CN114540894B - Sterilizing wear-resistant corrosion-resistant composite coating, preparation method thereof and sterilizing wear-resistant corrosion-resistant product - Google Patents
Sterilizing wear-resistant corrosion-resistant composite coating, preparation method thereof and sterilizing wear-resistant corrosion-resistant product Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 139
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 111
- 230000007797 corrosion Effects 0.000 title claims abstract description 66
- 238000005260 corrosion Methods 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 214
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 107
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 78
- 238000009713 electroplating Methods 0.000 claims abstract description 67
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 65
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 56
- 239000011651 chromium Substances 0.000 claims abstract description 56
- 238000007747 plating Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- LGPJVNLAZILZGQ-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](C)(C)C LGPJVNLAZILZGQ-UHFFFAOYSA-M 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 13
- 239000010410 layer Substances 0.000 description 156
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- 238000000089 atomic force micrograph Methods 0.000 description 22
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- 230000000007 visual effect Effects 0.000 description 12
- 229940107816 ammonium iodide Drugs 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
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- 241000588724 Escherichia coli Species 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AWEPEDSCQSZNCM-UHFFFAOYSA-M benzyl-dimethyl-octadecylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 AWEPEDSCQSZNCM-UHFFFAOYSA-M 0.000 description 2
- XFBTWIOCKNNLEK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XFBTWIOCKNNLEK-UHFFFAOYSA-M 0.000 description 2
- NIIMYDPJFSPDMS-UHFFFAOYSA-M benzyl-dodecyl-dimethylazanium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 NIIMYDPJFSPDMS-UHFFFAOYSA-M 0.000 description 2
- UYUFIKCFKMFRBU-UHFFFAOYSA-M benzyl-hexadecyl-dimethylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 UYUFIKCFKMFRBU-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YIFWXQBNRQNUON-UHFFFAOYSA-M dodecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+](C)(C)C YIFWXQBNRQNUON-UHFFFAOYSA-M 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
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- HIACZXUUKNSHAN-UHFFFAOYSA-M trimethyl(octadecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C HIACZXUUKNSHAN-UHFFFAOYSA-M 0.000 description 2
- AXRFZYRPSHSKBF-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCC[N+](C)(C)C AXRFZYRPSHSKBF-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- 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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/16—Electroplating with layers of varying thickness
-
- 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
-
- 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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
Abstract
A sterilization wear-resistant corrosion-resistant composite coating, a preparation method thereof and a sterilization wear-resistant corrosion-resistant product, wherein the sterilization wear-resistant corrosion-resistant composite coating comprises: the full gloss nickel layer, the microporous nickel layer and the decorative chromium composite sterilization layer are sequentially arranged on the base material; the decorative chromium composite sterilization layer and the microporous nickel layer are respectively provided with a nano needle structure, and are respectively formed by a first composite raw material containing a first bactericidal ammonium salt and a second composite raw material containing a second bactericidal ammonium salt, and the concentration of the first bactericidal ammonium salt in the first composite raw material is 50-The concentration of the second bactericidal ammonium salt in the second composite raw material is 100g/L and 50-100g/L. The sterilizing, wear-resisting and corrosion-resisting composite plating can be obtained only by a single electroplating method, has a good sterilizing effect, and does not need to be sprayed with nano Ag + 、Cu 2+ And can realize the effects of wear resistance and high corrosion resistance.
Description
Technical Field
The application relates to the field of sterilization and corrosion-resistant materials, in particular to a sterilization, wear-resistant and corrosion-resistant composite coating, a preparation method thereof and a sterilization, wear-resistant and corrosion-resistant product.
Background
Bacteria are a microorganism that is widely present in nature and is almost ubiquitous. Some pathogenic bacteria in bacteria can cause human body to infect various diseases, thereby threatening the health of human body. Along with the outbreak of new coronal pneumonia epidemic situation, the development of the large health industry is highly emphasized worldwide, and especially the attention of healthy kitchen and bathroom household products which can be sterilized and antiviral is paid. At present, a microporous nickel composite plating layer formed by electroplating a full gloss nickel layer, a microporous nickel layer and a decorative chromium layer can be adopted as a surface material of large hardware products (such as a shower, a faucet and the like) in kitchen and bathroom houses. Wherein, the formation of the microporous nickel layer can increase the corrosion protection of the plating layer.
Microporous nickel is characterized in that fine particles with poor conductivity are added on the basis of a bright nickel solution, nickel is continuously deposited on a part in the electroplating process, meanwhile, the particles are also brought into a plating layer, and discontinuous small holes (commonly called micropores) penetrating into a nickel layer are finally formed. When the part is corroded, the exposure area of the nickel layer is increased by the existence of the micropores, so that corrosion current is well dispersed, the corrosion current on the unit area of the surface of the part is greatly reduced, the corrosion speed is also reduced, and the concentrated deep strong corrosion is avoided, so that the corrosion resistance effect is achieved.
However, the product with the microporous nickel coating prepared by adopting the electroplating technology can not realize the sterilization and antibacterial functions temporarily,it is also usually necessary to spray a layer of Ag containing nanometer on its surface + 、Cu 2+ Or preparing Ag-containing bactericidal material by PVD technology + /Cu 2+ But Ag + 、Cu 2+ Is easily absorbed by pores of human skin, is unfavorable for human health, and has high cost of plating film by PVD method. In addition, most of the sterilization and antibacterial effects of kitchen and toilet products on the market at present are shown by detection reports of third-party institutions, and visualization cannot be achieved.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the application.
The application provides a sterilization, wear-resistance and corrosion-resistance composite plating layer, a preparation method thereof and a sterilization, wear-resistance and corrosion-resistance product, wherein the sterilization, wear-resistance and corrosion-resistance composite plating layer can be obtained only by a single electroplating method, has a good sterilization effect, and does not need to be sprayed with nano Ag + 、Cu 2+ And can realize the effects of wear resistance and high corrosion resistance.
The application provides a wear-resisting corrosion resistant composite coating disinfects, includes: an all-optical nickel layer, a microporous nickel layer and a decorative chromium composite sterilization layer; the all-optical nickel layer is arranged on a base material with the requirements of sterilization, wear resistance or corrosion resistance, the microporous nickel layer is arranged on the surface of one side of the all-optical nickel layer, which is far away from the base material, and the decorative chromium composite sterilization layer is arranged on the surface of one side of the microporous nickel layer, which is far away from the base material; the decorative chromium composite sterilization layer and the microporous nickel layer are respectively provided with a nano needle structure, and are respectively formed by a first composite raw material containing a first bactericidal ammonium salt and a second composite raw material containing a second bactericidal ammonium salt, wherein the concentration of the first bactericidal ammonium salt in the first composite raw material is 50-100g/L, and the concentration of the second bactericidal ammonium salt in the second composite raw material is 50-100g/L.
In an embodiment of the present application, the first bactericidal ammonium salt and the second bactericidal ammonium salt may each be independently selected from any one or more of alkyl quaternary ammonium iodide salt and alkyl aromatic alkyl quaternary ammonium iodide salt.
In embodiments of the present application, the alkyl groups in the alkyl quaternary ammonium iodide salt and the alkyl aromatic alkyl quaternary ammonium iodide salt may have a carbon chain length of 12 to 18.
In embodiments of the present application, the first bactericidal ammonium salt, the second bactericidal ammonium salt may each be independently selected from any one or more of dodecyl dimethyl benzyl ammonium iodide, dodecyl trimethyl ammonium iodide, tetradecyl dimethyl benzyl ammonium iodide, tetradecyl trimethyl ammonium iodide, hexadecyl dimethyl benzyl ammonium iodide, hexadecyl trimethyl ammonium iodide, octadecyl dimethyl benzyl ammonium iodide, and octadecyl trimethyl ammonium iodide.
In an embodiment of the present application, the raw materials of the decorative chromium composite sterilization layer may include: a first quaternary ammonium iodide salt with a concentration of 50-100g/L, anhydrous citric acid crystals with a concentration of 10-20g/L, sulfuric acid with a concentration of 1-5mL/L, solid chromic acid with a concentration of 200-450g/L, and decorative chromium additive CR 842 with a concentration of 5-15 mL/L.
In an embodiment of the present application, the raw materials of the microporous nickel layer may include: the second quaternary ammonium iodized salt with the concentration of 50-100g/L, anhydrous citric acid crystal with the concentration of 10-20g/L, nickel sulfate with the concentration of 150-400g/L, nickel chloride with the concentration of 60-120g/L, boric acid with the concentration of 30-80g/L, bright nickel ZD-220 with the concentration of 0.1-0.5mL/L, liquid additive MPS 800 with the concentration of 5-80mL/L and liquid additive Mark 904 with the concentration of 0.1-2 mL/L.
In an embodiment of the present application, the raw materials of the all-optical nickel layer may include: nickel sulfate with the concentration of 300-500g/L, nickel chloride with the concentration of 30-80g/L, boric acid with the concentration of 30-80g/L, a cylinder opener NIB-90 with the concentration of 5-10mL/L, a main gloss agent NIB-90 with the concentration of 1-3mL/L and a wetting agent Ni-66B with the concentration of 1-5 mL/L.
In an embodiment of the present application, the bactericidal, wear-resistant and corrosion-resistant composite coating may be silvery white.
In an embodiment of the present application, the thickness of the all-optical nickel layer may be 20-50 μm, the thickness of the microporous nickel layer may be 20-50 μm, and the thickness of the decorative chromium composite sterilization layer may be >0.5 μm.
The application also provides a preparation method of the bactericidal wear-resistant corrosion-resistant composite coating, which comprises the following steps:
(1) Pretreatment of the substrate: including polishing and cleaning treatments;
(2) Electroplating the all-optical nickel layer on the surface of the pretreated substrate;
(3) Electroplating the microporous nickel layer on the surface of the all-optical nickel layer;
(4) Electroplating the decorative chromium composite sterilization layer on the surface of the microporous nickel layer.
In an embodiment of the present application, the conditions for electroplating the all-optical nickel layer in step (2) may include: the temperature is 40-60 ℃, and the cathode current density is 3.5-10A/dm 2 The electroplating time is 600-2400s.
In an embodiment of the present application, the conditions for electroplating the microporous nickel layer in step (3) may include: the temperature is 40-60 ℃, and the cathode current density is 3-8A/dm 2 The electroplating time is 600-1800s.
In an embodiment of the present application, the conditions for electroplating the decorative chromium composite sterilization layer in step (4) may include: the temperature is 40-60 ℃, and the cathode current density is 5-20A/dm 2 The electroplating time is 300-900s.
The application also provides a sterilizing, wear-resisting and corrosion-resisting product, which comprises a base material and the sterilizing, wear-resisting and corrosion-resisting composite plating layer.
In embodiments of the present application, the substrate may be a metal substrate or a plastic substrate.
In an embodiment of the present application, the bactericidal abrasion-resistant and corrosion-resistant product is a bactericidal product for a kitchen or a toilet.
The sterilizing, wear-resisting and corrosion-resisting composite plating layer comprises an all-optical nickel layer, a microporous nickel layer and a decorative chromium composite sterilization layer, wherein the raw materials for forming the decorative chromium composite sterilization layer comprise sterilizing ammonium salt, so that the decorative chromium composite sterilization layer has a sterilization effect, the decorative chromium composite sterilization layer forms a nano needle structure, and the sterilization effect of the sterilizing, wear-resisting and corrosion-resisting composite plating layer is further enhanced; in addition, the raw materials for forming the microporous nickel layer can also comprise bactericidal ammonium salt, the microporous nickel layer can also form a nano needle structure, so that the bactericidal effect of the bactericidal wear-resistant corrosion-resistant composite plating layer can be further enhanced, and when the decorative chromium composite bactericidal layer on the surface layer is worn, the microporous nickel layer on the inner layer also has the bactericidal effect, and the bactericidal effect of the whole product is better and durable.
In addition, the sterilizing, wear-resisting and corrosion-resisting composite plating layer can obtain a good sterilizing effect only by a single electroplating method without spraying Ag-containing coating + 、Cu 2+ Preparation of Ag-containing composite material by PVD technique + /Cu 2+ Is a composite material of (a); in a word, the sterilizing wear-resistant corrosion-resistant composite coating provided by the embodiment of the application is low in cost, simple to prepare, and has a rapid and broad-spectrum sterilizing effect, and the sterilizing effect can be directly displayed through a high-definition display technology. In addition, the sterilization, wear resistance and corrosion resistance composite coating provided by the embodiment of the application also has the advantage of high corrosion resistance.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. Other advantages of the present application may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The accompanying drawings are included to provide an understanding of the technical aspects of the present application, and are incorporated in and constitute a part of this specification, illustrate the technical aspects of the present application and together with the examples of the present application, and not constitute a limitation of the technical aspects of the present application.
Fig. 1 is a schematic front view of a structure of a bactericidal, wear-resistant and corrosion-resistant composite coating according to an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of a microporous nickel layer of the bactericidal, wear-resistant and corrosion-resistant composite coating of example 1 of the present application;
FIG. 3 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the bactericidal, wear-resistant and corrosion-resistant product of example 1 of the present application;
FIG. 4 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 1 of the present application;
FIG. 5 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 2 of the present application;
FIG. 6 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 3 of the present application;
FIG. 7 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 4 of the present application;
FIG. 8 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 5 of the present application;
FIG. 9 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 6 of the present application;
FIG. 10 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 7 of the present application;
FIG. 11 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 8 of the present application;
FIG. 12 is an Atomic Force Microscope (AFM) image of the surface morphology of the semifinished product obtained in step (3) of example 1 of the present application;
FIG. 13 is a graph of experimental operation of the product of the example of the present application for 20000 times of friction;
FIG. 14 is a real-time visual microscope image of the bactericidal, wear-resistant and corrosion-resistant product of example 1 of the present application after 20000 times of friction, the left image is a visual microscope image of the surface of the bacteria resting sample after 2 minutes and starting to count time (1 s), and the right image is a visual microscope image of the surface of the bacteria resting sample after 2 minutes and starting to count time (2 s);
fig. 15 is a real-time visual microscope image of the comparative example 5 of the present application after 20000 times of friction, the upper image is a visual microscope image of the surface of the bacteria resting sample after 2 minutes and starting the time counting (1 s), and the lower image is a visual microscope image of the surface of the bacteria resting sample after 2 minutes and starting the time counting at 2 s.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail hereinafter with reference to the accompanying drawings. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.
The embodiment of the application provides a composite coating with sterilization, wear resistance and corrosion resistance, as shown in fig. 1, the composite coating with sterilization, wear resistance and corrosion resistance comprises: an all-optical nickel layer 10, a microporous nickel layer 20 and a decorative chromium composite sterilization layer 30; the all-optical nickel layer 10 is arranged on a substrate 100 with the requirements of sterilization, wear resistance or corrosion resistance, the microporous nickel layer 20 is arranged on the surface of the all-optical nickel layer 10, which is far away from the substrate 100, the microporous nickel layer 20 is provided with micropores 21, and the decorative chromium composite sterilization layer 30 is arranged on the surface of the microporous nickel layer 20, which is far away from the substrate 100;
the decorative chromium composite sterilization layer 30 and the microporous nickel layer 20 respectively have nanoneedle structures 31 and 22, are respectively formed by a first composite raw material containing a first bactericidal ammonium salt and a second composite raw material containing a second bactericidal ammonium salt, and the concentration of the first bactericidal ammonium salt in the first composite raw material is 50-100g/L, and the concentration of the second bactericidal ammonium salt in the second composite raw material is 50-100g/L.
The sterilizing, wear-resisting and corrosion-resisting composite plating layer comprises an all-optical nickel layer, a microporous nickel layer and a decorative chromium composite sterilization layer, wherein the raw materials for forming the decorative chromium composite sterilization layer comprise sterilizing ammonium salt, so that the decorative chromium composite sterilization layer has a sterilization effect, the decorative chromium composite sterilization layer forms a nano needle structure, and the sterilization effect of the sterilizing, wear-resisting and corrosion-resisting composite plating layer is further enhanced; in addition, the raw materials for forming the microporous nickel layer can also comprise bactericidal ammonium salt, the microporous nickel layer can also form a nano needle structure, so that the bactericidal effect of the bactericidal wear-resistant corrosion-resistant composite plating layer can be further enhanced, and when the decorative chromium composite bactericidal layer on the surface layer is worn, the microporous nickel layer on the inner layer also has the bactericidal effect, and the bactericidal effect of the whole product is better and durable.
In addition, the sterilizing, wear-resisting and corrosion-resisting composite plating layer can obtain a good sterilizing effect only by a single electroplating method without spraying Ag-containing coating + 、Cu 2+ Preparation of Ag-containing composite material by PVD technique + /Cu 2+ Is a composite material of (a); in a word, the sterilizing wear-resistant corrosion-resistant composite coating provided by the embodiment of the application has low cost, is simple to prepare, has rapid and broad-spectrum sterilizing effect, and can realize the sterilizing effectAnd the display is directly displayed by a high-definition display technology. In addition, the sterilization, wear resistance and corrosion resistance composite coating provided by the embodiment of the application also has the advantage of high corrosion resistance.
In the sterilization, wear-resistance and corrosion-resistance composite plating layer of the embodiment of the application, potential difference can be formed between the full-gloss nickel layer and the microporous nickel layer, so that the effect of high corrosion resistance is obtained.
In an embodiment of the present application, the first bactericidal ammonium salt and the second bactericidal ammonium salt may each be independently selected from any one or more of alkyl quaternary ammonium iodide salt and alkyl aromatic alkyl quaternary ammonium iodide salt.
In embodiments of the present application, the alkyl groups in the alkyl quaternary ammonium iodide salt and the alkyl aromatic alkyl quaternary ammonium iodide salt may have a carbon chain length of 12 to 18.
In embodiments of the present application, the first bactericidal ammonium salt, the second bactericidal ammonium salt may each be independently selected from any one or more of dodecyl dimethyl benzyl ammonium iodide, dodecyl trimethyl ammonium iodide, tetradecyl dimethyl benzyl ammonium iodide, tetradecyl trimethyl ammonium iodide, hexadecyl dimethyl benzyl ammonium iodide, hexadecyl trimethyl ammonium iodide, octadecyl dimethyl benzyl ammonium iodide, and octadecyl trimethyl ammonium iodide.
In an embodiment of the present application, the raw materials of the decorative chromium composite sterilization layer may include: a first quaternary ammonium iodide salt with a concentration of 50-100g/L, anhydrous citric acid crystals with a concentration of 10-20g/L, sulfuric acid with a concentration of 1-5mL/L, solid chromic acid with a concentration of 200-450g/L, and decorative chromium additive CR 842 with a concentration of 5-15 mL/L.
In an embodiment of the present application, the raw materials of the microporous nickel layer may include: the second quaternary ammonium iodized salt with the concentration of 50-100g/L, anhydrous citric acid crystal with the concentration of 10-20g/L, nickel sulfate with the concentration of 150-400g/L, nickel chloride with the concentration of 60-120g/L, boric acid with the concentration of 30-80g/L, bright nickel ZD-220 with the concentration of 0.1-0.5mL/L, liquid additive MPS 800 with the concentration of 5-80mL/L and liquid additive Mark 904 with the concentration of 0.1-2 mL/L.
In an embodiment of the present application, the raw materials of the all-optical nickel layer may include: nickel sulfate with the concentration of 300-500g/L, nickel chloride with the concentration of 30-80g/L, boric acid with the concentration of 30-80g/L, a cylinder opener NIB-90 with the concentration of 5-10mL/L, a main gloss agent NIB-90 with the concentration of 1-3mL/L and a wetting agent Ni-66B with the concentration of 1-5 mL/L.
In the description of the present application, the concentration (g/L, mL/L) of a certain raw material of the all-optical nickel layer, the microporous nickel layer or the decorative chromium composite sterilization layer refers to the concentration of the raw material in a mixed solution composed of all the raw materials of the all-optical nickel layer, the microporous nickel layer or the decorative chromium composite sterilization layer. The concentration of sulfuric acid is 1-5mL/L, namely the amount of sulfuric acid equivalent to 98 mass percent in the electroplating raw material of the 1L decorative chromium composite sterilization layer is 1-5mL, and of course, other mass fractions of sulfuric acid can be adopted as the raw material, and the amount of sulfuric acid can be converted according to the amount of pure sulfuric acid.
In an embodiment of the present application, the decorative chrome composite sterilization layer may be silvery white, so the sterilization highly corrosion-resistant composite plating layer may be silvery white.
In an embodiment of the present application, the thickness of the all-optical nickel layer may be 20-50 μm, the thickness of the microporous nickel layer may be 20-50 μm, and the thickness of the decorative chromium composite sterilization layer may be >0.5 μm.
The embodiment of the application also provides a preparation method of the sterilization, wear resistance and corrosion resistance composite coating, which comprises the following steps:
(1) Pretreatment of the substrate: including polishing and cleaning treatments;
(2) Electroplating the all-optical nickel layer on the surface of the pretreated substrate;
(3) Electroplating the microporous nickel layer on the surface of the all-optical nickel layer;
(4) Electroplating the decorative chromium composite sterilization layer on the surface of the microporous nickel layer.
In an embodiment of the present application, the cleaning treatment in the pretreatment in step (1) may include a fine cleaning process such as wax removal, oil removal, electrolysis, pure water cleaning, and the like.
In an embodiment of the present application, the conditions for electroplating the all-optical nickel layer in step (2) may include: the temperature is 40-60 ℃, and the cathode current density is 3.5-10A/dm 2 During electroplatingThe interval is 600-2400s.
In an embodiment of the present application, the conditions for electroplating the microporous nickel layer in step (3) may include: the temperature is 40-60 ℃, and the cathode current density is 3-8A/dm 2 The electroplating time is 600-1800s.
In an embodiment of the present application, the conditions for electroplating the decorative chromium composite sterilization layer in step (4) may include: the temperature is 40-60 ℃, and the cathode current density is 5-20A/dm 2 The electroplating time is 300-900s.
The embodiment of the application also provides a sterilizing, wear-resisting and corrosion-resisting product, which comprises a base material and the sterilizing, wear-resisting and corrosion-resisting composite plating layer.
In embodiments of the present application, the substrate may be a metal substrate such as an aluminum alloy, a copper alloy, a zinc alloy, a magnesium alloy, stainless steel, alloy steel, or the like, or a plastic substrate such as ABS, or the like.
In the embodiment of the application, the sterilization, wear-resistant and corrosion-resistant product can be a sterilization product for a kitchen or a bathroom, such as a vegetable basin, a cutter, a faucet, a hand basin, a pendant, a shower room handle, a shower room frame, and the like.
The cylinder opener NIB-90, the main gloss agent NIB-90 and the wetting agent Ni-66B used in the following examples and comparative examples were purchased from Xiamen Huahui New technology Co., ltd., bright nickel ZD-220, liquid additive MPS 800, liquid additive Mark 904 and decorative chromium additive CR 842 were purchased from America (China) chemical Co., ltd., ATOTECH, and cetyltrimethylammonium iodide was purchased from Jin Jinle chemical Co., ltd.
Example 1
(1) Pretreatment for electroplating
Polishing, fine cleaning (including wax removal, oil removal, electrolysis and pure water cleaning) and zinc dipping, copper preplating and other pretreatment are carried out on the magnesium alloy substrate;
(2) Electroplating an all-optical nickel layer on the surface of the pretreated substrate
The plating solution for forming the all-optical nickel layer comprises: nickel sulfate with the concentration of 350g/L, nickel chloride with the concentration of 40g/L, boric acid with the concentration of 45g/L, a cylinder opener NIB-90 with the concentration of 9mL/L, a main gloss agent NIB-90 with the concentration of 1.8mL/L and a wetting agent Ni-66B with the concentration of 2.5 mL/L;
the electroplating process conditions include: the temperature was 55℃and the cathode current density was 6A/dm 2 The electroplating time is 1200s;
(3) Electroplating a microporous nickel layer on the surface of the all-optical nickel layer
The plating solution for forming the microporous nickel layer includes: cetyl trimethyl ammonium iodide with the concentration of 50g/L, anhydrous citric acid crystal with the concentration of 10g/L, nickel sulfate with the concentration of 300g/L, nickel chloride with the concentration of 80g/L, boric acid with the concentration of 45g/L, bright nickel ZD-220 with the concentration of 0.2mL/L, liquid additive MPS 800 with the concentration of 45mL/L and liquid additive Mark 904 with the concentration of 0.4 mL/L;
the electroplating process conditions include: the temperature was 55℃and the cathode current density was 7A/dm 2 The electroplating time is 1200s;
(4) Electroplating decorative chromium composite sterilizing layer on the surface of the microporous nickel layer
The electroplating solution for forming the decorative chromium composite sterilization layer comprises the following components: cetyl trimethyl ammonium iodide with a concentration of 50g/L, anhydrous citric acid crystals with a concentration of 10g/L, sulfuric acid with a concentration of 2.5mL/L, solid chromic acid with a concentration of 350g/L, decorative chromium additive CR 842 with a concentration of 12 mL/L;
the electroplating process conditions include: the temperature was 55℃and the cathode current density was 12A/dm 2 The plating time was 900s.
Example 2
The preparation process was essentially the same as in example 1, except that: the concentration of the hexadecyl trimethyl ammonium iodide in the electroplating liquid adopted in the step (3) of electroplating the microporous nickel layer and in the electroplating liquid adopted in the step (4) of electroplating the decorative chromium composite sterilization layer is 100g/L.
Comparative example 1
The preparation process was essentially the same as in example 1, except that: the concentration of hexadecyl trimethyl ammonium iodide in the electroplating solution adopted in the step (3) of electroplating the microporous nickel layer and in the electroplating solution adopted in the step (4) of electroplating the decorative chromium composite sterilization layer is 150g/L.
Comparative example 2
The preparation process was essentially the same as in example 1, except that: the concentration of hexadecyl trimethyl ammonium iodide in the electroplating liquid adopted in the step (3) of electroplating the microporous nickel layer and in the electroplating liquid adopted in the step (4) of electroplating the decorative chromium composite sterilization layer is 0g/L.
Comparative example 3
The preparation process was essentially the same as in example 1, except that: in the electroplating solution adopted in the step (3) of electroplating the microporous nickel layer, the concentration of the anhydrous crystalline organic citric acid is 0g/L.
Comparative example 4
The preparation process was essentially the same as in example 1, except that: in the electroplating solution adopted in the step (3) of electroplating the microporous nickel layer, the concentration of hexadecyl trimethyl ammonium iodide is 0g/L.
Comparative example 5
The preparation process was essentially the same as in example 1, except that: in the electroplating solution adopted in the step (3) of electroplating the microporous nickel layer, the concentration of the anhydrous crystalline organic citric acid is 0g/L, and the concentration of the hexadecyl trimethyl ammonium iodide is 0g/L.
Comparative example 6
The preparation process was essentially the same as in example 1, except that: in the electroplating solution adopted in the step (4) of electroplating the decorative chromium composite sterilization layer, the concentration of the anhydrous crystalline organic citric acid is 0g/L.
Comparative example 7
The preparation process was essentially the same as in example 1, except that: in the electroplating solution adopted in the step (4) of electroplating the decorative chromium composite sterilization layer, the concentration of hexadecyl trimethyl ammonium iodide is 0g/L.
Comparative example 8
The preparation process was essentially the same as in example 1, except that: in the electroplating solution adopted in the step (4) of electroplating the decorative chromium composite sterilization layer, the concentration of the anhydrous crystalline organic citric acid is 0g/L, and the concentration of the hexadecyl trimethyl ammonium iodide is 0g/L.
And (3) observing the microporous nickel layer formed in the step (3) of the embodiment of the application by using a flying-sodium field emission scanning electron microscope Pharos G2 (resolution of 1.8 nm@15Kv). Fig. 2 is a scanning electron microscope image of the microporous nickel layer of the bactericidal, abrasion-resistant and corrosion-resistant composite coating layer of example 1 of the present application (the morphology of the microporous nickel layers of example 2 and comparative examples 1-8 is similar to that of fig. 2). It can be seen that the plating surface of example 1 forms a microporous nickel layer with micropores.
FIG. 3 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the bactericidal, wear-resistant and corrosion-resistant product of example 1 of the present application; FIG. 4 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 1 of the present application; FIG. 5 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 2 of the present application; FIG. 6 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite coating of the product of comparative example 3 of the present application; fig. 7 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite plating layer of the product of comparative example 4 of the present application. Fig. 8 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite plating layer of the product of comparative example 5 of the present application. Fig. 9 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite plating layer of the product of comparative example 6 of the present application. Fig. 10 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite plating layer of the product of comparative example 7 of the present application. Fig. 11 is an Atomic Force Microscope (AFM) image of the surface morphology of the composite plating layer of the product of comparative example 8 of the present application. The surface morphology Atomic Force Microscope (AFM) image is a decorative chromium composite layer formed in the step (4) by taking the surface on the side far away from the substrate as a test surface.
As can be seen from fig. 3 to 11, the decorative chrome composite layers of the bactericidal, wear-resistant and corrosion-resistant composite coatings of the products of the embodiment 1 and the comparative examples 3 to 5 of the present application form a nano needle structure, wherein the height of the nano needle of the decorative chrome composite bactericidal layer of the embodiment 1 is 20 to 50nm, the nano needle is agglomerated, and a certain interval exists between the agglomerated nano needles; in addition, the decorative chromium composite sterilization layer of the sterilization wear-resistant corrosion-resistant composite plating layer of embodiment 2 of the present application also forms a nanoneedle structure. However, the decorative chromium composite layers of the composite plating layers of comparative examples 1 to 2 and comparative examples 6 to 8 did not form a nanoneedle structure, indicating that formation of the nanoneedle structure requires participation of a quaternary ammonium salt such as cetyltrimethylammonium iodide and the like in a proper concentration and crystallization of anhydrous citric acid.
FIG. 12 is an Atomic Force Microscope (AFM) image of the surface morphology of the semi-finished product obtained in step (3) of example 1 of the present application. The Atomic Force Microscope (AFM) image of the surface morphology is that of a microporous nickel layer as a test surface. It can be seen that the microporous nickel layer of example 1 of the present application does form a nanoneedle structure.
The corrosion resistance of the products of the examples and comparative examples was tested by the CASS salt spray test method according to the Chinese national standard GB/T6461-2002. The test results are shown in Table 1.
The products of examples and comparative examples were tested for their antibacterial properties (tested using E.coli) according to the national standard GB/T21510-2008. The results are shown in Table 1.
The products of examples and comparative examples were rubbed 20000 times according to the chinese national standard GB/T9266-2009 (fig. 13 is an experimental operation chart of the example product rubbed 20000 times), and the surfaces of the examples and comparative examples before and after rubbing (for the example product, placed on the surface of the decorative chrome composite sterilizing layer) on the side far from the substrate were placed with escherichia coli according to the chinese national standard GB/T21510-2008 annex C, and left for 2 minutes, and then the state of bacteria on the surfaces thereof was observed with a double transmission biological microscope.
It was observed that the bacteria on the surface of the sterilized product of the example were stationary before rubbing 20000 times; however, bacteria on the surfaces of the products of comparative examples 1-2 and 6-8 were flowing all the time, and the number of flowing bacteria was almost unchanged. After 20000 times friction, the bacteria on the surface of the sterilized product of examples 1-2 remained still; however, bacteria on the surfaces of the products of comparative examples 1-2 and 6-8 were always flowing, and the number of flowing bacteria was almost unchanged, and bacteria on the surfaces of the products of comparative examples 3-5 also began to flow, because the decorative chromium composite sterilization layer on the surfaces of the products had been worn off, affecting the sterilization effect. Wherein, fig. 14 is a real-time visual microscopic image of the bactericidal abrasion-resistant corrosion-resistant product of example 1 after friction 20000 times, the left image is a visual microscopic image of the bacteria standing on the surface of the sample for 2min and starting to count (1 s), the right image is a visual microscopic image of the bacteria standing on the surface of the sample for 2min and starting to count for 2s, and the state observed by the microscopic image after starting to count for 2s is the same as the state observed by starting to count, so that the bacteria are still, and the bacteria are killed. Fig. 15 is a real-time visual microscopic image of the bactericidal product of comparative example 5 after friction 20000 times, the upper image is a visual microscopic image of the bacteria standing on the surface of the sample for 2min and starting to count time (1 st s), the lower image is a visual microscopic image of the bacteria standing on the surface of the sample for 2min and starting to count time (2 s), wherein the upper image and the lower image have more bacteria flowing (the bacteria position in the circle can be seen to change), and the number of flowing bacteria is almost unchanged.
TABLE 1
It can be seen from examples and comparative examples that the products containing the microporous nickel layer of the examples and comparative examples have high corrosion resistance, and the CASS salt spray effect of the products can reach a level of 48h 9.
As can be seen from comparative examples 1-2 and comparative examples 1-2, when the concentration of hexadecyl trimethyl ammonium iodide is 50-100g/L, the bactericidal composite coating of the product can form a nano needle structure, and the product has a good bactericidal effect. When the concentration of hexadecyl trimethyl ammonium iodide is increased to 150g/L, the sterilizing composite coating of the product does not form a nano needle structure, and the sterilizing of the product on escherichia coli is reduced to 84.2 percent.
As can be seen from comparative examples 1-2 and comparative examples 3-5, compared with the bactericidal, wear-resistant and corrosion-resistant composite plating layers with the nano-needle structure in both the double plating layers (the microporous nickel layer and the decorative chromium composite bactericidal layer), the bactericidal, wear-resistant and corrosion-resistant composite plating layer with the nano-needle structure in the single plating layer (the decorative chromium composite bactericidal layer) has a significantly reduced antibacterial rate after 20000 times of friction, which indicates that the bactericidal, wear-resistant and corrosion-resistant composite plating layers with the nano-needle structure in both the double plating layers have a longer bactericidal effect.
In a word, the sterilization effect of the sterilization, wear resistance and corrosion resistance composite coating can be directly displayed by adopting a double-transmission high-definition display technology, and the sterilization effect of the sterilization, wear resistance and corrosion resistance composite coating with the nano needle structure on both double coatings is obviously superior to that of the sterilization, wear resistance and corrosion resistance composite coating with the nano needle structure on a single coating.
Although the embodiments disclosed in the present application are described above, the embodiments are only used for facilitating understanding of the present application, and are not intended to limit the present application. Any person skilled in the art to which this application pertains will be able to make any modifications and variations in form and detail of implementation without departing from the spirit and scope of the disclosure, but the scope of the application is still subject to the scope of the claims appended hereto.
Claims (10)
1. A bactericidal, wear resistant and corrosion resistant composite coating, comprising: an all-optical nickel layer, a microporous nickel layer and a decorative chromium composite sterilization layer; the all-optical nickel layer is arranged on a base material with the requirements of sterilization, wear resistance or corrosion resistance, the microporous nickel layer is arranged on the surface of one side of the all-optical nickel layer, which is far away from the base material, and the decorative chromium composite sterilization layer is arranged on the surface of one side of the microporous nickel layer, which is far away from the base material; the decorative chromium composite sterilization layer and the microporous nickel layer are both provided with a nano needle structure;
wherein, the raw materials of the decorative chromium composite sterilization layer comprise: cetyl trimethyl ammonium iodide with the concentration of 50-100g/L, anhydrous citric acid crystal with the concentration of 10-20g/L, sulfuric acid with the concentration of 1-5mL/L, solid chromic acid with the concentration of 200-450g/L and decorative chromium additive CR 842 with the concentration of 5-15 mL/L;
the microporous nickel layer comprises the following raw materials: cetyl trimethyl ammonium iodide with the concentration of 50-100g/L, anhydrous citric acid crystal with the concentration of 10-20g/L, nickel sulfate with the concentration of 150-400g/L, nickel chloride with the concentration of 60-120g/L, boric acid with the concentration of 30-80g/L, bright nickel ZD-220 with the concentration of 0.1-0.5mL/L, liquid additive MPS 800 with the concentration of 5-80mL/L and liquid additive Mark 904 with the concentration of 0.1-2 mL/L;
the thickness of the all-optical nickel layer is 20-50 mu m, the thickness of the microporous nickel layer is 20-50 mu m, and the thickness of the decorative chromium composite sterilization layer is more than 0.5 mu m.
2. The bactericidal, wear-resistant and corrosion-resistant composite coating according to claim 1, wherein the raw materials of the all-optical nickel layer comprise: nickel sulfate with the concentration of 300-500g/L, nickel chloride with the concentration of 30-80g/L, boric acid with the concentration of 30-80g/L, a cylinder opener NIB-90 with the concentration of 5-10mL/L, a main gloss agent NIB-90 with the concentration of 1-3mL/L and a wetting agent Ni-66B with the concentration of 1-5 mL/L.
3. The bactericidal, wear-resistant and corrosion-resistant composite coating according to claim 1, wherein the bactericidal, wear-resistant and corrosion-resistant composite coating is silvery white.
4. A method of producing a bactericidal, abrasion-resistant and corrosion-resistant composite coating according to any one of claims 1 to 3, comprising:
(1) Pretreatment of the substrate: including polishing and cleaning treatments;
(2) Electroplating the all-optical nickel layer on the surface of the pretreated substrate;
(3) Electroplating the microporous nickel layer on the surface of the all-optical nickel layer;
(4) Electroplating the decorative chromium composite sterilization layer on the surface of the microporous nickel layer.
5. The method of claim 4, wherein the conditions for plating the all-optical nickel layer in step (2) include: the temperature is 40-60 ℃, and the cathode current density is 3.5-10A/dm 2 The electroplating time is 600-2400s.
6. The method of claim 4, wherein the conditions for electroplating the microporous nickel layer in step (3) include: the temperature is 40-60 ℃, and the cathode current density is 3-8A/dm 2 The electroplating time is 600-1800s.
7. The method of claim 4, wherein the conditions for electroplating the decorative chromium composite bactericidal layer in step (4) include: the temperature is 40-60 ℃, and the cathode current density is 5-20A/dm 2 The electroplating time is 300-900s.
8. A sterilized wear-resistant corrosion-resistant product comprising a substrate and the sterilized wear-resistant corrosion-resistant composite coating according to any one of claims 1 to 3.
9. The sterilized, abrasion resistant and corrosion resistant product of claim 8, wherein the substrate is a metal substrate or a plastic substrate.
10. The sterilizing, wear-resistant and corrosion-resistant product according to claim 8 or 9, wherein the sterilizing, wear-resistant and corrosion-resistant product is a sterilizing product for kitchens or toilets.
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