl can be combined with the formed pre-oxide through hydrogen bond or condensation polymerization to form an inorganic-organic compound, further, the reaction is carried out for 20-24 hours at 100-120 ℃, so that the corresponding hydroxide is converted into the oxide, the crystal of the corresponding oxide is perfectly grown, and finally, the lithium-containing mesoporous vanadium pentoxide is obtained through the steps of filtering, washing, drying, calcining and the like.
The invention also provides a preparation method of the mildew-proof glass, which comprises the following steps: respectively weighing quartz sand, calcium carbonate, magnesium oxide, aluminum oxide, sodium carbonate, potassium carbonate, tungsten dioxide, germanium dioxide, zirconium dioxide and lithium-containing mesoporous vanadium pentoxide which are glass batch materials according to the amount of the glass oxide; the components of the glass batch are uniformly mixed, and the mixture is put into a float glass melting furnace for melting, clarification, forming and annealing, and then sulfur dioxide surface treatment is carried out to obtain the mildew-proof glass.
Preferably, the glass melting temperature is 1450-1475 ℃, the clarification temperature is 1510-1535 ℃, the molding temperature is 940-960 ℃, and the annealing temperature is 556-560 ℃. The sulfur dioxide surface treatment comprises the following specific steps: the glass plate enters the heat insulation box for continuous SO after being annealed2Surface treatment, the temperature in the heat preservation box is 535 toContinuously introducing SO at 550 DEG C2，SO2The flow velocity of (2) is 0.5 to 1.0m3/h。
The invention adds WO into the glass body3、GeO2、ZrO2The amphoteric meta-acidic metal oxide can effectively inhibit the glass from mildewing, and the W is6+、Ge4+、Zr4+The ionic radius is smaller than that of alkali metal ion Na+、K+The radius of the alkali-containing glass is that during the diffusion process of the mixed alkali glass, vacancies left by smaller ions can block the movement of large ions, thereby playing a blocking effect on the diffusion of alkali metal ions to the surface of the glass and inhibiting the alkali precipitation process on the surface of the glass to a certain extent. When the surface of the glass is wet, hydrogen ions in water are exchanged with sodium ions in the glass to generate sodium hydroxide, the amphoteric meta-acid metal oxide reacts with the sodium hydroxide to generate corresponding metal salt, and the metal salt serving as a protective layer on the surface of the glass can inhibit the sodium hydroxide from permeating into the glass and prevent OH-Reacts with the "oxygen bridge" structure in the glass "skeleton" resulting in erosion of the glass network. In which WO3Also has the characteristic of heat radiation blocking, GeO2Has the functions of high-temperature fluxing and glass melting acceleration, and ZrO2The strength of the glass can be improved, and the water resistance of the glass can be improved. Furthermore, the present inventors have found that by combining the above-mentioned WO3+GeO2+ZrO2The dosage is controlled within a certain range, preferably 0.5-3%, more preferably 1-2.5%, the optical band gap of the glass is reduced, the structure is more compact and complete, and the volume density, the oxygen atom stacking density and the bending strength of the glass are increased.
According to the invention, the lithium-containing mesoporous vanadium pentoxide is added into the glass body, so that the mildew-proof effect of the glass is further enhanced. The vanadium pentoxide has an open two-dimensional layered structure, V is positioned in the middle of a square pyramid surrounded by 5O atoms, and the V atoms and the 5O atoms form 5V-O bonds, and the structure of the vanadium pentoxide can be regarded as VO4The tetrahedral units are combined into a chain through bridge oxygen, the chain and the chain form a saw-tooth layered arrangement structure through the action of double bond oxygen and V on the next chain, the structure and the silicon-oxygen tetrahedron are easily combined into a bond, and the glass is addedThe average number of the bridge oxygen in the glass network structure improves the chemical stability of the glass. Vanadium pentoxide is an amphoteric, meta-acidic metal oxide which cooperates with the above-mentioned WO3、GeO2、ZrO2Exhibits excellent antifungal effect, has weak van der Waals force or hydrogen bond between layers, and can insert metallic Li+At high temperature, oxygen released by vanadium pentoxide can promote glass clarification, and Li is formed2O promotes glass melting and homogenization, Li+The ionic radius is the smallest in alkali metal, and the ionic radius is easy to enter a glass structure network, so that the surface gloss of the glass can be improved, and the strength of the glass can be enhanced; li+The bonding force with O atoms is stronger than that of Na+When the glass is wet, H+With Li in glass+The lithium hydroxide is stronger in stability and weaker in alkalinity than the sodium hydroxide, and further weathering of the sodium hydroxide lye on the glass can be effectively delayed.
The invention carries out SO after annealing the glass plate2Surface treatment, on the one hand, prolongs the annealing time and improves the compactness and chemical stability of the glass by improving the annealing quality, and on the other hand, SO2And Na2O undergoes dealkalization chemical reaction to generate Na2SO4Na for activating the surface layer of glass+Reduced content of Na in the surface layer2SO4Also has a certain protection effect, thereby delaying the glass from mildewing.
Compared with the prior art, the invention has the following beneficial effects: according to the mildew-proof glass, a certain amount of amphoteric metal oxide and lithium-containing mesoporous vanadium pentoxide are added into the glass body, so that the prepared glass has an excellent mildew-proof effect; the glass batch adapts to a float glass production process, is simple in preparation process, has the general excellent performance of the traditional float glass, overcomes the defect that the float glass is easy to mildew, and compared with the existing mildew-proof measures, the glass batch provided by the invention starts from a glass body, fundamentally solves the problem of glass mildew, and meets the requirement of realizing the ultra-long-time mildew-proof of high-end glass.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
The preparation of the lithium-containing mesoporous vanadium pentoxide in the embodiment comprises the following steps:
(1) 606g of triblock copolymer Pluronic F127 is dissolved in an ethanol aqueous solution (the volume ratio of ethanol to water is 2:1) at 35 ℃, and the mixing ratio of the Pluronic F127 to the ethanol aqueous solution is 1g:10mL, so as to obtain a template solution;
(2) 234g of ammonium metavanadate and 69g of lithium nitrate are dissolved in 7650g of water, and the solution is stirred and dissolved to obtain V, Li-containing precursor solution;
(3) dropwise adding the V, Li-containing precursor solution obtained in the step (2) into the template solution obtained in the step (1), stirring while adding, adding ammonia water to adjust the pH value to 9, stirring and reacting at 40 ℃ for 12 hours to obtain suspension containing flocculent precipitates, then placing the mixed system into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting at 120 ℃ for 20 hours to obtain a crystallized product; filtering the crystallized product, washing the precipitate with water, drying the precipitate for 2h at 100 ℃, finally heating the precipitate to 550 ℃ at the speed of 2 ℃/min in the air atmosphere, and roasting the precipitate for 4h at 550 ℃ to obtain the lithium-containing mesoporous vanadium pentoxide.
Example 2
The preparation of the lithium-containing mesoporous vanadium pentoxide in the embodiment comprises the following steps:
(1) 1116g of triblock copolymer Pluronic F127 is dissolved in an ethanol aqueous solution (the volume ratio of ethanol to water is 2:1) at 40 ℃, and the mixing ratio of the Pluronic F127 to the ethanol aqueous solution is 1g:12mL, so as to obtain a template solution;
(2) 234g of ammonium metavanadate and 138g of lithium nitrate are dissolved in 7650g of water, and the solution is stirred and dissolved to obtain V, Li-containing precursor solution;
(3) dropwise adding the V, Li-containing precursor solution obtained in the step (2) into the template solution obtained in the step (1), stirring while adding, adding ammonia water to adjust the pH value to 8, stirring and reacting for 24 hours at 35 ℃ to obtain suspension containing flocculent precipitates, then placing the mixed system into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 100 ℃ to obtain a crystallized product; filtering crystallized products, washing precipitates with water, drying for 2h at 100 ℃, finally heating to 450 ℃ at the speed of 2 ℃/min in the air atmosphere, and roasting for 6h at 450 ℃ to obtain the lithium-containing mesoporous vanadium pentoxide.
Examples 3 to 8
The preparation of the mildewproof glass of the present examples 3 to 8 comprises the following components in percentage by weight:
the preparation method comprises the following steps: respectively weighing quartz sand, calcium carbonate, magnesium oxide, aluminum oxide, sodium carbonate, potassium carbonate, tungsten dioxide, germanium dioxide, zirconium dioxide and lithium-containing mesoporous vanadium pentoxide which are glass batch materials according to the amount of the glass oxide shown in the table; uniformly mixing all components of a glass batch, putting the mixture into a float glass melting furnace for high-temperature melting to form a solution, wherein the melting temperature is 1450 ℃, the solution flows into a working pool after being clarified and homogenized, the clarification and homogenization temperature is 1510 ℃, the solution enters a forming tin bath from a launder in the working pool to form a strip-shaped continuous glass plate, the forming temperature of the glass plate in the tin bath is 940 ℃, the strip-shaped continuous glass plate is sent into an annealing kiln from the tin bath for annealing treatment, the annealing temperature is 556 ℃, the annealed glass plate enters an insulation box for sulfur dioxide surface treatment, the temperature in the insulation box is 535 ℃, and SO is continuously introduced into the insulation box for sulfur dioxide surface treatment2，SO2Flow velocity of 0.5m3And h, obtaining the mildew-proof glass.
Comparative example 1
Comparative example 1 a mould proof glass was prepared comprising the following components in weight percent: SiO 2273％、CaO 8.5％、MgO 3％、Al2O31％、Na2O 12％、K20.5 percent of O and 2 percent of lithium-containing mesoporous vanadium pentoxide.
Comparative example 1 is compared with example 3 with the difference that no WO is present3+GeO2+ZrO2。
The preparation procedure is as in example 1.
Comparative example 2
Comparative example 2 preparation of a mold-proof glass comprising the following weightsThe components in percentage by weight are as follows: SiO 2273％、CaO 8.5％、MgO 3％、Al2O31％、Na2O 12％、K2O 0.5％、WO30.5％、GeO21% and ZrO20.5％。
Comparative example 2 is compared with example 3 except that lithium-containing mesoporous vanadium pentoxide is not contained.
The preparation procedure is as in example 1.
Comparative example 3
Comparative example 3 a mould proof glass was prepared comprising the following components in weight percent: SiO 2272.5％、CaO8.5％、MgO 3％、Al2O31％、Na2O 12％、K2O 0.5％、ZrO20.5 percent and lithium-containing mesoporous vanadium pentoxide 2 percent.
Comparative example 3 is compared with example 3 with the difference that no WO is included3And GeO2。
The preparation procedure is as in example 1.
Comparative example 4
Comparative example 4 a mould proof glass was prepared comprising the following components in weight percent: SiO 2272.5％、CaO8.5％、MgO 3％、Al2O31％、Na2O 12％、K2O 0.5％、WO30.5 percent and lithium-containing mesoporous vanadium pentoxide 2 percent.
Comparative example 4 compares with example 3 with the difference that no GeO is present2And ZrO2。
The preparation procedure is as in example 1.
Comparative example 5
Comparative example 5 a mould proof glass was prepared comprising the following components in weight percent: SiO 2272％、CaO 8.5％、MgO 3％、Al2O31％、Na2O 12％、K2O 0.5％、WO30.5％、ZrO20.5% and V2O52％。
Comparative example 5 compares with example 3 with the difference that no GeO is present2And with V2O5Replacing lithium-containing mesoporous vanadium pentoxide.
The preparation procedure is as in example 1.
Comparative example 6
Comparative example 6 a mould proof glass was prepared comprising the following components in weight percent: SiO 2274％、CaO 8.5％、MgO 3％、Al2O31％、Na2O 12％、K2O 0.5％、WO30.5% and ZrO20.5％。
Comparative example 6 is compared with example 3 with the difference that no GeO is present2And lithium-containing mesoporous vanadium pentoxide.
The preparation procedure is as in example 1.
Comparative example 7
Comparative example 7 a mould proof glass was prepared comprising the following components in weight percent: SiO 2275％、CaO 8.5％、MgO 3％、Al2O31％、Na2O12% and K2O 0.5％。
Comparative example 7 is compared with example 3 with the difference that no WO is present3、GeO2、ZrO2And lithium-containing mesoporous vanadium pentoxide.
The preparation procedure is as in example 1.
Test I, determination of glass anti-mildew Property
1. Test samples: examples 3 to 8 and comparative examples 1 to 7.
2. The test method comprises the following steps: dividing test samples into 13 groups, namely, 3-8 groups and 1-7 groups of examples and 1-7 groups, respectively, testing the groups by using the mildew-proof glass prepared in the 3-8 and 1-7 groups, respectively, testing 3 glass samples in each group, repeating the test for 3 times, placing the glass in a constant temperature and humidity box, setting the temperature to be 58 +/-2 ℃ and the relative humidity to be 95%, carrying out continuous tests in the constant temperature and humidity box, taking out the glass after 7 days, 14 days and 21 days respectively, observing the mildew condition on the surface of the glass under sunlight, and detecting the alkali precipitation amount (the size of the sample is 25.4 multiplied by 25.4mm) of each group of glass by using an atomic absorption spectrophotometer, wherein the concrete steps are as follows: drying the glass under infrared lamp, placing in 500mL beaker, soaking with 30mL deionized water for half an hour, and turning the glass over with stirring several times to keep each part of the glass all in and outWhen the ionized water contacts with the alkali, the precipitated alkali is dissolved in the water. Then the glass is taken out, the leachate from the beaker is transferred into a 100mL volumetric flask, the sample and the beaker are rinsed three times with deionized water, and all the rinsing solution flows into the volumetric flask, 5mL of buffer solution is added, and the solution is diluted to the scale. Buffer CsCl solution was used, and 3mL of 2000ppm CsCl was added to 50mL of the leachate. According to different varieties of precipitated alkali, different reference solutions, Na, are adopted2NaCl (spectral purity) and K for O2The O is diluted into a standard solution of 50ppm by KCl (spectral purity) prepared into a stock solution of 1000 ppm. During the determination, reference solutions of 0.2 ppm, 0.4 ppm, 0.6 ppm and 0.8ppm are prepared respectively according to different alkali precipitation amount values, and a standard curve is drawn.
Measuring R in the leaching solution by using an atomic absorption spectrophotometer2The concentration of O, the amount of alkali precipitated per unit area (S) can be calculated by calculating the ratio of S to (CV)/A, S: amount of alkali precipitated per unit surface (R)2Oμg/cm2) C, C: leachate concentration (ppm), V: leachate volume (mL), a: full surface area (cm) of moldy glass2)。
3. And (3) testing results: see table 1.
TABLE 1 results of determination of the anti-mildew Properties of the glasses
The results show that the mildew-proof glass prepared in the embodiments 3-8 of the invention has better mildew-proof performance and better effect than the mildew-proof glass prepared in the comparative examples 1-7. In the strong mildew test, only the mildew-proof glasses prepared in the examples 5 and 8 have slight haze after 21 days of the test, the mildew-proof glasses prepared in the other examples 3-4 and 6-7 have no obvious change, and the alkali-separating amount of the glasses in each test group is consistent with the appearance change trend and the mildew degree of the glasses, and the larger the alkali-separating amount is, the more serious the mildew degree of the glasses is. The mildew-proof glass has small alkali precipitation amount in a strengthening mildew test, and is not easy to mildew.
Test II, determination of Long-term glass resistance to mildew
The mold-proof glasses obtained in example 3 and comparative examples 1 to 7 were stored at room temperature (25. + -. 2 ℃ C.), humidity (relative humidity 60. + -. 10 ℃ C.), shade, and with contaminants such as scum, and the mold-formation time of the glasses was observed, and the results are shown in Table 2.
TABLE 2 Long-term anti-mildew Properties of the glasses
| Group of | Time (day) for mildew to occur |
| Example 3 | 748 |
| Comparative example 1 | 334 |
| Comparative example 2 | 371 |
| Comparative example 3 | 420 |
| Comparative example 4 | 447 |
| Comparative example 5 | 480 |
| Comparative example 6 | 345 |
| Comparative example 7 | 226 |
The result shows that the mildew-proof glass prepared in the embodiment 3 of the invention has long-acting mildew-proof effect, and the mildew-proof glass can be stored in a severe and easily mildewed environment for more than 2 years, and the effect is better than that of the mildew-proof glass prepared in the comparative examples 1-7.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. The mildew-proof glass is characterized by comprising the following components in percentage by weight: SiO 2268～77％、CaO 5～12％、MgO 0～5％、Al2O30～3％、Na2O 10～18％、K2O 0～2％、WO30～1％、GeO20.05～2％、ZrO20.01-1% of lithium-containing mesoporous vanadium pentoxide and 1-3.5% of lithium-containing mesoporous vanadium pentoxide, wherein WO3+GeO2+ZrO20.5～3％。
2. The mold-proof glass according to claim 1, comprising the following components in percentage by weight: SiO 2270～75％、CaO 8～10％、MgO 2～4％、Al2O30.5～1.5％、Na2O 10～14％、K2O 0.5～1％、WO30.1～0.5％、GeO20.5～1.5％、ZrO20.1-0.5% of lithium-containing mesoporous vanadium pentoxide and 1.5-3% of lithium-containing mesoporous vanadium pentoxide, wherein WO3+GeO2+ZrO21～2.5％。
3. The mold-proof glass according to claim 1 or 2, wherein the lithium-containing medium isLi and V in porous vanadium pentoxide2O5The molar ratio of (A) to (B) is 1-3: 1.
4. The mold-proof glass according to claim 3, wherein Li and V in the lithium-containing mesoporous vanadium pentoxide2O5Is 1: 1.
5. The mold-proof glass according to claim 4, wherein the preparation of the lithium-containing mesoporous vanadium pentoxide comprises the following steps:
(1) dissolving a triblock copolymer Pluronic F127 in an ethanol water solution at 35-40 ℃ to obtain a template solution;
(2) dissolving ammonium metavanadate and lithium nitrate in water, and stirring for dissolving to obtain V, Li-containing precursor solution;
(3) dropwise adding the V, Li-containing precursor solution obtained in the step (2) into the template solution obtained in the step (1), stirring while adding, adding ammonia water to adjust the pH value to 8-9, stirring and reacting at 35-40 ℃ for 12-24 h to obtain a suspension containing flocculent precipitates, then placing the mixed system into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting at 100-120 ℃ for 20-24 h to obtain a crystallized product; and filtering, washing, drying and calcining the crystallized product to obtain the lithium-containing mesoporous vanadium pentoxide.
6. The mildew-proof glass according to claim 5, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 2:1, and the mixing ratio of Pluronic F127 to the ethanol aqueous solution is 1g: 10-12 mL.
7. The mildew-proof glass according to claim 5, wherein the mixing molar ratio of the ammonium metavanadate, the lithium nitrate and the water is 2 (1-3): 425; the dosage of the Pluronic F127 is 2-3 times of the total mass of the ammonium metavanadate and the lithium nitrate.
8. A method of making a mildewproof glass according to any one of claims 1 to 7, comprising the steps of: respectively weighing quartz sand, calcium carbonate, magnesium oxide, aluminum oxide, sodium carbonate, potassium carbonate, tungsten dioxide, germanium dioxide, zirconium dioxide and lithium-containing mesoporous vanadium pentoxide as glass batch according to the amount of the glass oxide in claim 1; the components of the glass batch are uniformly mixed, and the mixture is put into a float glass melting furnace for melting, clarification, forming and annealing, and then sulfur dioxide surface treatment is carried out to obtain the mildew-proof glass.
9. The preparation method according to claim 8, wherein the glass melting temperature is 1450-1475 ℃, the fining temperature is 1510-1535 ℃, the forming temperature is 940-960 ℃, and the annealing temperature is 556-560 ℃.
10. The preparation method according to claim 8, wherein the sulfur dioxide surface treatment comprises the following specific steps: the glass plate enters the heat insulation box for continuous SO after being annealed2Surface treatment is carried out, the temperature in the heat preservation box is 535-550 ℃, and SO is continuously introduced2，SO2The flow velocity of (2) is 0.5 to 1.0m3/h。
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