CN115110127B - Hydrophobic bright silver film for inhibiting microbial dirt adhesion growth and preparation method thereof - Google Patents
Hydrophobic bright silver film for inhibiting microbial dirt adhesion growth and preparation method thereof Download PDFInfo
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- CN115110127B CN115110127B CN202210852394.8A CN202210852394A CN115110127B CN 115110127 B CN115110127 B CN 115110127B CN 202210852394 A CN202210852394 A CN 202210852394A CN 115110127 B CN115110127 B CN 115110127B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000004332 silver Substances 0.000 title claims abstract description 97
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 96
- 230000000813 microbial effect Effects 0.000 title claims abstract description 50
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims description 34
- VMAQYKGITHDWKL-UHFFFAOYSA-N 5-methylimidazolidine-2,4-dione Chemical group CC1NC(=O)NC1=O VMAQYKGITHDWKL-UHFFFAOYSA-N 0.000 claims description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 229960002317 succinimide Drugs 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 238000005282 brightening Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000001464 adherent effect Effects 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- -1 salt potassium pyrophosphate Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 3
- 238000009713 electroplating Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 58
- 244000005700 microbiome Species 0.000 abstract description 23
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 12
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 239000010409 thin film Substances 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 4
- 230000002147 killing effect Effects 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- 230000028327 secretion Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 241000295146 Gallionellaceae Species 0.000 description 13
- 239000010963 304 stainless steel Substances 0.000 description 12
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 12
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 10
- 230000001580 bacterial effect Effects 0.000 description 9
- 238000005238 degreasing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000011109 contamination Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000012569 microbial contaminant Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- VMAQYKGITHDWKL-REOHCLBHSA-N (5S)-5-methylimidazolidine-2,4-dione Chemical compound C[C@@H]1NC(=O)NC1=O VMAQYKGITHDWKL-REOHCLBHSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XKGBJFSOWOKVKH-UHFFFAOYSA-N 1,3-dichloro-5-methylimidazolidine-2,4-dione Chemical compound CC1N(Cl)C(=O)N(Cl)C1=O XKGBJFSOWOKVKH-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PQRDTUFVDILINV-UHFFFAOYSA-N bcdmh Chemical compound CC1(C)N(Cl)C(=O)N(Br)C1=O PQRDTUFVDILINV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 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 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
-
- 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
- C25D5/20—Electroplating using ultrasonics, vibrations
-
- 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to the technical field of inhibiting microbial fouling from adhering and growing, and particularly provides a hydrophobic bright silver film for inhibiting microbial fouling from adhering and growing and a preparation method thereof. The film is a silver film with superhydrophobicity and brightness obtained by electrodepositing silver, and as silver has the capability of killing bacteria, the total extracellular secretion of microbial dirt is reduced, the structure is cavitated, and the protein is denatured, so that the whole dirt grows slowly, and the initial adhesion and growth of microorganisms on the surface of the silver film are inhibited, so that the dirt inhibiting effect is formed. On the surface of the bright silver film, the adhesion of microbial dirt on the surface is reduced, so that the adhesion of the microbial dirt is reduced. As the hydrophobicity of the silver thin film surface increases, the adhesion of microorganisms is further reduced. Based on the synergistic effects, the superhydrophobic bright silver film prepared by the invention can effectively inhibit the growth of microbial dirt and the adhesion of the microbial dirt on the surface of the superhydrophobic bright silver film.
Description
Technical Field
The present invention belongs to the field of microbial fouling inhibiting technology for preventing microbial adhesion in flow limiter, heat exchanger, etc. and to prevent metal microbial corrosion in marine water pipe network and city water pipe network. In particular to a hydrophobic bright silver film for inhibiting microbial dirt adhesion growth and a preparation method thereof.
Background
A large amount of microorganisms exist in the natural water environment, and in long-time use, the microorganisms can cause pollution in a water circulation pipe network and runaway of a flow controller on the water pipe network due to adhesion of the microorganisms; the attachment to the recycle condenser results in failure of the heat exchanger. The adhesion of the metal wall can also cause the degradation of the water environmental quality and the corrosion of metal in the urban pipe network, especially when the ocean resource is developed greatly in China, the adhesion of microbial dirt is inhibited, and the corrosion of microbial metal in the ocean environment is prevented.
In a water body, the formation of microbial fouling is divided into a plurality of stages, and the formation of the microbial fouling is cleared, so that the microbial fouling is vital to inhibiting the adhesion growth of the microbial fouling. The early stages of microbial fouling are the microbial attachment and biofilm formation stages. The microorganism adhesion process in the water environment comprises 4 stages of bacteria initial adhesion, biomembrane adhesion period, growth period, maturation period and peeling period. The organic molecules and a small amount of bacteria are adhered to the surface of a substrate, and adhered under the actions of chemical bonding, electrostatic action, mechanical linkage or diffusion, and can fall off from the surface of the substrate under the actions of stripping, plane shearing, non-plane shearing and the like, so that the substrate is in a reversible adhesion stage, microorganisms are firmly adhered to the surface by utilizing polymers secreted by the microorganisms, enter an irreversible adhesion stage, and after the irreversible adhesion, the biological film continues to grow, and the mature and stripping stages are reached after a period of days or weeks, so that the adhesion and fixation of the microorganisms on the surface of the material are very complex dynamic processes and are influenced by a plurality of factors. Studies have shown that the amount of attachment of microorganisms is related to the nature of the material (toxicity of the material to the microorganism); and as the surface roughness of the material increases, the adhesion amount of microbial fouling increases; while positively correlating with the hydrophobicity of the material surface.
Many studies so far use silver or cuprous oxide as a material for inhibiting microorganism adhesion growth, such as silver film or nano cuprous oxide, and the principle is to utilize the capability of killing bacteria, the total extracellular secretion of microbial dirt is reduced, the structure is cavitated, protein is denatured, and the whole growth of the dirt is slow. The effect of inhibiting the initial adhesion and growth of microorganisms on the surface and forming scale inhibition is achieved. There is also a method in which the surface of a metal is modified with a silane coupling agent to form a hydrophobic structure on the surface, thereby inhibiting the adhesion growth of microbial fouling. In view of the effects currently used, the effect of inhibiting the attached growth of microorganisms is not very satisfactory in any of the methods.
Disclosure of Invention
In order to solve the problems of blockage of a flow controller, heat insulation of a heat exchanger, metal corrosion caused by microorganisms and the like caused by the attachment of microbial dirt in a water system, the invention combines the sterilization effect of a silver film with a bright surface silver film which is difficult to attach by the microorganisms, and provides a hydrophobic bright silver film for inhibiting the attachment growth of the microbial dirt and a preparation method thereof.
In order to evaluate the capability of the super-hydrophobic bright silver film to inhibit the adhesion growth of microbial pollutants, 304 stainless steel is selected as a substrate (of course, other substrates with metal surfaces besides 304 stainless steel substrate can be used), and the super-hydrophobic bright silver film is electrodeposited on the surface of the substrate. In order to obtain a silver film with good adhesion strength, the substrate is subjected to a pretreatment of electroplated copper before the electrodeposition of the silver film is performed. The preparation method of the super-hydrophobic bright silver film adopts an electrodeposition method. The silver electrodeposit base solution is composed of silver nitrate as main salt, succinimide as complexing agent and potassium pyrophosphate as conducting salt. The concentration of silver nitrate ranges from 10g/L to 100g/L, when the concentration is lower than 10g/L, the quality of the electrodeposited silver film is reduced due to the too low concentration, and when the concentration is higher than 100g/L, the obtained silver film can become loose due to the too high concentration, and the optimal concentration range of the silver nitrate is 30 g/L to 60g/L. The optimal concentration range of the complexing agent succinimide is 50-100 g/L, and the concentration range of the conductive salt potassium pyrophosphate is 50-120 g/L. Needless to say, other reagents commonly used in the electrodeposition field can be selected for the conductive salt and complexing agent, but for the brightening agent of the present invention, the best combination with potassium pyrophosphate and succinimide is possible.
In order to obtain a stable silver electrodepositing solution, the pH of the silver electrodepositing solution is controlled to be between 8 and 11, and for example, KOH or NaOH may be used to adjust the pH of the silver electrodepositing solution.
The silver electrodeposition solution has a wide operating temperature range, can be set between 10 and 50 ℃ and has a current density range of 0.1 to 2A/dm 2.
In order to obtain a bright silver film, a brightening agent of 5-methyl hydantoin or a derivative thereof is added into the silver electrodeposition solution, wherein the concentration range of the brightening agent is 5-30 g/L, and the optimal concentration range is 10-20 g/L. The silver electrodepositing brightening agent can use 5-methyl hydantoin, partial derivative thereof has good brightening agent effect, and the structural formula of the derivative isWherein R 1 = H or CH 3;R2＝H、CH3, cl or Br; r 3＝H、CH3, cl or Br.
To further facilitate the inhibition of the adherent growth of microbial contaminants, silver particles having a particle size of about 20-800nm are added to the above silver electrodeposition solution, whereby a superhydrophobic and bright silver film can be obtained. Needless to say, the smaller the particle size of the silver particles is, the better, but the very small particles of silver bring about a sharp increase in cost, and when the particles of silver are large, the assistance of ultrasonic vibration is sufficient to uniformly composite electrodeposit the silver particles into the silver thin film. According to the invention, the silver film has a sterilization effect and is combined with the bright and hydrophobic surface silver film which is difficult to adhere to by microorganisms, so that the silver film with the necessary bright characteristic and superhydrophobic effect is obtained, and the adhesion growth of microbial dirt can be better inhibited.
Compared with the prior art, the invention has the following beneficial effects: the invention combines the sterilization effect of the silver film with the bright surface silver film which is difficult to adhere to by microorganisms, and provides the superhydrophobic bright silver film for inhibiting the adhesion growth of microorganism dirt. On the surface of the bright silver film, the adhesion of microbial dirt on the surface is reduced, so that the adhesion of the microbial dirt is reduced. As the hydrophobicity of the silver thin film surface increases, the adhesion of microorganisms is further reduced. Based on the synergistic effects, the hydrophobic bright silver film prepared by the invention can effectively inhibit the growth of microbial dirt and the adhesion of the microbial dirt on the surface of the hydrophobic bright silver film, and the inhibition effect of the microbial adhesion growth in 108h adsorption period can be improved by about 31% compared with that of the hydrophobic bright silver film without adding the brightening agent.
Drawings
FIG. 1 is an SEM image of an electrodeposited silver film, wherein A is absent of 5-methylhydantoin; b is 15 g/L5-methyl hydantoin.
FIG. 2 is an SEM image after 500nm silver particles are added.
Fig. 3 contact angles of electrodeposited silver films under different conditions.
Detailed Description
The invention is further illustrated below with reference to examples. Examples detailed embodiments and specific procedures are given, but the scope of the present invention is not limited to the following examples.
To effectively illustrate the effect of the present invention, a 304 stainless steel sheet of 1.5×4cm (thickness of 0.5 mm) was first prepared, after degreasing by alkali washing, a copper pretreatment was performed on the surface thereof, and then it was placed in a silver base plating solution (silver nitrate, succinimide, potassium pyrophosphate, pH of the solution was adjusted with KOH) for electrodeposition, the condition of which was 30 ℃. If a bright silver film is desired, 5-methylhydantoin or a derivative thereof may be added to the solutionProperties comparable to those of 5-methylhydantoin were obtained, and the following specific examples are not to be construed one by one. Further, if a superhydrophobic bright silver film is desired, nano silver particles may be added to the silver solution. If the nano silver particles are added without adding the brightening agent, the obtained substrate surface has the defects of roughness and poor hydrophobic property, and can not well inhibit adhesion and growth of microorganisms.
In order to evaluate the capability of the superhydrophobic bright silver film in inhibiting the adhesion growth of microbial pollutants, the cultured iron bacteria are prepared into diluted bacterial suspension according to the ratio of 1:100, the diluted bacterial suspension is placed in different beakers, test pieces are respectively and vertically suspended in beakers containing the cultured iron bacteria solution, the beakers are placed in a simulated heating environment at 30 ℃, and the microbial fouling experimental period is 108 hours. The mass of the sample before and after the experiment was weighed using an electronic analytical balance to measure how much microbial contamination was attached to the sample. To evaluate the ability of the superhydrophobic bright silver film to inhibit the growth of microbial contaminants by adhesion, experimental iron bacteria were cultivated. The prepared culture medium was sterilized in an autoclave at 0.1mp and 120℃for 20min. And cooling the culture medium in a purification workbench, and sterilizing by an ultraviolet lamp for 15min. 10ml of strain is taken by an inoculation gun, the inoculation amount is 1%, and the strain is inoculated into 1000 ml of culture medium, and is cultivated for 72 hours at a constant temperature of 30 ℃ in a constant temperature incubator.
The following examples are given in order to illustrate the present invention, and the claims are not limited to the reaction conditions and the raw material concentrations set forth in the following examples.
Example 1
A1.5X4cm (thickness of 0.5 mm) 304 stainless steel sheet after degreasing and pre-copper plating treatment was subjected to electrodeposition for 30min at a current density of 0.3A/dm 2 by adjusting the pH of the solution to 8 with KOH in an electrodeposition solution of 10g/L of silver nitrate, 50g/L of succinimide and 60g/L of potassium pyrophosphate, and an electrodeposited silver film test piece was obtained. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours. The mass of the test piece before and after the experiment was weighed using an electronic analytical balance, and other experimental conditions and results are shown in example 1 of table 1.
Example 2
A sample of a 304 stainless steel sheet 1.5X4cm (thickness: 0.5 mm) after degreasing and pre-copper plating was subjected to electrodeposition in a solution of 45g/L of silver nitrate, 50g/L of succinimide, 60g/L of potassium pyrophosphate and 15g/L of 5-methylhydantoin, and the pH of the solution was adjusted to 10 with KOH, and a current density of 0.3A/dm 2 was applied at 25℃for an electrodeposition time of 30 minutes to obtain an electrodeposited silver film sample. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours. The mass of the test piece before and after the experiment was weighed using an electronic analytical balance, and other experimental conditions and results are shown in example 2 of table 1.
Example 3
A304 stainless steel sheet of 1.5X4cm (thickness of 0.5 mm) after degreasing and pre-copper plating treatment was subjected to electrodeposition for 30 minutes in an electrodeposition solution of 45g/L of silver nitrate, 50g/L of succinimide, 60g/L of potassium pyrophosphate, 15g/L of 5-methylhydantoin and 3g/L of 500nm silver powder, and the pH of the solution was adjusted to 10 with KOH, and under irradiation of ultrasonic waves at 25℃a current density of 0.3A/dm 2 was applied. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours. The mass of the test piece before and after the test was weighed using an electronic analytical balance, and other test conditions and results are shown in example 3 of Table 1, and it can be seen that there was almost no attached iron bacterial microbial contamination on the test piece.
Example 4
A304 stainless steel sheet of 1.5X4cm (thickness of 0.5 mm) after degreasing and copper pretreatment was subjected to electrodeposition in a solution of 60g/L of silver nitrate, 70g/L of succinimide, 100g/L of potassium pyrophosphate, 15g/L of 5, 5-dimethylhydantoin and 3g/L of 500nm silver powder, and the pH of the solution was adjusted to 10 with KOH, and under irradiation of ultrasonic waves at 25℃a current density of 0.3A/dm 2 was applied for an electrodeposition time of 30 minutes to obtain an electrodeposited silver film test piece. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours. The mass of the test piece before and after the test was weighed using an electronic analytical balance, and other test conditions and results are shown in example 4 of Table 1, and it can be seen that there was almost no attached iron bacterial microbial contamination on the test piece.
Example 5
A sample of the 1.5X4cm (thickness: 0.5 mm) 304 stainless steel sheet after degreasing and pre-copper plating was subjected to an electrodeposition solution of 100g/L of silver nitrate, 100g/L of succinimide, 120g/L of potassium pyrophosphate, 5g/L of 3-bromo-1-chloro-5, 5-dimethylhydantoin and 2g/L of 300nm silver powder, and the pH of the solution was adjusted to 10 with KOH, and an electrodeposited silver film was obtained by applying a current density of 0.6A/dm 2 under irradiation of ultrasonic waves at 25℃for 15 minutes. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours. The mass of the test piece before and after the test was weighed using an electronic analytical balance, and other test conditions and results are shown in example 5 of Table 1, and it can be seen that there was almost no attached iron bacterial microbial contamination on the test piece.
Example 6
A304 stainless steel sheet of 1.5x4cm (thickness of 0.5 mm) after degreasing and copper pretreatment was subjected to electrodeposition in a solution of 45g/L of silver nitrate, 50g/L of succinimide, 60g/L of potassium pyrophosphate, 20g/L of 1, 3-dichloro-5-methylhydantoin and 2g/L of silver powder of 800nm, the pH of the solution was adjusted to 10 with KOH, and a current density of 1A/dm 2 was applied under irradiation of ultrasonic waves at 25℃for 10 minutes to obtain an electrodeposited silver film test piece. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours. The mass of the test piece before and after the test was weighed using an electronic analytical balance, and other test conditions and results are shown in example 6 of Table 1, and it can be seen that there was almost no attached iron bacterial microbial contamination on the test piece.
TABLE 1 variation of mass of test pieces for inhibiting iron bacteria adsorption under different electrodeposition example conditions
Comparative example 1
A1.5X4cm (thickness: 0.5 mm) 304 stainless steel sheet after degreasing and pre-copper plating treatment was weighed to a mass of 2.0683g, and the test piece was vertically hung in a beaker containing a cultured iron bacteria solution at 30℃for a period of 108 hours, and then weighed to 2.1964g. It can be seen that a large number of iron bacteria microorganisms were attached to the surface of the 304 stainless steel coupon without electrodeposited silver film.
Comparative example 2
A sample of a 304 stainless steel sheet 1.5X4cm (thickness: 0.5 mm) after degreasing and pre-copper plating was subjected to electrodeposition in a solution of 45g/L of silver nitrate, 50g/L of sodium citrate, 60g/L of sodium nitrate and 15g/L of 5-methylhydantoin, to adjust the pH of the solution to 10 with KOH, and at 25℃a current density of 0.3A/dm 2 was applied for an electrodeposition time of 30 minutes, to obtain an electrodeposited silver film sample. The test piece obtained was not shiny and the weighed mass was 2.9123g. The test piece was suspended vertically in a beaker containing the cultured iron bacteria solution at 30℃for a period of 108 hours and weighed to be 2.9754 hours. The mass change before and after adsorption of the microbial contaminants was 0.0631g.
As can be seen from the results of comparative example 1, a large amount of iron bacterial microbial contamination occurred on the 304 stainless steel due to the absence of the electrodeposited silver film. From the results of example 1 in table 1, it was found that when a silver thin film was present on 304 stainless steel, the presence of iron bacterial microbial contamination was sufficiently suppressed, and when the silver surface was a hydrophobic and bright thin film, the presence of iron bacterial microbial contamination was hardly seen on the silver thin film surface of 304 stainless steel substrate, and the mass change was only 0.0038g, as shown in table 3. As is clear from comparative example 2, although silver has an inhibitory effect on the growth of microbial fouling, the bright silver layer can further inhibit the adhesion of microorganisms, and further, compared with the results of examples, the bright and hydrophobic silver layer has a remarkable inhibitory effect on the adhesion growth of microbial fouling. From the results, it is found that the adhesion growth of microbial contaminants on the surface of the substrate can be effectively inhibited by constructing the superhydrophobic bright silver film.
FIG. 1 is an electron microscopic image of a silver thin film obtained by adjusting the pH of a solution to 10 with KOH in an electrodeposition solution of 45g/L of silver nitrate, 50g/L of succinimide, and 60g/L of potassium pyrophosphate, and applying a current density of 0.3A/dm 2 at 25℃for 30 minutes. In FIG. 1A is 5-methylhydantoin without added brightening agent and in FIG. 1B is 15 g/L5-methylhydantoin. As can be seen from the electron microscope picture of fig. 1, after adding 5-methylhydantoin to the silver electrodeposition solution, the obtained electrodeposited film was very flat and also very bright in appearance.
FIG. 2 is an electron microscope image obtained by adding 3g/L of 500nm silver particles to the electrodeposition solution corresponding to B in FIG. 1.
FIG. 3 shows the contact angle of electrodeposited silver film under various conditions, A in FIG. 3 is the contact angle measured for a silver film without the brightening agent 5-methylhydantoin, at an angle of 110.2, when 15 g/L5-methylhydantoin is added, the silver film obtained becomes shiny, and the contact angle increases to 129.6, and the hydrophobicity of the surface of the silver film increases. When the addition of 0.5g/L of 500nm silver particles is continued, the obtained silver film becomes rough before addition, but the surface of the silver film is still bright, the contact angle of the silver film is continuously increased to 141.4 degrees, the concentration contact angle of the silver particles is continuously increased, when the concentration of the silver particles is 3g/L, the contact angle of the silver film reaches the maximum value of 152.2 degrees, the contact angle of the silver nanoparticles is continuously increased, and the contact angle of the silver film is reduced.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (5)
1. A method for preparing a hydrophobic bright silver film for inhibiting microbial fouling adhesion growth, which is characterized by comprising the following steps: preparing a silver film on the surface of a substrate with a metal surface in an electrodeposition mode, wherein the electrodeposition liquid comprises soluble silver salt and a brightening agent; the brightening agent is 5-methyl hydantoin or derivatives thereofThe method also comprises a copper electroplating pretreatment step before electrodeposition;
the concentration range of the soluble silver salt in the electrodeposition liquid is 10-100 g/L, the concentration range of the complexing agent succinimide is 50-100 g/L, and the concentration range of the conductive salt potassium pyrophosphate is 50-120 g/L;
nano silver particles of 20-800nm are also dispersed in the electrodeposition liquid, and ultrasonic irradiation is assisted in the electrodeposition process; the addition amount of silver nano particles in the electrodeposition liquid is 0.3-5g/L;
The pH value of the electrodeposition liquid is 8-11;
in the structure of the 5-methylhydantoin derivative, R 1 = H or CH 3;R2 = H、CH3, cl or Br; r 3 = H、CH3, cl or Br.
2. The method for preparing a hydrophobic bright silver film for inhibiting the adherent growth of microbial foulants according to claim 1, wherein: the pH of the electrodepositing solution is adjusted using potassium hydroxide and/or sodium hydroxide.
3. The method for preparing a hydrophobic bright silver film for inhibiting the adherent growth of microbial foulants according to claim 1, wherein: the electrodeposition temperature is 10-50 ℃, and the current density range is 0.1-2A/dm 2;
The concentration of 5-methyl hydantoin or its derivative in the electrodeposition liquid is 5-30 g/L.
4. The method for preparing a hydrophobic bright silver film for inhibiting the adherent growth of microbial foulants according to claim 1, wherein: the soluble silver salt is silver nitrate, and the concentration range of the silver nitrate in the electrodeposition liquid is 30-60 g/L;
and/or the concentration of 5-methylhydantoin or derivatives thereof is in the range of 10 to 20 g/L.
5. A hydrophobic bright silver film produced by the production method of a hydrophobic bright silver film for inhibiting the adhesion growth of microbial foulants according to any one of claims 1 to 4.
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| CN103397355A (en) * | 2013-07-19 | 2013-11-20 | 哈尔滨工业大学 | Cyanide-free electrosilvering solution applicable to high-speed electroplating and electroplating process |
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| CN107313084B (en) * | 2017-08-10 | 2019-03-01 | 佛山市南博旺环保科技有限公司 | A kind of alkaline non-cyanide plate silver plating solution and silver-coating method |
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| CN103397355A (en) * | 2013-07-19 | 2013-11-20 | 哈尔滨工业大学 | Cyanide-free electrosilvering solution applicable to high-speed electroplating and electroplating process |
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