CN112853420A - Fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and preparation method thereof - Google Patents
Fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and preparation method thereof Download PDFInfo
- Publication number
- CN112853420A CN112853420A CN202110050185.7A CN202110050185A CN112853420A CN 112853420 A CN112853420 A CN 112853420A CN 202110050185 A CN202110050185 A CN 202110050185A CN 112853420 A CN112853420 A CN 112853420A
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- temperature
- combination
- time
- electrochemical deposition
- 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.)
- Granted
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 107
- 239000010935 stainless steel Substances 0.000 title claims abstract description 105
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 44
- 238000004140 cleaning Methods 0.000 title claims abstract description 37
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 36
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004070 electrodeposition Methods 0.000 claims abstract description 32
- 238000002791 soaking Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 235000021313 oleic acid Nutrition 0.000 claims description 6
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 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 claims description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 4
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 241000700605 Viruses Species 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229940098424 potassium pyrophosphate Drugs 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims 1
- 230000002155 anti-virotic effect Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 4
- 235000011083 sodium citrates Nutrition 0.000 description 4
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 235000021360 Myristic acid Nutrition 0.000 description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000001476 sodium potassium tartrate Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 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
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002362 hafnium Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth metal salt Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明提供一种无氟超疏水自清洁抗菌防霉抗病毒不锈钢及其制备方法，所述制备方法包括以下步骤：(1)对预处理后的不锈钢进行电解活化处理，得到表面活化不锈钢；(2)对步骤(1)所述表面活化不锈钢进行电化学沉积处理，得到具有沉积层的不锈钢；(3)对步骤(2)得到的所述具有沉积层的不锈钢依次进行加热氧化、浸泡修饰以及烘干得到所述无氟超疏水自清洁抗菌防霉抗病毒不锈钢。所述不锈钢表面膜层均匀致密，可有效阻止污染物黏附，具有自清洁功能；且膜层具有优异的、广谱长效的抗菌防霉抗病毒效果；所述制备方法高效环保，可实现零排放。The present invention provides a fluorine-free super-hydrophobic self-cleaning antibacterial, anti-mildew, and anti-virus stainless steel and a preparation method thereof. The preparation method comprises the following steps: (1) electrolytically activate the pretreated stainless steel to obtain surface-activated stainless steel; ( 2) performing electrochemical deposition treatment on the surface-activated stainless steel in step (1) to obtain stainless steel with a deposited layer; (3) sequentially performing heating oxidation, soaking modification and The fluorine-free super-hydrophobic self-cleaning antibacterial, mildew-proof and anti-virus stainless steel is obtained by drying. The stainless steel surface film layer is uniform and dense, can effectively prevent the adhesion of pollutants, and has a self-cleaning function; and the film layer has excellent, broad-spectrum and long-lasting antibacterial, mildew, and antiviral effects; the preparation method is efficient and environmentally friendly, and can achieve zero emission.
Description
Technical Field
The invention belongs to the technical field of stainless steel surface treatment, relates to stainless steel and a preparation method thereof, and particularly relates to fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof.
Background
In the prior art, hydrophobic stainless steel is usually obtained by modifying with fluorine-containing substances, but the fluorine-containing substances not only seriously damage the environment, but also have biotoxicity and are one of the most difficult degradable organic pollutants. In addition, the surface of the fluorine-containing hydrophobic stainless steel has the function of preventing bacterial adhesion in a short time, and does not have the performances of long-acting antibiosis, mildew prevention, virus resistance and the like.
CN111519112A discloses a preparation method of a multilayer antibacterial stainless steel material, which comprises a substrate steel material and a steel double-layer structure forming a surface antibacterial layer, wherein a double-layer composite material formed by metallurgically combining a substrate material and a surface layer material is formed by a double-layer composite casting method, a double-layer composite plate obtained by continuous casting is cut at a fixed length to obtain a double-layer plate blank with a fixed length, the double-layer plate blank is rolled to obtain the antibacterial stainless steel material, a semi-finished product is obtained by heat treatment, rolling and stamping, the semi-finished product is subjected to antibacterial heat treatment, coarse grinding, fine grinding, polishing, cleaning and other procedures, and then is dried and packaged to obtain a finished product. The invention has lower processing cost and larger thickness of the antibacterial layer. Although the stainless steel prepared by the method has certain antibacterial performance, the surface of the stainless steel does not have super-hydrophobic performance.
CN107815679A discloses a simple method for preparing a heat-resistant super-hydrophobic coating on a stainless steel surface, belongs to the field of metal surface treatment, and aims to improve the hydrophobic property of the stainless steel surface and avoid the problem that water vapor is condensed into water drops on the stainless steel surface. The preparation method of the heat-resistant super-hydrophobic coating comprises the following steps: 1. firstly, ultrasonically cleaning stainless steel by using acetone, then carrying out alkali cleaning by using NaOH solution, and finally ultrasonically cleaning by using deionized water; 2. carrying out acid washing and activating treatment on the cleaned stainless steel by using HF with the mass fraction of 10%; 3. soaking the stainless steel subjected to surface activation treatment into a rare earth metal salt or hafnium salt water solution for chemical conversion treatment; 4. and (3) placing the stainless steel with the metal oxide deposited on the surface in a vacuum environment with the pressure of <1Pa for treatment to finish the preparation of the heat-resistant super-hydrophobic coating on the surface of the stainless steel. The method provides a method for preparing the super-hydrophobic coating on the surface of the stainless steel, but the coating has no antibacterial property.
Disclosure of Invention
In order to solve the technical problems, the invention provides the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and the preparation method thereof, wherein the surface film layer of the stainless steel is uniform and compact, can effectively prevent pollutants from adhering, and has a self-cleaning function; the film layer has excellent, broad-spectrum and long-acting antibacterial, mildewproof and antiviral effects; the preparation method is efficient and environment-friendly, and can realize zero emission.
In order to achieve the technical effects, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) carrying out electrolytic activation treatment on the pretreated stainless steel to obtain surface activated stainless steel;
(2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) to obtain stainless steel with a deposition layer;
(3) and (3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel.
According to the invention, firstly, pretreatment is carried out, then electrolytic activation is carried out to remove a passivation film, meanwhile, antibacterial components are loaded, then, electrochemical deposition and heating oxidation are carried out to prepare a micro-nano structure on the surface of stainless steel, and finally, low-surface-energy substance modification treatment is carried out.
As a preferable technical scheme of the invention, the pretreatment in the step (1) comprises alkali washing oil removal and water washing.
As a preferable embodiment of the present invention, the composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) includes, in terms of mass percentage:
the mass% of the antibacterial agent may be 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%, the mass% of the activator may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, the mass% of the accelerator may be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%, and the mass% of the activator may be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
In the invention, the antibacterial agent is added into the electrolytic activation solution, and the effective antibacterial component is loaded on the surface while the passivation film is removed and the metal crystalline structure is exposed to provide a good surface state for the subsequent process, so that the film layer has the functions of antibiosis, mildew prevention, antivirus and the like.
Preferably, the antimicrobial agent comprises any one of silver nitrate, silver sulfate or cerium nitrate, or a combination of at least two of these, typical but non-limiting examples being: a combination of silver nitrate and silver sulfate, a combination of silver sulfate and cerium nitrate, a combination of cerium nitrate and silver nitrate, or a combination of silver nitrate, silver sulfate and cerium nitrate, and the like.
Preferably, the activator comprises any one of, or a combination of at least two of, sulfuric acid, phosphoric acid, boric acid, citric acid or oxalic acid, typical but non-limiting examples of which are: a combination of sulfuric acid and phosphoric acid, a combination of phosphoric acid and boric acid, a combination of boric acid and citric acid, a combination of oxalic acid and sulfuric acid, or a combination of sulfuric acid, phosphoric acid, and boric acid, and the like.
Preferably, the accelerator comprises any one of, or a combination of at least two of, ammonium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate or disodium ethylenediaminetetraacetate, typical but non-limiting examples of which are: a combination of ammonium sulfate and disodium hydrogen phosphate, a combination of disodium hydrogen phosphate and dipotassium hydrogen phosphate, a combination of dipotassium hydrogen phosphate and disodium ethylenediaminetetraacetate, a combination of ammonium sulfate and disodium ethylenediaminetetraacetate, or a combination of ammonium sulfate, disodium hydrogen phosphate and dipotassium hydrogen phosphate, and the like.
Preferably, the active agent comprises sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
As a preferable technical scheme of the invention, the current density of the electrolytic activation in the step (1) is 0.1-10A/dm2E.g. 0.2A/dm2、0.5A/dm2、1A/dm2、2A/dm2、3A/dm2、4A/dm2、5A/dm2、6A/dm2、7A/dm2、8A/dm2Or 9A/dm2And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the voltage for the electrolytic activation in step (1) is 0.1-5V, such as 0.2V, 0.5V, 1V, 1.5V, 2V, 2.5V, 3V, 3.5V, 4V or 4.5V, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature for the electrolytic activation in step (1) is 15 to 35 ℃, such as 16 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃ or 34 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time for electrolytic activation in step (1) is 1-10 min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the deposition solution for electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1-3% of soluble metal salt;
5-15% of a complexing agent;
3-10% of alkali;
the balance being water.
The mass percentage of the soluble metal salt may be 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, or 2.8%, the mass percentage of the complexing agent may be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%, and the mass percentage of the base may be 4%, 5%, 6%, 7%, 8%, or 9%, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
According to the invention, the electrolyte in the bath solution can be dispersed and distributed under the action of constant-temperature magnetic stirring, the film is more uniform, and then the electrolyte is heated and oxidized to generate oxide particles on the surface, so that a micro-nano structure is obtained, the surface free energy is reduced, and the surface hydrophobicity is improved.
Preferably, the soluble metal salt comprises any one of copper sulphate, zinc sulphate or nickel sulphate, or a combination of at least two of these, typical but non-limiting examples being: combinations of copper sulfate and zinc sulfate, zinc sulfate and nickel sulfate, nickel sulfate and copper sulfate, or copper sulfate, zinc sulfate and nickel sulfate, and the like.
Preferably, the complexing agent comprises any one of, or a combination of at least two of, potassium sodium tartrate, sodium pyrophosphate, potassium pyrophosphate or sodium citrate, typical but non-limiting examples of which are: sodium potassium tartrate and sodium pyrophosphate, sodium pyrophosphate and potassium pyrophosphate, potassium pyrophosphate and sodium citrate, sodium citrate and sodium potassium tartrate, or potassium sodium tartrate, sodium pyrophosphate and potassium pyrophosphate, and the like.
Preferably, the base comprises sodium hydroxide.
As a preferable technical scheme of the invention, the current density of the electrochemical deposition in the step (2) is 1-100 mA/dm2E.g. 2mA/dm2、5mA/dm2、10mA/dm2、20mA/dm2、30mA/dm2、40mA/dm2、50mA/dm2、60mA/dm2、70mA/dm2、80mA/dm2Or 90mA/dm2And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the voltage of the electrochemical deposition in step (2) is 0.1-2V, such as 0.2V, 0.5V, 0.8V, 1V, 1.2V, 1.5V or 1.8V, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the electrochemical deposition in step (2) is 25-75 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the electrochemical deposition in step (2) is 40-60 min, such as 42min, 45min, 48min, 50min, 52min, 55min or 58min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the electrochemical deposition in step (2) is performed under stirring at a rate of 60 to 150rpm, such as 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, and the like, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.1-1% of a low surface energy compound;
0.05-15% of a coupling agent;
the balance being solvent.
The mass percentage of the low surface energy compound may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%, and the mass percentage of the coupling agent may be 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, or 14%, but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
According to the invention, stainless steel is placed in low surface energy fluorine-free modification liquid added with a coupling agent for modification treatment and then is dried and cured to obtain the super-hydrophobic self-cleaning surface, and the addition of the coupling agent can improve the binding force between a modified substance and a metal matrix, improve the compactness of a film layer and enhance the durability of the film layer.
Preferably, the low surface energy compound comprises any one of stearic acid, myristic acid, oleic acid or hydrogen-containing silicone oil, or a combination of at least two of these, typical but non-limiting examples being: combinations of stearic acid and myristic acid, myristic acid and oleic acid, oleic acid and hydrogen-containing silicone oil, hydrogen-containing silicone oil and stearic acid, or stearic acid, myristic acid and oleic acid, and the like.
Preferably, the coupling agent comprises any one of KH550, KH602, KH792 or KH570, or a combination of at least two of these, typical but non-limiting examples being: a combination of KH550 and KH602, a combination of KH602 and KH792, a combination of KH792 and KH570, a combination of KH570 and KH550, a combination of KH550, KH602 and KH792, or the like.
Preferably, the solvent comprises any one of ethanol, methanol or ethylene glycol or a combination of at least two of the following typical but non-limiting examples: a combination of ethanol and methanol, a combination of methanol and ethylene glycol, a combination of ethylene glycol and ethanol, or a combination of ethanol, methanol, and ethylene glycol, and the like.
In a preferred embodiment of the present invention, the temperature of the thermal oxidation in the step (3) is 100 to 200 ℃, for example, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or 190 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the time for the thermal oxidation in step (3) is 1 to 2 hours, such as 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature for the soaking modification in step (3) is 40-60 ℃, such as 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃ or 58 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the soaking modification time in the step (3) is 12-36 h, such as 13h, 15h, 18h, 21h, 24h, 27h, 30h, 33h or 35h, but not limited to the recited values, and other values in the range of the recited values are also applicable.
Preferably, the temperature of the drying treatment in step (3) is 60 to 80 ℃, such as 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 78 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time in step (3) is 30-90 min, such as 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min or 85min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the preparation method of the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel comprises the following steps:
(1) carrying out electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 0.1-10A/dm2The voltage is 0.1-5V, the temperature is 15-35 ℃, and the time is 1-10 min, so as to obtain the surface activated stainless steel;
(2) carrying out electrochemical deposition treatment on the surface activated stainless steel obtained in the step (1) under stirring, wherein the current density of the electrochemical deposition is 1-100 mA/dm2The voltage is 0.1-2V, the temperature is 25-75 ℃, the time is 40-60 min, and the stirring speed is 60-150 rpm, so that the stainless steel with the deposited layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 100-200 ℃, and the time is 1-2 h; the temperature of the soaking modification is 40-60 ℃, and the time is 12-36 h; the drying temperature is 60-80 ℃, and the drying time is 30-90 min.
The invention also aims to provide the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which is prepared by any one of the preparation methods of the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof, wherein the static contact angle of the super-hydrophobic surface of the stainless steel can reach more than 150 degrees, the rolling angle is less than 8 degrees, the surface film layer is uniform and compact, the adhesion of pollutants can be effectively prevented, and the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel has a self-cleaning function;
(2) the invention provides a fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof, wherein a film layer of the stainless steel has excellent, broad-spectrum and long-acting antibacterial mildew-proof antiviral effects; (3) the invention provides fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and a preparation method thereof.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 0.1A/dm2The voltage is 0.1V, the temperature is 15 ℃, and the time is 10min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface activated stainless steel of the step (1) to electrochemical deposition treatment under stirring, wherein the current density of the electrochemical deposition is 1mA/dm2The voltage is 0.1V, the temperature is 25 ℃, the time is 60min, and the stirring speed is 60rpm, so that the stainless steel with the deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 100 ℃, and the time is 2 h; the temperature of the soaking modification is 40 ℃, and the time is 36 h; the drying temperature is 60 ℃ and the drying time is 90 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1% of copper sulfate;
5% of potassium sodium tartrate;
3% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.1 percent of stearic acid;
KH550 0.05％；
the balance of ethanol.
Example 2
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 10A/dm2The voltage is 5V, the temperature is 35 ℃, and the time is 1min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface-activated stainless steel of step (1) to an electrochemical deposition treatment with stirring, the electrochemical deposition having a current density of 100mA/dm2The voltage is 2V, the temperature is 75 ℃, the time is 40min, the stirring speed is 150rpm, and the stainless steel with a deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 200 ℃, and the time is 1 h; the temperature of the soaking modification is 60 ℃, and the time is 12 hours; the drying temperature is 80 deg.C, and the drying time is 30 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
3 percent of zinc sulfate;
15% of sodium pyrophosphate;
10% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
1% of myristic acid;
KH602 15％；
the balance being methanol.
Example 3
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 1A/dm2The voltage is 1V, the temperature is 20 ℃, and the time is 8min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface-activated stainless steel of step (1) to an electrochemical deposition treatment with stirring, wherein the current density of the electrochemical deposition is 10mA/dm2The voltage is 0.5V, the temperature is 35 ℃, the time is 55min, and the stirring speed is 80rpm, so that the stainless steel with the deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 120 ℃, and the time is 1.8 h; the temperature of the soaking modification is 45 ℃, and the time is 30 hours; the drying temperature is 65 ℃ and the drying time is 75 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
1.5 percent of nickel sulfate;
8% of potassium pyrophosphate;
5% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.5 percent of oleic acid;
KH792 1.5％；
the balance being ethylene glycol.
Example 4
The embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
the embodiment provides a preparation method of fluorine-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel, which comprises the following steps:
(1) performing electrolytic activation treatment on the pretreated stainless steel, wherein the current density of the electrolytic activation is 8A/dm2The voltage is 4V, the temperature is 30 ℃, and the time is 8min, so as to obtain the surface activated stainless steel;
(2) subjecting the surface activated stainless steel of step (1) to electrochemical deposition treatment under stirring, wherein the current density of the electrochemical deposition is 80mA/dm2The voltage is 1V, the temperature is 60 ℃, the time is 45min, and the stirring speed is 120rpm, so that the stainless steel with the deposition layer is obtained;
(3) sequentially heating, oxidizing, soaking, modifying and drying the stainless steel with the deposition layer obtained in the step (2) to obtain the fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel;
wherein the temperature of the heating oxidation is 180 ℃, and the time is 1.2 h; the temperature of the soaking modification is 55 ℃, and the time is 18 h; the drying temperature is 75 ℃ and the drying time is 40 min.
The composition of the electrolytic activation solution used in the electrolytic activation treatment in the step (1) comprises the following components in percentage by mass:
the deposition solution obtained by the electrochemical deposition in the step (2) comprises the following components in percentage by mass:
2 percent of copper sulfate;
10% of sodium citrate;
7% of sodium hydroxide;
the balance being water.
The soaking solution used for soaking modification in the step (3) comprises the following components in percentage by mass:
0.5 percent of hydrogen-containing silicone oil;
KH570 10％；
the balance of ethanol.
Comparative example 1
This comparative example was carried out under the same conditions as in example 4 except that the electrolytic activation treatment of step (1) was not carried out.
Comparative example 2
In this comparative example, the same conditions as in example 4 were used except that silver nitrate was not added to the electrolytic activation solution in step (1) and that an equivalent amount of silver nitrate was added to the immersion solution.
Comparative example 3
This comparative example was conducted under the same conditions as in example 4 except that the heat oxidation treatment was not conducted in step (3).
The static contact angle and the rolling angle of the surfaces of the stainless steels prepared in examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in table 1.
Static contact angle and rolling angle were measured using a video contact angle measuring instrument model OCA 15Pro from Datapysics.
TABLE 1
The stainless steels prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for their antibacterial, antifungal and antiviral properties, and the results are shown in table 2.
And (3) testing antibacterial performance: the antibacterial rate of Escherichia coli and Staphylococcus aureus is tested according to GB/T21510-.
And (3) testing the mildew resistance: refer to GB/T24346-2009 evaluation of mildew resistance of textiles.
And (3) testing antiviral performance: the anti-H1N 1 and H3N2 influenza virus rates are detected by referring to ISO18184:2014(E) textile anti-virus performance test method.
TABLE 2
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110050185.7A CN112853420B (en) | 2021-01-14 | 2021-01-14 | A kind of fluorine-free super-hydrophobic self-cleaning antibacterial anti-mildew anti-virus stainless steel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110050185.7A CN112853420B (en) | 2021-01-14 | 2021-01-14 | A kind of fluorine-free super-hydrophobic self-cleaning antibacterial anti-mildew anti-virus stainless steel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112853420A true CN112853420A (en) | 2021-05-28 |
| CN112853420B CN112853420B (en) | 2022-05-24 |
Family
ID=76006109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110050185.7A Expired - Fee Related CN112853420B (en) | 2021-01-14 | 2021-01-14 | A kind of fluorine-free super-hydrophobic self-cleaning antibacterial anti-mildew anti-virus stainless steel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112853420B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113737239A (en) * | 2021-08-30 | 2021-12-03 | 凯瑞电子(诸城)有限公司 | Liquid formula for preventing pressure sensor metal shell from being oxidized and treatment process |
| CN116159724A (en) * | 2022-12-13 | 2023-05-26 | 安徽同曦高科新材料股份有限公司 | Stainless steel material surface antibacterial and antiviral modification method |
| CN116369318A (en) * | 2023-01-12 | 2023-07-04 | 上海心尔新材料科技股份有限公司 | Long-acting disinfection and sterilization solid material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088297A (en) * | 2015-07-09 | 2015-11-25 | 吉林大学 | Preparation method of bionic oil-water separation copper net |
| KR20160041713A (en) * | 2014-10-08 | 2016-04-18 | 포항공과대학교 산학협력단 | Electrochemical modifying method for stainless steel |
| CN106835219A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
| CN107523817A (en) * | 2017-08-25 | 2017-12-29 | 华南理工大学 | A kind of preparation method of the controllable super-hydrophobic film layer of surface wettability |
| CN110359044A (en) * | 2019-08-14 | 2019-10-22 | 重庆大学 | A kind of preparation method of steel matrix surface ultra-hydrophobic water film |
| CN110724992A (en) * | 2019-09-27 | 2020-01-24 | 江苏科技大学 | Method for preparing corrosion-resistant super-hydrophobic film on surface of aluminum alloy |
| CN112030208A (en) * | 2020-09-02 | 2020-12-04 | 中国石油大学(华东) | Method for preparing super-hydrophobic nickel disulfide coating on surface of stainless steel mesh |
| CN112160001A (en) * | 2020-09-25 | 2021-01-01 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral oxidized stainless steel and preparation method thereof |
-
2021
- 2021-01-14 CN CN202110050185.7A patent/CN112853420B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160041713A (en) * | 2014-10-08 | 2016-04-18 | 포항공과대학교 산학협력단 | Electrochemical modifying method for stainless steel |
| CN105088297A (en) * | 2015-07-09 | 2015-11-25 | 吉林大学 | Preparation method of bionic oil-water separation copper net |
| CN106835219A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
| CN107523817A (en) * | 2017-08-25 | 2017-12-29 | 华南理工大学 | A kind of preparation method of the controllable super-hydrophobic film layer of surface wettability |
| CN110359044A (en) * | 2019-08-14 | 2019-10-22 | 重庆大学 | A kind of preparation method of steel matrix surface ultra-hydrophobic water film |
| CN110724992A (en) * | 2019-09-27 | 2020-01-24 | 江苏科技大学 | Method for preparing corrosion-resistant super-hydrophobic film on surface of aluminum alloy |
| CN112030208A (en) * | 2020-09-02 | 2020-12-04 | 中国石油大学(华东) | Method for preparing super-hydrophobic nickel disulfide coating on surface of stainless steel mesh |
| CN112160001A (en) * | 2020-09-25 | 2021-01-01 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral oxidized stainless steel and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 于守武等: "《高分子材料改性 原理及技术》", 31 May 2015, 知识产权出版社 * |
| 张允诚: "《电镀手册 第3版》", 31 January 2007, 国防工业出版社 * |
| 张莉等: "《强化冷凝传热界面调控技术》", 31 December 2017, 华东理工大学出版社 * |
| 胡明辉: "《电镀企业现场管理与技术》", 30 September 2012, 国防工业出版社 * |
| 黄家强: ""基于阳极氧化的430抗菌不锈钢制备研究"", 《工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113737239A (en) * | 2021-08-30 | 2021-12-03 | 凯瑞电子(诸城)有限公司 | Liquid formula for preventing pressure sensor metal shell from being oxidized and treatment process |
| CN116159724A (en) * | 2022-12-13 | 2023-05-26 | 安徽同曦高科新材料股份有限公司 | Stainless steel material surface antibacterial and antiviral modification method |
| CN116369318A (en) * | 2023-01-12 | 2023-07-04 | 上海心尔新材料科技股份有限公司 | Long-acting disinfection and sterilization solid material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112853420B (en) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112853420A (en) | Fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and preparation method thereof | |
| CN105368304B (en) | Anticorrosive paint and preparation method thereof | |
| JP3295404B2 (en) | Coating for improved resin dust resistance | |
| EP3385405B1 (en) | Chromium-free surface-treated tinplate, production method and surface treating agent therefor | |
| CN105256342B (en) | A kind of super hydrophobic surface based on copper and preparation method thereof | |
| Shabani-Nooshabadi et al. | Electrosynthesis of a polyaniline/zeolite nanocomposite coating on copper in a three-step process and the effect of current density on its corrosion protection performance | |
| JP5809351B2 (en) | Surface treatment agent for autodeposition type copper and method for producing copper-containing substrate with resin film | |
| US20080169199A1 (en) | Trivalent chromium electroplating solution and an electroplating process with the solution | |
| WO2020034929A1 (en) | Anti-oxidation electrochemical treatment method for copper material | |
| CN102634805B (en) | Method for preparing magnesium alloy with super-hydrophobic layer on surface | |
| CN112144273A (en) | Preparation method of multifunctional fabric surface with super-hydrophobic and conductive functions | |
| WO2014042412A1 (en) | Method for surface-treating copper foil and copper foil surface-treated thereby | |
| CN110783025B (en) | A kind of anti-oxidation conductive copper nanowire film and its preparation method and application | |
| CN101942654A (en) | Method for immersing superhydrophobic surface of aluminum alloy in one step | |
| CN105862093A (en) | Method for electroplating Ni-Cr-PTFE composite coating in ionic liquid | |
| CN109385630B (en) | One-step preparation process of zinc-based coating super-hydrophobic functional surface | |
| US20080156652A1 (en) | Cyanide-free pre-treating solution for electroplating copper coating layer on zinc alloy surface and a pre-treating method thereof | |
| CN112458502A (en) | Electroplating method of ultrathin coating for neodymium iron boron | |
| JP2008202118A (en) | Method of modifying anodic oxide film | |
| CN104726875A (en) | Method for preparation of super-hydrophobic CuO film on steel surface | |
| CN101537490B (en) | Preparation method of nickel-phosphorus alloy-coated iron powder | |
| CN109023460A (en) | A kind of method of magnesium lithium alloy electroplating surface zinc | |
| CN112813468A (en) | Preparation method of super-hydrophobic double-layer anti-corrosion coating | |
| CN110184636B (en) | Method for preparing hydrotalcite film on aluminum surface in situ by multi-potential step method | |
| CN107190295A (en) | A kind of super-double-hydrophobic surface of conductive material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221108 Address after: 233705 No. 601, Weiliu Road, economic development zone, Guzhen County, Bengbu City, Anhui Province Patentee after: Anhui Tongxi hi tech new material Co.,Ltd. Address before: 211100 No. 1355 Shuanglong Avenue, Jiangning District, Nanjing City, Jiangsu Province Patentee before: TONGXI GROUP Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220524 |