CN114686103A - 一种超疏水复合防腐蚀涂层及其构筑方法和应用 - Google Patents
一种超疏水复合防腐蚀涂层及其构筑方法和应用 Download PDFInfo
- Publication number
- CN114686103A CN114686103A CN202210327120.7A CN202210327120A CN114686103A CN 114686103 A CN114686103 A CN 114686103A CN 202210327120 A CN202210327120 A CN 202210327120A CN 114686103 A CN114686103 A CN 114686103A
- Authority
- CN
- China
- Prior art keywords
- super
- hydrophobic
- mos
- znpa
- zif
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 89
- 239000011248 coating agent Substances 0.000 title claims abstract description 87
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000005260 corrosion Methods 0.000 title claims abstract description 62
- 238000010276 construction Methods 0.000 title claims description 12
- 239000000463 material Substances 0.000 claims abstract description 74
- 239000002114 nanocomposite Substances 0.000 claims abstract description 72
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 37
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 29
- 238000009210 therapy by ultrasound Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001723 curing Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 3
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 claims description 3
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 abstract description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 235000002949 phytic acid Nutrition 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 244000137852 Petrea volubilis Species 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000005028 tinplate Substances 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical class S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Images
Classifications
-
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/546—No clear coat specified each layer being cured, at least partially, separately
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- 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
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
本发明公开了一种超疏水复合防腐蚀涂层的构筑方法,采用改性剂对ZnPA@ZIF‑8/PDA‑MoS2纳米复合材料进行超疏水改性制备超疏水ZnPA@ZIF‑8/PDA‑MoS2纳米复合材料。通过层层喷涂法将成膜物质、交联剂、超疏水ZnPA@ZIF‑8/PDA‑MoS2纳米复合材料依次喷涂于金属基体表面,得到超疏水复合防腐蚀涂层,该涂层能够极大地提高金属基体的防腐蚀性能。首先超疏水ZnPA@ZIF‑8/PDA‑MoS2纳米复合材料位于涂层的顶层,能够隔绝腐蚀环境中水分子的透过,大大削弱水分子在涂层中的渗透能力;其次超疏水ZnPA@ZIF‑8/PDA‑MoS2纳米复合材料中的MoS2能够延长腐蚀介质在涂层内部的扩散途径及时间,ZnPA@ZIF‑8纳米粒子中的植酸锌及2‑甲基咪唑能够发挥自修复性能,减缓金属的腐蚀速率;最后利用交联剂增强了成膜物质与超疏水ZnPA@ZIF‑8/PDA‑MoS2纳米复合材料之间的结合力,提高复合涂层的使用寿命。
Description
技术领域
本发明属于防腐蚀涂层技术领域,具体涉及一种超疏水复合防腐蚀涂层及其构筑方法和应用。
背景技术
金属腐蚀造成了巨大的经济损失和环境污染,甚至威胁人类健康安全。据统计,全球每年约有20%的金属材料因被腐蚀而无法回收,因此,寻求一种能够减缓金属腐蚀的防腐蚀涂层构筑方法是各国及金属行业的当务之急。
现有研究中,有机-无机复合涂层是当前的研究热点。通常采用物理共混法或化学原位聚合法以有机聚合物为成膜物质,无机纳米粒子为填料,协同提高涂层的防腐蚀性能。但由于无机纳米粒子的引入量较小,且与有机聚合物之间结合力较差,因此复合涂层的防腐蚀性能提升有限,无法做到长期防腐。
发明内容
为了克服上述现有技术的缺点,本发明的目的在于提供一种超疏水复合防腐蚀涂层及其构筑方法和应用,以解决无机纳米粒子引入量较少,且与有机聚合物间结合力较差,防腐效果不佳的问题。
为了达到上述目的,本发明采用以下技术方案予以实现:
本发明公开了一种超疏水复合防腐蚀涂层的构筑方法,包括以下步骤:
步骤1),将改性剂与无水乙醇混合均匀,形成混合溶液,在冰浴条件下,向混合溶液中加入ZnPA@ZIF-8/PDA-MoS2纳米复合材料,超声、搅拌、洗涤干燥,得到超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料;
步骤2),采用层层喷涂法,将成膜物质均匀喷涂于金属基体表面,干燥固化后形成一层涂层,将交联剂与溶剂混合均匀喷涂于涂层表面,然后将超疏水 ZnPA@ZIF-8/PDA-MoS2纳米复合材料在溶剂中超声分散,喷涂于涂层的顶层,真空干燥固化后进行室温干燥,得到超疏水复合防腐蚀涂层。
优选地,步骤1)中,改性剂、无水乙醇与ZnPA@ZIF-8/PDA-MoS2纳米复合材料的质量比为(0.25~0.40):(5~15):(0.05~0.15)。
优选地,步骤1)中,所述改性剂为硅烷偶联剂KH-550、硅烷偶联剂KH-570、六甲基二硅氮烷、1H,1H,2H,2H全氟辛基三乙氧基硅烷或1H,1H,2H,2H-全氟癸基三乙氧基硅烷。
优选地,步骤1)中,所述混合均匀为磁力搅拌0.5~2.0h。
优选地,步骤1)中,所述超声为先在超声细胞粉碎机中超声5~15min,随后转移至超声波清洗器中继续超声20~40min,结束后磁力搅拌20~30h。
优选地,步骤2)中,交联剂与溶剂的质量比为(0.01~0.05):(3~8),超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料与溶剂的质量比为(0.10~0.20):(8~12);成膜物质的用量为333~500g/m2,交联剂的用量为3.33~16.67g/m2,超疏水 ZnPA@ZIF-8/PDA-MoS2纳米复合材料的用量为33.33~66.67g/m2。
优选地,步骤2)中,所述成膜物质为聚丙烯酸酯乳液、聚氨酯乳液或环氧树脂。
优选地,步骤2)中,所述交联剂为三亚乙基四胺交联剂、氮丙啶交联剂或六氢邻苯二甲酸酐交联剂;溶剂为无水乙醇或丙酮。
优选地,步骤2)中,超声分散30~60min,在85℃下真空干燥固化20~40min,室温干燥20~30h。
本发明还公开了上述构筑方法得到的超疏水复合防腐蚀涂层,所述超疏水复合防腐蚀涂层的水接触角为161.9°,在10-2Hz时阻抗模量为106.15Ω·cm2。
本发明还公开了上述超疏水复合防腐蚀涂层在制备金属防腐材料中的应用。
与现有技术相比,本发明具有以下有益效果:
本发明公开了一种超疏水复合防腐蚀涂层的构筑方法,首先采用改性剂对 ZnPA@ZIF-8/PDA-MoS2纳米复合材料进行疏水改性,制备了一种超疏水 ZnPA@ZIF-8/PDA-MoS2纳米复合材料,然后利用层层喷涂法将成膜物质、交联剂、超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料依次喷涂于金属基体表面制备超疏水复合防腐蚀涂层。一方面,引入较多的超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料,喷涂于涂层的顶层,能够隔绝腐蚀环境中水分子的透过,大大削弱水分子在涂层中的渗透能力,发挥物理屏蔽作用;另一方面,超疏水 ZnPA@ZIF-8/PDA-MoS2纳米复合材料中的二维层状材料MoS2能够延长腐蚀介质在涂层内部的扩散途径及时间,ZnPA@ZIF-8纳米粒子中的缓蚀剂植酸锌即2- 甲基咪唑能够发挥自修复性能,减缓金属的腐蚀速率。另外,交联剂的存在增强了成膜物质与超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料间的结合力,提高了复合涂层的使用寿命。通过层层喷涂法所制备的这种兼具被动与主动防护功能的超疏水复合防腐蚀涂层,协同提升了金属基体的防腐蚀性能。此外,层层喷涂法作为一种简单通用的复合涂层制备方法,不仅可以克服物理共混法或化学原位聚合法的缺点,又能够根据各种材料的特性对涂层进行结构设计,从而充分发挥每种材料的优势,获得防腐蚀性能优异的复合涂层。
本发明还公开了上述制备方法得到的超疏水复合防腐蚀涂层,与空白样、层层喷涂法所制复合涂层相比,本发明所制备的超疏水复合防腐蚀涂层具有优异的防腐蚀性能,其在频率为10-2Hz时,阻抗模量分别提高了3.90和1.86个数量级,达到106.15Ω·cm2。
附图说明
图1为本发明ZnPA@ZIF-8/PDA-MoS2纳米复合材料的水接触角图;
图2为本发明超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料的水接触角图;
图3为本发明层层喷涂法所制备复合涂层的水接触角图;
图4为本发明层层喷涂法所制备超疏水复合防腐蚀涂层的水接触角图;
图5为本发明空白样在3.5wt%NaCl溶液中的Nyquist图;
图6为本发明层层喷涂法所制备复合涂层在3.5wt%NaCl溶液中的Nyquist 图;
图7为本发明层层喷涂法所制备超疏水复合防腐蚀涂层在3.5wt%NaCl溶液中的Nyquist图;
图8为本发明空白样、层层喷涂法所制备的复合涂层与超疏水复合防腐蚀涂层在3.5wt%NaCl溶液中的Bode图。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分的实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。
需要说明的是,本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象,而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换,以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外,术语“包括”和“具有”以及他们的任何变形,意图在于覆盖不排他的包含,例如,包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元,而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
本发明中ZnPA@ZIF-8/PDA-MoS2纳米复合材料的制备过程如下:
首先将MoS2在无水乙醇中超声分散,再向其中加入Tris(三羟甲基氨基甲烷)缓冲溶液,继续超声。将盐酸多巴胺加入上述混合液中于室温下磁力搅拌,反应结束后离心、洗涤、干燥收集产物,得到聚多巴胺改性二硫化钼纳米粒子 (PDA-MoS2)。其次将植酸锌(ZnPA)的水溶液在超声搅拌条件下缓慢加入至 PDA-MoS2纳米粒子的水溶液中。随后,将上述混合溶液缓慢滴加至2-甲基咪唑 (2-MI)的水溶液中,恒温搅拌反应。最后,离心、洗涤、干燥收集产物,得到ZnPA@ZIF-8/PDA-MoS2纳米复合材料。
下面结合附图对本发明做进一步详细描述:
实施例1:
(1)将0.28g硅烷偶联剂KH-550与5g无水乙醇磁力搅拌0.5h至混合均匀。之后,在冰浴条件下,向上述混合溶液中加入0.05g ZnPA@ZIF-8/PDA-MoS2纳米复合材料,在超声细胞粉碎机中超声5min,随后转移至超声波清洗器中继续超声20min,结束后磁力搅拌20h,洗涤干燥得到超疏水 ZnPA@ZIF-8/PDA-MoS2纳米复合材料。
(2)采用层层喷涂法,首先将1.0g聚丙烯酸酯乳液均匀喷涂于800目砂纸打磨后的马口铁金属基体表面,在真空烘箱中85℃干燥固化5min;然后将0.01g 三亚乙基四胺交联剂与3g丙酮混合均匀,继续喷涂于上述涂层表面;最后将0.10 g超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料分散于8g丙酮中超声30min后喷涂于涂层的顶层,在真空烘箱中85℃干燥固化20min后室温干燥20h,得到超疏水复合防腐蚀涂层。
实施例2:
(1)将0.30g硅烷偶联剂KH-570与7g无水乙醇磁力搅拌0.6h至混合均匀。之后,在冰浴条件下,向上述混合溶液中加入0.07g ZnPA@ZIF-8/PDA-MoS2纳米复合材料,在超声细胞粉碎机中超声7min,随后转移至超声波清洗器中继续超声24min,结束后磁力搅拌22h,洗涤干燥得到超疏水 ZnPA@ZIF-8/PDA-MoS2纳米复合材料。
(2)采用层层喷涂法,首先将1.1g聚丙烯酸酯乳液均匀喷涂于800目砂纸打磨后的马口铁金属基体表面,在真空烘箱中85℃干燥固化7min;然后将0.02g 氮丙啶交联剂与4g无水乙醇混合均匀,继续喷涂于上述涂层表面;最后将0.12g 超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料分散于9g无水乙醇中超声36min 后喷涂于涂层的顶层,在真空烘箱中85℃干燥固化24min后室温干燥22h,得到超疏水复合防腐蚀涂层。
实施例3:
(1)将0.33g六甲基二硅氮烷与9g无水乙醇磁力搅拌0.8h至混合均匀。之后,在冰浴条件下,向上述混合溶液中加入0.09g ZnPA@ZIF-8/PDA-MoS2纳米复合材料,在超声细胞粉碎机中超声9min,随后转移至超声波清洗器中继续超声28min,结束后磁力搅拌24h,洗涤干燥得到超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料。
(2)采用层层喷涂法,首先将1.2g聚氨酯乳液均匀喷涂于800目砂纸打磨后的马口铁金属基体表面,在真空烘箱中85℃干燥固化9min;然后将0.03g六氢邻苯二甲酸酐交联剂与5g无水乙醇混合均匀,继续喷涂于上述涂层表面;最后将0.14g超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料分散于10g无水乙醇中超声42min后喷涂于涂层的顶层,在真空烘箱中85℃干燥固化28min后室温干燥24h,得到超疏水复合防腐蚀涂层。
实施例4:
(1)将0.36g 1H,1H,2H,2H-全氟辛基三乙氧基硅烷与11g无水乙醇磁力搅拌1.0h至混合均匀。之后,在冰浴条件下,向上述混合溶液中加入0.11g ZnPA@ZIF-8/PDA-MoS2纳米复合材料,在超声细胞粉碎机中超声11min,随后转移至超声波清洗器中继续超声32min,结束后磁力搅拌26h,洗涤干燥得到超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料。
(2)采用层层喷涂法,首先将1.3g环氧树脂均匀喷涂于800目砂纸打磨后的马口铁金属基体表面,在真空烘箱中85℃干燥固化11min;然后将0.04g六氢邻苯二甲酸酐交联剂与6g丙酮混合均匀,继续喷涂于上述涂层表面;最后将0.16 g超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料分散于11g丙酮中超声48min后喷涂于涂层的顶层,在真空烘箱中85℃干燥固化32min后室温干燥26h,得到超疏水复合防腐蚀涂层。
实施例5:
(1)将0.39g 1H,1H,2H,2H-全氟癸基三乙氧基硅烷与13g无水乙醇磁力搅拌1.2h至混合均匀。之后,在冰浴条件下,向上述混合溶液中加入0.13g ZnPA@ZIF-8/PDA-MoS2纳米复合材料,在超声细胞粉碎机中超声13min,随后转移至超声波清洗器中继续超声36min,结束后磁力搅拌28h,洗涤干燥得到超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料。
(2)采用层层喷涂法,首先将1.4g聚氨酯乳液均匀喷涂于800目砂纸打磨后的马口铁金属基体表面,在真空烘箱中85℃干燥固化13min;然后将0.05g 六氢邻苯二甲酸酐交联剂与7g丙酮混合均匀,继续喷涂于上述涂层表面;最后将0.18g超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料分散于12g丙酮中超声 54min后喷涂于涂层的顶层,在真空烘箱中85℃干燥固化36min后室温干燥28 h,得到超疏水复合防腐蚀涂层。
对上述实施例制备的超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料的疏水性能进行研究,以实施例4为例,图1与图2分别为ZnPA@ZIF-8/PDA-MoS2纳米复合材料和采用实施例4制备的超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料的水接触角测试照片,从图中可以看出ZnPA@ZIF-8/PDA-MoS2纳米复合材料的水接触角为118.0°,超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料的水接触角为 159.3°,说明ZnPA@ZIF-8/PDA-MoS2纳米复合材料成功进行了超疏水改性。
图3与图4分别为层层喷涂法所制备复合涂层和采用实施例4制备的超疏水复合防腐蚀涂层的水接触角测试照片,从图中可以看出超疏水复合防腐蚀涂层的水接触角达到了161.9°,与层层喷涂法所制备复合涂层的水接触角相比显著增大,说明成功得到了超疏水复合防腐蚀涂层。其中,层层喷涂法所制备复合涂层的过程为:将超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料换成 ZnPA@ZIF-8/PDA-MoS2纳米复合材料,其余工艺与制备超疏水复合防腐蚀涂层的步骤相同。
图5、图6、图7和图8为空白样800目砂纸打磨后的马口铁、层层喷涂法所制备复合涂层与超疏水复合防腐蚀涂层在3.5wt%NaCl溶液中的Nyquist图和 Bode图。从图5、图6、图7和图8中可以看出,超疏水复合防腐蚀涂层的半圆弧直径最大,阻抗模量最高,防腐蚀性能最好。与空白样、层层喷涂法所制备复合涂层相比,超疏水复合防腐蚀涂层在频率为10- 2Hz时,阻抗模量分别提高了 3.90和1.86个数量级,高达106.15Ω·cm2。
综上所述,利用本发明制备的超疏水复合防腐蚀涂层,1)采用改性剂对 ZnPA@ZIF-8/PDA-MoS2纳米复合材料进行超疏水改性;2)采用层层喷涂法,将成膜物质、交联剂、超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料依次喷涂于金属表面,干燥后得到超疏水复合防腐蚀涂层。与空白样、层层喷涂法所制备复合涂层相比,采用本发明方法所制备的超疏水复合防腐蚀涂层在频率为10-2Hz时,其阻抗模量分别提高了3.90和1.86个数量级,达到106.15Ω·cm2,具有优异的防腐蚀性能。
以上内容仅为说明本发明的技术思想,不能以此限定本发明的保护范围,凡是按照本发明提出的技术思想,在技术方案基础上所做的任何改动,均落入本发明权利要求书的保护范围之内。
Claims (10)
1.一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,包括以下步骤:
步骤1),将改性剂与无水乙醇混合均匀,形成混合溶液,在冰浴条件下,向混合溶液中加入ZnPA@ZIF-8/PDA-MoS2纳米复合材料,超声、搅拌、洗涤干燥,得到超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料;
步骤2),采用层层喷涂法,将成膜物质均匀喷涂于金属基体表面,干燥固化后形成一层涂层,将交联剂与溶剂混合均匀喷涂于涂层表面,然后将超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料在溶剂中超声分散,喷涂于涂层的顶层,真空干燥固化后进行室温干燥,得到超疏水复合防腐蚀涂层。
2.根据权利要求1所述的超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤1)中,改性剂、无水乙醇与ZnPA@ZIF-8/PDA-MoS2纳米复合材料的质量比为(0.25~0.40):(5~15):(0.05~0.15)。
3.根据权利要求1所述的一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤1)中,所述改性剂为硅烷偶联剂KH-550、硅烷偶联剂KH-570、六甲基二硅氮烷、1H,1H,2H,2H全氟辛基三乙氧基硅烷或1H,1H,2H,2H-全氟癸基三乙氧基硅烷。
4.根据权利要求1所述的一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤1)中,所述超声为先在超声细胞粉碎机中超声5~15min,随后转移至超声波清洗器中继续超声20~40min,结束后磁力搅拌20~30h。
5.根据权利要求1所述的一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤2)中,交联剂与溶剂的质量比为(0.01~0.05):(3~8),超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料与溶剂的质量比为(0.10~0.20):(8~12);成膜物质的用量为333~500g/m2,交联剂的用量为3.33~16.67g/m2,超疏水ZnPA@ZIF-8/PDA-MoS2纳米复合材料的用量为33.33~66.67g/m2。
6.根据权利要求1所述的一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤2)中,所述成膜物质为聚丙烯酸酯乳液、聚氨酯乳液或环氧树脂。
7.根据权利要求1所述的一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤2)中,所述交联剂为三亚乙基四胺交联剂、氮丙啶交联剂或六氢邻苯二甲酸酐交联剂;溶剂为无水乙醇或丙酮。
8.根据权利要求1所述的一种超疏水复合防腐蚀涂层的构筑方法,其特征在于,步骤2)中,超声分散30~60min,在85℃下真空干燥固化20~40min,室温干燥20~30h。
9.一种基于权利要求1~8任一项所述构筑方法得到的超疏水复合防腐蚀涂层,其特征在于,所述超疏水复合防腐蚀涂层的水接触角为161.9°,在10-2Hz时阻抗模量为106.15Ω·cm2。
10.权利要求9所述的超疏水复合防腐蚀涂层在制备金属防腐材料中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210327120.7A CN114686103A (zh) | 2022-03-30 | 2022-03-30 | 一种超疏水复合防腐蚀涂层及其构筑方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210327120.7A CN114686103A (zh) | 2022-03-30 | 2022-03-30 | 一种超疏水复合防腐蚀涂层及其构筑方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114686103A true CN114686103A (zh) | 2022-07-01 |
Family
ID=82140915
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210327120.7A Pending CN114686103A (zh) | 2022-03-30 | 2022-03-30 | 一种超疏水复合防腐蚀涂层及其构筑方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114686103A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116786384A (zh) * | 2023-08-03 | 2023-09-22 | 绵阳麦思威尔科技有限公司 | 一种复合型自愈合防腐涂层材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104141226A (zh) * | 2014-07-30 | 2014-11-12 | 陕西科技大学 | 利用层层组装在皮革表面构筑超疏水涂层的方法 |
CN108855831A (zh) * | 2018-07-10 | 2018-11-23 | 陕西科技大学 | 一种防腐蚀型金属涂层的构筑方法 |
CN109370408A (zh) * | 2018-10-11 | 2019-02-22 | 河北工业大学 | 水性聚氨酯与疏水改性的无机纳米粒子复合制备超疏水涂层的方法 |
CN113185898A (zh) * | 2021-05-18 | 2021-07-30 | 南昌航空大学 | 一种采用喷涂法制备超疏水双功能涂层的方法 |
CN114045497A (zh) * | 2021-11-09 | 2022-02-15 | 陕西科技大学 | 植酸锌@沸石咪唑酯骨架-8/二硫化钼纳米复合材料及其制备方法和应用 |
-
2022
- 2022-03-30 CN CN202210327120.7A patent/CN114686103A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104141226A (zh) * | 2014-07-30 | 2014-11-12 | 陕西科技大学 | 利用层层组装在皮革表面构筑超疏水涂层的方法 |
CN108855831A (zh) * | 2018-07-10 | 2018-11-23 | 陕西科技大学 | 一种防腐蚀型金属涂层的构筑方法 |
CN109370408A (zh) * | 2018-10-11 | 2019-02-22 | 河北工业大学 | 水性聚氨酯与疏水改性的无机纳米粒子复合制备超疏水涂层的方法 |
CN113185898A (zh) * | 2021-05-18 | 2021-07-30 | 南昌航空大学 | 一种采用喷涂法制备超疏水双功能涂层的方法 |
CN114045497A (zh) * | 2021-11-09 | 2022-02-15 | 陕西科技大学 | 植酸锌@沸石咪唑酯骨架-8/二硫化钼纳米复合材料及其制备方法和应用 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116786384A (zh) * | 2023-08-03 | 2023-09-22 | 绵阳麦思威尔科技有限公司 | 一种复合型自愈合防腐涂层材料及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6925680B2 (ja) | 塗料の製造方法、および自己修復コーティング層の調製方法 | |
CN106046287B (zh) | 一种石墨烯改性水性聚氨酯的制备方法 | |
CN110054965B (zh) | 改性氧化石墨烯共固化水性环氧树脂涂料及其制备方法 | |
CN105885564B (zh) | 全有机多重氟化环氧超疏水复合涂料及其制备方法和使用方法 | |
CN106947373B (zh) | 含丙烯酸酯聚合物表面改性纳米SiO2微球的阳离子电沉积涂料 | |
CN111822296A (zh) | 一种铝合金表面超疏水复合涂层的制备方法 | |
CN113004736A (zh) | 一种改性氮化硼纳米片的制备方法及其在提高水性有机防护涂料耐腐蚀性能中的应用 | |
CN108384438A (zh) | 一种阳极氧化耐钢丝绒抗指纹纳米uv涂料 | |
CN108727947A (zh) | 一种氧化石墨烯杂化防腐涂料及制备方法 | |
CN108948949A (zh) | 一种导电防腐涂料及其制备方法 | |
CN107964097A (zh) | 还原氧化石墨烯、四氧化三铁和聚苯胺的三元纳米复合材料制备方法及应用 | |
CN114686103A (zh) | 一种超疏水复合防腐蚀涂层及其构筑方法和应用 | |
CN111892857A (zh) | 一种工业管道防腐粉末涂料及其制备方法 | |
TWI490254B (zh) | 無機鈍化塗料、其形成方法、及所形成之無機鈍化保護膜 | |
CN110358395A (zh) | 一种基于石墨烯的耐腐蚀涂层及其制备方法 | |
CN106833247A (zh) | 一种环保型氟碳防腐涂料及其制备方法 | |
CN110467838A (zh) | 一种水性导电涂料及其制备方法 | |
CN112662270A (zh) | 一种改性氧化石墨烯环氧复合防腐涂料的制备方法 | |
CN110305563A (zh) | 一种抑菌防腐蚀水性环氧涂料的制备方法 | |
CN109251661A (zh) | 一种超高性能环氧底漆及其制备方法 | |
CN109294426A (zh) | 一种含有空心玻璃微珠的超疏水涂层及其制备方法 | |
CN109054475A (zh) | 一种环保型高效防腐水性涂料及其合成方法 | |
CN106496553B (zh) | 具有电化学防腐作用的碳纳米管/聚苯胺复合材料、制备方法及应用 | |
CN109880479A (zh) | 一种双组份水性石墨烯环氧富锌涂料及其制作方法 | |
CN109796845A (zh) | 用于金属表面的环氧树脂/蒙脱石纳米复合涂料及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220701 |
|
RJ01 | Rejection of invention patent application after publication |