CN113174148A - White pigment for self-cleaning external wall and preparation method thereof - Google Patents
White pigment for self-cleaning external wall and preparation method thereof Download PDFInfo
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- CN113174148A CN113174148A CN202110424307.4A CN202110424307A CN113174148A CN 113174148 A CN113174148 A CN 113174148A CN 202110424307 A CN202110424307 A CN 202110424307A CN 113174148 A CN113174148 A CN 113174148A
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- Prior art keywords
- titanium dioxide
- self
- silicon
- white pigment
- phosphorus
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- 238000004140 cleaning Methods 0.000 title claims abstract description 39
- 239000012463 white pigment Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000004408 titanium dioxide Substances 0.000 claims description 72
- 239000002002 slurry Substances 0.000 claims description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 46
- 229910052710 silicon Inorganic materials 0.000 claims description 46
- 239000010703 silicon Substances 0.000 claims description 46
- 239000011247 coating layer Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 42
- 239000010410 layer Substances 0.000 claims description 40
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 26
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 25
- MJYCNMNFXMMHDL-UHFFFAOYSA-N [P].[Si].[Ti] Chemical compound [P].[Si].[Ti] MJYCNMNFXMMHDL-UHFFFAOYSA-N 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 8
- 229910001679 gibbsite Inorganic materials 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 67
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 27
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 239000000049 pigment Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910021426 porous silicon Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 235000011008 sodium phosphates Nutrition 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3623—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/363—Drying, calcination
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a white pigment for a self-cleaning outer wall and a preparation method thereof. In the invention, TiO is mixed with2The pigment and the photocatalysis performance are effectively combined, the white pigment with the titanium white pigment performance and the self-cleaning capability of the coating film is developed,used for outdoor building coatings, can provide high whiteness, high hiding power and good self-cleaning performance.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide preparation, and particularly relates to a white pigment for a self-cleaning external wall and a preparation method thereof.
Background
The contradiction between rapid economic development and environmental tolerance is more and more prominent, haze prevention and control and treatment become more and more important, and the self-cleaning coating produced by transportation has self-cleaning capability in the use process, conforms to the energy-saving and environment-friendly concept of people in a large environment, and is widely applied to the industries of buildings, medical treatment, chemical industry and the like. Especially, the building outer wall coating has a self-cleaning function, so that the service life of the coating can be prolonged, and the coating is always as new.
Titanium dioxide (surface treatment is carried out on rutile type to obtain titanium dioxide) is an inorganic pigment with the highest refractive index, and high whiteness is shown due to the high refractive index, so that the titanium dioxide is widely applied to the fields of coating, papermaking, plastics, printing ink, chemical fiber, rubber and the like as an inorganic white pigment. The common coating titanium dioxide only has pigment performance, and other organic or inorganic photocatalytic substances are additionally added in the self-cleaning function, so that the coating prepared by the method has more added materials, and the requirements of system compatibility and material dispersibility on the preparation process and equipment are high.
The existing photocatalytic material has the following technical problems: the catalytic performance is good, the application system can cause the service life of the coating film to be greatly shortened, the catalytic performance is poor, and the requirement of the self-cleaning coating can not be met. In the invention, TiO is mixed with2The pigment and the photocatalysis performance are effectively combined, and the white pigment for the self-cleaning outer wall and the preparation method thereof are developed, wherein the white pigment has the titanium white pigment performance and simultaneously endows the coating film with the self-cleaning capability, so as to solve the technical problems.
Disclosure of Invention
The invention aims to provide a white pigment for a self-cleaning outer wall and a preparation method thereof to overcome the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
the white pigment for the self-cleaning outer wall comprises a titanium dioxide base material and an envelope layer positioned on the surface of the titanium dioxide base material, wherein the envelope layer sequentially comprises a silicon envelope layer, a titanium-silicon-phosphorus composite envelope layer and an aluminum envelope layer containing various crystal structures from inside to outside.
Preferably, the titanium-silicon-phosphorus composite coating layer is formed by simultaneously adding phosphorus-doped nano titanium dioxide, a silicon source and a pH regulator under the condition that the pH value is 7.0-8.0, wherein the adding amount of the phosphorus-doped nano titanium dioxide material is rutile TiO2The amount of the silicon source is 5.0-10.0% of that of the titanium dioxide base material, and the addition amount of the silicon source is SiO2The content of the titanium dioxide is 2.8-8.8% of that of the titanium dioxide base material.
Preferably, the aluminum coating layer is formed by adding alkaline aluminum salt and then adjusting the pH to 5.5-6.5 by using a pH regulator, wherein the adding amount of the aluminum salt is Al2O32.5-3.5% of the titanium dioxide base material; the various crystalline structures include amorphous, boehmite, and gibbsite crystalline forms.
The preparation method of the white pigment for the self-cleaning exterior wall comprises the following steps:
s1: adding a silicon source into the titanium dioxide-based material slurry to form a silicon coating layer;
s2: then, adding nano titanium dioxide doped with phosphorus, a silicon source and a pH regulator into the slurry at the same time, and homogenizing to form a titanium-silicon-phosphorus composite coating layer;
s3: and adding aluminum salt and a pH regulator into the slurry, and homogenizing to form an aluminum coating layer containing various crystal structures.
Preferably, the phosphorus-doped nano titanium dioxide material is added in the amount of rutile type TiO in step S22The amount of the silicon source is 5.0-10.0% of that of the titanium dioxide base material, and the addition amount of the silicon source is SiO2The titanium dioxide base material accounts for 2.8-8.8%, the pH of the slurry is controlled to be 7.0-8.0, and then the titanium-silicon-phosphorus composite coating layer is formed through homogenization.
Preferably, the phosphorus-doped nano titanium dioxide is prepared by the following steps: taking metatitanic acid solution, adding phosphate, wherein the dosage of metatitanic acid and phosphate is TiO2And P2O5The mass ratio is (1-10): 1, the pH is adjusted to 10.0-12.5, the calcination is carried out at 350-550 ℃, and then the grinding is carried out to obtain the catalyst.
Preferably, the calcining time is 2.5-6.0 h, the nano slurry with the solid content of 45-50% is prepared after crushing, and the nano slurry is ground until no precipitate exists after being placed for more than 7 days; when the grinding fluid is used, the grinding fluid is diluted by 2-10 times and then ground again.
Preferably, the phosphorus-doped nano titanium dioxide, the silicon source and the pH regulator are added for 20-40 min, and the homogenization time is 30-40 min.
Preferably, in step S3, the aluminum salt is a basic aluminum salt, and after the basic aluminum salt is added, the pH is adjusted to 5.5-6.5 with a pH adjuster, and the aluminum-coated layer is formed by homogenization; the aluminum salt is added in an amount of Al2O3The content of the titanium dioxide is 2.5-3.5% of that of the titanium dioxide base material.
Preferably, the alkaline aluminum salt is sodium metaaluminate, and the pH regulator regulates the pH reduction gradient to be 0.1-0.5/min.
Compared with the prior art, the invention has the following advantages:
1. in the invention, TiO is mixed with2Pigments and photocatalystsThe performance is effectively combined, and the titanium white pigment performance is developed and the self-cleaning capability is simultaneously endowed to the coating;
2. the existing photocatalytic material has the technical problems that the catalytic performance is good, the application system can cause the service life of a coating film to be greatly shortened, the catalytic performance is poor, and the requirement of a self-cleaning coating cannot be met;
3. the invention coats a compact, uniform and continuous silicon coating layer on the innermost layer of titanium dioxide, and coats nano TiO with a proper amount of silicon on the second layer2Forming TiO with silicon as a skeleton2And a P-filled three-dimensional photocatalytic film layer, wherein the outermost layer is coated with an alumina film layer (containing amorphous boehmite, boehmite and gibbsite) with a plurality of crystal structures which are orderly arranged to form a multifunctional aluminum film layer, so that high dispersion and chalking resistance are provided in the coating;
4. the titanium dioxide prepared by the invention is used for outdoor building coatings, and can provide high whiteness, high covering and self-cleaning performance.
Drawings
FIG. 1 is an electron microscope transmission test chart of a comparative sample;
FIG. 2 is an electron microscope transmission test chart of sample No. 1 obtained in example 1;
FIG. 3 is an electron microscope transmission test chart of sample No. 2 obtained in example 2;
FIGS. 4 to 5 are transmission electron micrographs of sample No. 3 obtained in example 3.
Detailed Description
The white pigment for the self-cleaning outer wall comprises a titanium dioxide base material and a coating layer positioned on the surface of the titanium dioxide base material, wherein the coating layer sequentially comprises a silicon coating layer, a titanium-silicon-phosphorus composite coating layer and an aluminum coating layer containing various crystal structures from inside to outside.
According to the white pigment for the self-cleaning outer wall, the inner core is titanium dioxide, and then the surface of the titanium dioxide is sequentially provided with a silicon coating layer, a titanium-silicon-phosphorus composite coating layer and an aluminum coating layer containing various crystal structures from inside to outside. Firstly, the innermost layer is coated with a silicon coating layer, so that direct irradiation of ultraviolet light on titanium dioxide particles on the inner layer can be prevented, the generation of photocatalytic reaction is avoided, the aging and degradation of a coating system are avoided, meanwhile, the contact between the titanium dioxide on the inner layer and a titanium-silicon-phosphorus composite coating layer with photocatalytic performance on the second layer can also be avoided, the formation of synergistic reaction is avoided, more active electrons and holes are generated, more free radicals are formed, the degradation of a matrix is increased, and from the overall effect, the compact silicon coating layer on the innermost layer completely and absolutely prevents the contact between the titanium dioxide and the titanium-silicon-phosphorus composite coating layer, and the resin, a coating system dispersing agent, a wetting agent and the like, so that the necessary pigment properties of the white pigment hue, the covering power, the weather resistance and the like for the self-cleaning exterior wall paint are ensured; the second layer is a three-dimensional photocatalytic film layer formed by titanium-silicon-phosphorus, wherein a silicon film layer of a porous framework provides a large number of micropores, so that the high-efficiency Ti-P doped photocatalytic nano material can be bonded with the porous silicon framework material through chemical activity bonding and is orderly filled in the porous silicon framework; on one hand, the porous silicon framework has high nano titanium capture rate and reduces the loss of nano titanium, and on the other hand, the porous silicon framework endows the nano Ti-P hybrid material with high dispersibility, thereby avoiding mutual crowding and reducing the photocatalytic efficiency; therefore, the titanium-silicon-phosphorus composite coating layer has high-efficiency photocatalytic activity and endows the pigment with good self-cleaning capability; the outermost layer is coated with an alumina film layer (containing amorphous, boehmite and gibbsite) with various crystal structures in ordered arrangement, the inner layer is formed by adsorbing amorphous alumina outside the titanium-silicon-phosphorus composite coating film layer, nano titanium dioxide is locked on the surface of particles to prevent the nano titanium dioxide from losing, the outer layer is formed with a boehmite and gibbsite alumina mixed film layer, and active hydroxyl groups on the surfaces of the boehmite and gibbsite alumina film layers endow the product with excellent dispersibility in a coating system.
Therefore, the present invention provides TiO2The pigment and the photocatalysis performance are effectively combined, and the white pigment which has the titanium white pigment performance and simultaneously endows the coating film with self-cleaning capability is developed and used for an outdoor building coating, and can provide high whiteness, high covering and good self-cleaning performance.
Preferably, the titanium-silicon-phosphorus composite coating layer is prepared by simultaneously adding phosphorus-doped nano titanium dioxideSilicon source and pH regulator at pH 7.0-8.0, and the nanometer titania material doped with phosphorus is rutile TiO2The amount of the silicon source is 5.0-10.0% of that of the titanium dioxide base material, and the amount of the silicon source is SiO2The content of the titanium dioxide is 2.8-8.8% of that of the titanium dioxide base material.
Preferably, the phosphorus-doped nano titanium dioxide is prepared by the following steps: taking metatitanic acid solution, adding phosphate, wherein the dosage of metatitanic acid and phosphate is TiO2And P2O5The mass ratio is (1-10): 1, the pH is adjusted to 10.0-12.5, the mixture is washed by water until the conductivity of the filtrate is less than 80 mus/cm, the mixture is calcined at 350-550 ℃, and then the mixture is crushed and ground to obtain the catalyst. The metatitanic acid and the phosphate are calcined together, and then the nano-scale phosphorus doped titanium dioxide is obtained after crushing and grinding.
Preferably, the calcining time is 2.5-6.0 hours, the nano slurry with the solid content of 45-50% is prepared after crushing, the nano slurry is fully ground until the nano slurry is placed for more than 7 days without precipitation, the grinding is generally carried out for 40-60 min, and if the precipitation is generated, the treatment is carried out again; when the grinding fluid is used, the grinding fluid is diluted by 2-10 times and then ground again.
Preferably, the aluminum coating layer is formed by adding alkaline aluminum salt and then adjusting the pH to 5.5-6.5 by using a pH regulator, wherein the adding amount of the aluminum salt is Al2O32.5-3.5% of the titanium dioxide base material; the various crystalline structures include amorphous, boehmite, and gibbsite crystalline forms.
The preparation method of the white pigment for the self-cleaning exterior wall comprises the following steps:
s1: adding a silicon source into the titanium dioxide-based material slurry to form a silicon coating layer;
s2: then, adding nano titanium dioxide doped with phosphorus, a silicon source and a pH regulator into the slurry at the same time, and homogenizing to form a titanium-silicon-phosphorus composite coating layer;
s3: and adding aluminum salt and a pH regulator into the slurry, and homogenizing to form an aluminum coating layer containing various crystal structures.
By the method, the titanium dioxide can be sequentially coated with the silicon coating layer, the titanium-silicon-phosphorus composite coating layer and the aluminum coating layer with various crystal structures, so that the white pigment with the titanium white pigment performance and the self-cleaning capability is obtained.
The titanium dioxide-based material slurry and the silicon coating layer can be prepared by a conventional method. The prepared titanium dioxide-based material slurry preferably has an average particle size D50 of less than 0.345 μm, a particle size distribution PSD of less than 1.50, and a concentration of TiO2The amount is 280-340 g/L, TiO2The content of the rutile type in the gold is more than 99.3 percent, and the temperature is 80-95 ℃. The titanium dioxide has proper particle size and concentration, and is beneficial to the subsequent silicon particle precipitation at a certain temperature, thereby obtaining the uniform and compact coating effect.
The invention provides a preferable preparation method of a silicon coating layer, which comprises the following steps:
adding silicon source (sodium silicate and/or potassium silicate) into the slurry in SiO2The content of the silicon source is 2.4-2.8% of that of the titanium dioxide base material, after the silicon source is added, the pH of the slurry is adjusted to 6.3-6.7 by adopting a pH regulator within 150-250 min, and the slurry is stirred and homogenized for 30-40 min. In the method, the silicon source is slowly deposited on the surface of titanium dioxide particles for a long time, which is beneficial to obtaining a compact silicon film layer.
Preferably, the nano titanium dioxide material doped with phosphorus in the step S2 is added in rutile type TiO2The amount of the silicon source is 5.0-10.0% of that of the titanium dioxide base material, and the amount of the silicon source is SiO2The content of the titanium dioxide is 2.8-8.8% of the titanium dioxide base material, the pH value of the slurry is controlled to be 7.0-8.0, and then the slurry is homogenized to form the titanium-silicon-phosphorus composite coating layer. Compared with the common titanium source, the phosphorus-doped nano-scale titanium dioxide has excellent specific surface area and micropores and higher photocatalytic activity.
Preferably, the phosphorus-doped nano titanium dioxide is prepared by the following steps: taking metatitanic acid solution, adding phosphate, and using the amount of metatitanic acid and phosphate as TiO2And P2O5The mass ratio is (1-10): 1, the pH is adjusted to 10.0-12.5, the calcination is carried out at 350-550 ℃, and then the grinding is carried out to obtain the catalyst. The metatitanic acid and the phosphate are calcined together, and then the nano-scale phosphorus doped titanium dioxide is obtained after crushing and grinding. Firstly, phosphorus is doped in the nano titanium dioxide, on one hand, the nano titanium dioxide is doped with the phosphorusThe titanium dioxide has higher photocatalytic activity, and on the other hand, the phosphorus element is beneficial to the dispersion of particles in the grinding process, thereby being beneficial to the stability of grinding slurry, reducing agglomeration and being more beneficial to subsequent coating.
Preferably, the calcination time is 2.5-6.0 h, the nano slurry with the solid content of 45-50% is prepared after crushing, and the nano slurry is ground until no precipitate exists after being placed for more than 7 days; when the grinding fluid is used, the grinding fluid is diluted by 2-10 times and then ground again. The nano slurry is fully ground to prevent the nano particles from agglomerating and settling, and is diluted and ground again when in use, so that the dispersibility of the nano titanium dioxide particles can be further ensured, and the coating is facilitated.
The phosphate can be selected from sodium hexametaphosphate, sodium hydrogen phosphate, sodium phosphate, potassium hydrogen phosphate and potassium phosphate.
Preferably, the adding time of the phosphorus-doped nano titanium dioxide, the silicon source and the pH regulator is 20-40 min, the homogenizing time is 30-40 min, the deposition time of the silicon source is obviously shorter than that of the inner silicon coating layer during preparation, so that a loose porous silicon framework is formed, the phosphorus-titanium is embedded among the frameworks, and the titanium-silicon-phosphorus composite coating layer with good photocatalytic activity is formed.
Preferably, the aluminum salt in the step S3 is a basic aluminum salt, and after the basic aluminum salt is added, the pH is adjusted to 5.5-6.5 with a pH adjuster, and the mixture is homogenized to form an aluminum-coated film layer; aluminum salt is added in an amount of Al2O3Calculated by 2.5-3.5% of the titanium dioxide base material. The alkaline aluminum salt is preferably sodium metaaluminate, the pH value of the alkaline aluminum salt is about 13-14, the pH value of the system is gradually reduced through a pH regulator after the alkaline aluminum salt is added until the pH value is reduced to subacidity (pH value is 5.5-6.5), and aluminum is orderly precipitated under alkaline, neutral and subacidity conditions to obtain an aluminum coating layer with various crystal structures including amorphous, boehmite and gibbsite crystal structures, so that a multifunctional aluminum coating layer is formed. In order to ensure that aluminum is uniformly precipitated under different pH conditions, the pH regulator regulates the pH to reduce the gradient to 0.1-0.5/min.
The pH regulator can adopt inorganic acid or inorganic base; the inorganic acid can be H2SO4、HCl、HNO3、H3PO4Preferably dilute H2SO4The concentration of the solution is 100-300 g/L; the inorganic base can be at least one of NaOH, KOH or ammonia water, preferably NaOH solution, and has a concentration of 100-300 g/L.
Example 1
Nano TiO 22Preparation: taking metatitanic acid solution, adding potassium phosphate, and TiO in proportion of metatitanic acid to potassium phosphate2/P2O5Adjusting the pH value to 10.0 at 1:1, and washing with water until the conductivity of the filtrate is less than 80 mus/cm; calcining for 4.0h at 450 ℃, crushing to obtain P-doped nano titanium dioxide, preparing into 45% aqueous solution, grinding for 60min by adopting zirconia beads with the diameter of 0.3-0.4 mm, and standing for more than 7d without precipitation; when in use, the mixture is diluted by 2 times and then ground again; a nano-1 solution;
taking 300g/L rutile type TiO2Slurry (rutile content > 99.3%), D50:0.320 μm, PSD:1.44, temperature 90 deg.C; adding 100g/L sodium silicate solution accounting for 2.5 percent of the mass fraction of the titanium dioxide in the slurry within 30 min; adjusting pH to 6.5 with 10% sulfuric acid solution for 180min, stirring and homogenizing for 30 min; adding a nano-1 solution accounting for 5% of the mass fraction of the titanium dioxide in the slurry, a 100g/L sodium silicate solution accounting for 2.8% of the mass fraction of the titanium dioxide in the slurry and a 10% dilute sulfuric acid solution regulator to ensure that the pH is 7.0, adding for 30min and homogenizing for 30 min; then adding 160g/L sodium metaaluminate solution accounting for 2.8 percent of the mass fraction of the titanium dioxide in the slurry, adjusting the pH to 6.5 by using dilute sulfuric acid solution, reducing the gradient of the pH by 0.1/min, homogenizing for 80min, washing with water, drying and crushing to obtain a sample No. 1.
Comparative example 1 (silicon-aluminum coating, prepared by general method)
Taking 300g/L rutile type TiO2Slurry (rutile content > 99.3%), D50:0.320 μm, PSD:1.44, temperature 90 deg.C; adding 100g/L sodium silicate solution accounting for 5.3 percent of the mass fraction of the titanium dioxide in the slurry within 30 min; adjusting pH to 6.5 with 10% sulfuric acid solution for 180min, stirring and homogenizing for 30 min; adding 160g/L sodium metaaluminate solution accounting for 2.8 percent of the mass fraction of the titanium dioxide in the slurry and 10 percent sulfuric acid solution, enabling the pH value to be 8.0 in parallel flow for 120min, homogenizing for 30min, adjusting the pH value to be 6.5 by using dilute sulfuric acid, adjusting the time for 30min, and homogenizing for 80 min; washed with water, dried and crushed to obtain a comparative sample No. 1.
Example 2
Nano TiO 22Preparation: adding potassium pyrophosphate into metatitanic acid solution, wherein the addition amount of metatitanic acid and potassium pyrophosphate is TiO2/P2O5Adding the mixture according to the ratio of 5:1, adjusting the pH value to 11.8 by ammonia water, and washing the mixture by water until the conductivity of the filtrate is less than 80 mus/cm; calcining for 2.5h at 350 ℃, crushing to obtain P-doped nano titanium dioxide, preparing into 47.5% aqueous solution, grinding for 50min by adopting zirconia beads with the diameter of 0.2-0.3 mm, and standing for more than 7d without precipitation; when in use, the mixture is diluted by 10 times and then ground again;
taking 280g/L rutile type TiO2Slurry (rutile content > 99.3%), D50: 0.345 μm, PSD: 1.50, the temperature is 80 ℃; adding 100g/L sodium silicate solution accounting for 2.4 percent of the mass fraction of the titanium dioxide in the slurry within 25 min; adjusting pH to 6.5 with 10% sulfuric acid solution at 150min, stirring and homogenizing for 30 min; adding a nano-2 solution accounting for 7.5 percent of the mass fraction of the titanium dioxide in the slurry, a 100g/L sodium silicate solution accounting for 5.8 percent of the mass fraction of the titanium dioxide in the slurry and a pH regulator to ensure that the pH is 8.0, wherein the adding time is 20min, and the homogenizing time is 30 min; adding 160g/L sodium metaaluminate solution with titanium dioxide mass percent of 2.5% in the slurry, adjusting pH to 5.5 with 10% sulfuric acid solution, reducing pH gradient by 0.5/min, homogenizing for 60min, washing with water, drying, and pulverizing to obtain # 2 sample.
Example 3
Nano TiO 22Preparation: adding sodium phosphate into metatitanic acid solution, wherein the addition amount of metatitanic acid and sodium phosphate is TiO2/P2O5Adding the mixture according to the proportion of 10:1, adjusting the pH value to 12.5 by ammonia water, and washing the mixture by water until the conductivity of the filtrate is less than 80 mus/cm; calcining at 550 ℃ for 2.5h, crushing to obtain P-doped nano titanium dioxide, preparing into 50% aqueous solution, grinding for 60min by adopting zirconia beads with the diameter of 0.2-0.3 mm, and standing for more than 7d without precipitation; when in use, the mixture is diluted by 5 times and then ground again; a nano-3 solution;
340g/L rutile type TiO is taken2Slurry (rutile content > 99.3%), D50:0.334 μm, PSD:1.48, temperature 95 deg.C; adding 100g/L sodium silicate solution accounting for 2.8 percent of the mass fraction of the titanium dioxide in the slurry within 40 min; using 10% sulfuric acid solution inAdjusting pH to 6.5 within 200min, stirring and homogenizing for 40 min; adding 100g/L sodium silicate solution and pH regulator, wherein the sodium silicate solution accounts for 10-3% of the mass fraction of the titanium dioxide in the slurry and 8.8% of the mass fraction of the titanium dioxide in the slurry, and the pH regulator ensures that the pH is 7.5, the adding time is 40min, and the homogenizing time is 40 min; adding 160g/L sodium metaaluminate solution accounting for 3.5% of the mass fraction of the titanium dioxide in the slurry, adjusting the pH to 5.8 by using 10% sulfuric acid solution, reducing the gradient of the pH for 0.2min, homogenizing for 80min, washing with water, drying and crushing to obtain a sample No. 3.
FIG. 1 is an electron microscope transmission test chart of a comparison sample, and FIGS. 2 to 4 are electron microscope transmission test charts of samples obtained in examples 1 to 3, respectively, and it can be seen from FIG. 1 that the film layer of the comparison sample is compact in surface and uneven in coating layer, and it can be seen from FIGS. 2 to 5 that the sample film layer obtained in the examples of the present application has uniform surface and particulate-like substances distributed around the film layer, which is a film layer of a titanium-silicon-phosphorus layer and an outer polycrystalline aluminum film layer, and it can be seen that the surface coating is very successful.
Application test comparison
The samples prepared in examples 1-3 and comparative example were subjected to the chroma and hiding power test of the aqueous emulsion paint system and the weather resistance and hydrophobic angle test of the building exterior wall paint system by the conventional method, and the results are shown in tables 1-3.
TABLE 1 sample chroma and hiding test results in aqueous latex paint system
| Sample name | L* | a* | b* | Coverage ratio | 20° | 60° | 85° |
| Sample No. 1 | 94.92 | -0.6 | 0.74 | 84.6 | 12.5 | 58.8 | 82.6 |
| Comparison No. 1# | 94.75 | -0.6 | 0.93 | 84.09 | 12.6 | 58.8 | 79.3 |
| Sample No. 2# | 95.02 | -0.6 | 0.62 | 85.35 | 15.8 | 66.8 | 84.9 |
| Sample No. 3 | 94.78 | -0.59 | 0.75 | 84.56 | 11.6 | 57.6 | 81.1 |
Table 2 testing of samples for weatherability data in building exterior wall paint systems
Table 3 hydrophobic angle test data for samples in building exterior wall paint system
As can be seen from Table 1, the weather resistance of the titanium dioxide prepared by the invention is higher in whiteness and higher in coverage than that of a comparative sample; as can be seen from Table 2, the weather resistance of the titanium dioxide prepared by the invention is slightly improved compared with that of the comparative sample. As can be seen from Table 3, the contact angle of the titanium dioxide prepared by the method changes greatly along with time, which shows that the photocatalytic activity is high and the self-cleaning capability is strong; the combination of the three tables shows that the coating prepared by the method can provide high whiteness, high covering and self-cleaning performance when being used for outdoor building coatings.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The white pigment for the self-cleaning outer wall is characterized by comprising a titanium dioxide base material and an envelope layer positioned on the surface of the titanium dioxide base material, wherein the envelope layer sequentially comprises a silicon envelope layer, a titanium-silicon-phosphorus composite envelope layer and an aluminum envelope layer containing various crystal structures from inside to outside.
2. A white pigment for self-cleaning exterior walls according to claim 1,
the titanium-silicon-phosphorus composite coating layer is formed by simultaneously adding phosphorus-doped nano titanium dioxide, a silicon source and a pH regulator under the condition that the pH value is 7.0-8.0, wherein the adding amount of the phosphorus-doped nano titanium dioxide material is rutile TiO2The amount of the silicon source is 5.0-10.0% of that of the titanium dioxide base material, and the addition amount of the silicon source is SiO2The content of the titanium dioxide is 2.8-8.8% of that of the titanium dioxide base material.
3. A white pigment for self-cleaning exterior walls according to claim 1,
the aluminum coating layer is formed by adding alkaline aluminum salt and then adjusting the pH to 5.5-6.5 by using a pH regulator, wherein the adding amount of the aluminum salt is Al2O32.5-3.5% of the titanium dioxide base material; the various crystalline structures include amorphous, boehmite, and gibbsite crystalline forms.
4. The method for preparing the white pigment for the self-cleaning exterior wall as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
s1: adding a silicon source into the titanium dioxide-based material slurry to form a silicon coating layer;
s2: then, adding nano titanium dioxide doped with phosphorus, a silicon source and a pH regulator into the slurry at the same time, and homogenizing to form a titanium-silicon-phosphorus composite coating layer;
s3: and adding aluminum salt and a pH regulator into the slurry, and homogenizing to form an aluminum coating layer containing various crystal structures.
5. A method for preparing a white pigment for self-cleaning exterior walls as claimed in claim 4,
the adding amount of the phosphorus-doped nano titanium dioxide material in the step S2 is rutile TiO2The amount of the silicon source is 5.0-10.0% of that of the titanium dioxide base material, and the addition amount of the silicon source is SiO2The titanium dioxide base material accounts for 2.8-8.8%, the pH of the slurry is controlled to be 7.0-8.0, and then the titanium-silicon-phosphorus composite coating layer is formed through homogenization.
6. A method for preparing a white pigment for self-cleaning exterior walls as claimed in claim 5,
the phosphorus-doped nano titanium dioxide is prepared by the following steps: taking metatitanic acid solution, adding phosphate, wherein the dosage of metatitanic acid and phosphate is TiO2And P2O5The mass ratio is (1-10): 1, the pH is adjusted to 10.0-12.5, the calcination is carried out at 350-550 ℃, and then the grinding is carried out to obtain the catalyst.
7. A method for preparing a white pigment for self-cleaning exterior walls as claimed in claim 6,
the calcination time is 2.5-6.0 h, the nano slurry with the solid content of 45-50% is prepared after crushing, and the nano slurry is ground until no precipitate exists after being placed for more than 7 days; when the grinding fluid is used, the grinding fluid is diluted by 2-10 times and then ground again.
8. A method for preparing a white pigment for self-cleaning exterior walls as claimed in claim 5,
the adding time of the phosphorus-doped nano titanium dioxide, the silicon source and the pH regulator is 20-40 min, and the homogenizing time is 30-40 min.
9. A method for preparing a white pigment for self-cleaning exterior walls as claimed in claim 4,
in step S3, the aluminum salt is a basic aluminum salt, and after the basic aluminum salt is added, a pH regulator is usedAdjusting the pH value to 5.5-6.5, and homogenizing to form the aluminum coating layer; the aluminum salt is added in an amount of Al2O3The content of the titanium dioxide is 2.5-3.5% of that of the titanium dioxide base material.
10. The method for preparing a white pigment for self-cleaning exterior walls as claimed in claim 9,
the alkaline aluminum salt is sodium metaaluminate, and the pH regulator regulates the pH to reduce the gradient to 0.1-0.5/min.
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