CN109112589B - Preparation of Co-TiO on metal surface2Super-hydrophobic nano composite coating and preparation method thereof - Google Patents
Preparation of Co-TiO on metal surface2Super-hydrophobic nano composite coating and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 title claims abstract description 35
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004140 cleaning Methods 0.000 claims abstract description 21
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- 229910001369 Brass Inorganic materials 0.000 claims description 13
- 239000010951 brass Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 2
- 235000021360 Myristic acid Nutrition 0.000 claims description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 4
- 238000000861 blow drying Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
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- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
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- 238000004378 air conditioning Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XKGUZGHMWUIYDR-UHFFFAOYSA-N benzyl n-(3-fluoro-4-morpholin-4-ylphenyl)carbamate Chemical compound C=1C=C(N2CCOCC2)C(F)=CC=1NC(=O)OCC1=CC=CC=C1 XKGUZGHMWUIYDR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- 239000011800 void material Substances 0.000 description 1
Images
Classifications
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- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a method for preparing Co-TiO on the surface of metal2The preparation process of super hydrophobic nanometer composite coating includes the first polishing, cleaning and blowing to the surface of metal. Then preparing metal cobalt salt, long-branched alkanoic acid and TiO2Dissolving complexing agent and surfactant in ethanol overnight, stirring and ultrasonically vibrating uniformly to obtain the electroplating solution. Electroplating with the metal as cathode and pure platinum or graphite carbon as anode, cleaning the cathode after electroplating, and blow-drying to obtain Co-TiO coated workpiece2The invention not only realizes the super-hydrophobicity of the metal surface, but also endows the surface with sterilization and photocatalysis performances, the obtained coating is compact, the contact angle is 155-160 degrees, the rolling angle is close to 0 degree, and the TiO is compact2The content of the electroplating solution is 20-30%, the electroplating solution is simple to prepare, environment-friendly, easy to operate in the electroplating process, and can be widely popularized and used.
Description
Technical Field
The invention relates to the technical field of nano composite electroplating, in particular to a method for preparing Co-TiO on the surface of metal2A super-hydrophobic nano composite coating and a preparation method thereof.
Background
The metal material is widely applied to daily life of people, common metal materials are easily corroded and worn by water vapor and oxygen in air to damage the common metal materials, so that researchers are always striving to find an effective material protection method, the current mature interface technology is an electroplating process, the process method is successfully popularized and used in industry due to low cost and simple equipment, but along with the fact that the performance requirements of the materials in market production requirements are higher and higher, the traditional single metal coating can not meet the requirements of hardness, wear resistance, corrosion resistance and high temperature resistance of the coating, and the coating is replaced by a nano composite coating.
Nanomaterials have many properties such as large specific surface area, quantum effects, and interfacial effects. Nano TiO 22Is a better environment-friendly material, namely anatase type TiO2Has excellent photocatalytic performance and antibacterial capacity, and can be widely applied to water treatment, air purification, sterilization, coating and the like, so that the photocatalyst has good commercial application value. Watkins and colleagues printed shark skin surface with polymer and ceramic composite, and added TiO2Nanoparticles with no addition of TiO2Surface contrast of nanoparticles with TiO addition2The surface of the nanoparticles killed more than 95% of E.coli and 80% of S.aureus.
Since Jiang lei research group reveals the super-hydrophobic and self-cleaning mechanism of lotus leaf surface, how to prepare super-hydrophobic surface gets the attention of general scientists, and the current method for preparing super-hydrophobic on metal surface mainly comprises chemical etching method, anodic oxidation method, vapor deposition method, thermal spraying method and electroplating method. In comparison, the electroplating method has the advantages of simple equipment, low cost, convenience in large-area preparation and the like, application No. 201310301855.3 discloses a method for preparing a super-hydrophobic cobalt coating on a metal surface, the super-hydrophobic cobalt coating is prepared in one step by preparing an electroplating solution containing cobalt salt and long-branched alkanoic acid, application No. 201110152051.2 discloses a method for preparing a super-hydrophobic nickel coating by using a nickel electroplating solution, and the used nickel electroplating solution takes choline chloride ionic liquid as a solvent and nickel salt as a solute.
The super-hydrophobic metal coating is widely applied to corrosion prevention and drag reduction of the surface of a ship, and can improve the performances of self-cleaning, anti-icing and the like of the metal surface2Super-hydrophobic nano-meterComposite coating, super-hydrophobic and photocatalytic properties on the surface, and TiO addition2The nanometer particles and the cobalt metal can form codeposition on the workpiece to be plated to form fine and compact plating layers containing the cobalt metal and solid particles, and the plating layers have fewer gaps than the traditional pure cobalt plating layers and are more corrosion-resistant. The preparation method is simple, has low requirements on equipment, and is easy to industrially popularize and use in a large area.
Disclosure of Invention
The invention provides a method for preparing Co-TiO on the surface of metal on the premise of higher requirements on the surface performance of the material2Super-hydrophobic nano composite coating and preparation method thereof, TiO with photocatalytic activity2Uniformly dispersed in the super-hydrophobic cobalt coating to be firmly combined together. Co-TiO prepared by the invention2The super-hydrophobic nano composite coating has good hydrophobic property and good bactericidal property on the surface, can effectively decompose organic matters under visible light, and has wide application prospect in the fields of navigation, air conditioning and automobiles.
The invention is realized by the following technical scheme.
Preparation of Co-TiO on metal surface2The method for preparing the super-hydrophobic nano composite coating comprises the following steps:
(1) pretreatment of the metal surface: firstly, polishing the metal surface by using sand paper, then carrying out ultrasonic cleaning by using a surfactant, then carrying out ultrasonic cleaning by using acetone, finally cleaning by using dilute sulfuric acid, and drying for later use;
(2) preparing electroplating solution; mixing metal cobalt salt, long-branched alkanoic acid, complexing agent, surfactant and nano-grade TiO2Adding the solution into ethanol, magnetically stirring, and then ultrasonically shaking uniformly to obtain an electroplating solution;
(3) taking the metal workpiece to be plated obtained in the step (1) as a cathode, taking a platinum sheet or carbon as an anode, electroplating in the electroplating solution prepared in the step (2), then washing the cathode with ethanol, and drying to obtain Co-TiO on the metal surface2And (3) a super-hydrophobic nano composite coating.
Preferably, the sand paper in the step (1) is 800 meshes and 400 meshes.
Preferably, the metal is stainless steel and brass conductive metal material.
Preferably, the surfactant is sodium dodecyl benzene sulfonate.
Preferably, the concentration of the dilute sulfuric acid is 0.5-2 mol/l.
Preferably, the ultrasonic cleaning time is 10 min-20 min.
Preferably, the time for washing with dilute sulfuric acid is 30-60 s.
Preferably, the metallic cobalt salt in step (2) is cobalt chloride or cobalt sulfate.
Preferably, the concentration of the metal cobalt salt in the electroplating solution is 0.05-0.2 mol/l.
Preferably, the long-branched alkanoic acid in the step (2) is stearic acid, myristic acid or stearic acid.
Preferably, the concentration of the long-chain branched alkanoic acid in the plating solution is 0.05 to 0.3 mol/l.
Preferably, the complexing agent in the step (2) is sodium citrate, sodium gluconate or ammonium citrate.
Preferably, the concentration of the complexing agent in the electroplating solution is 40-100 g/l.
Preferably, the surfactant in step (2) is one or both of sodium dodecylbenzene sulfonate and sodium dodecylsulfate.
Preferably, the concentration of the surfactant in the electroplating solution is 0.01 to 0.2 g/l.
Preferably, TiO described in step (2)2Is anatase type, has the specification of 10 nm-100 nm and the size of 10 nm-100 nm.
Preferably, the TiO is2The concentration in the plating solution is 10g/l to 20 g/l.
Preferably, in the step (2), an ultrasonic instrument with power of 200W-500W is adopted for ultrasonic treatment for 10-20 min, and a magnetic stirrer with power of 200-.
Preferably, the power supply for electroplating in the step (3) is an alternating current power supply, the voltage is set to be 15-30V, the electroplating time is 5-30 min, the temperature of the electroplating solution is room temperature, and the electroplating solution is stirred under a magnetic stirrer all the time in the electroplating process to ensure that the electroplating solution is uniformly dispersed.
Co-TiO prepared by the above-described method2And (3) a super-hydrophobic nano composite coating.
Compared with the prior art, the invention has the following advantages:
(1) the doped nano particles promote the metal coating to be dispersed more uniformly, the coating is more compact, the void ratio is greatly reduced, and the coating is more corrosion-resistant.
(2) Anatase TiO2The addition of the nano particles endows the super-hydrophobic surface with certain photocatalytic performance, has good bactericidal capability under visible light, inhibits the growth of microorganisms on the metal surface, and can decompose organic matters on the surface.
(3) The electroplating solution has simple formula and low production cost, does not need expensive equipment and is convenient for large-scale preparation.
(4) The prepared super-hydrophobic surface is flat and uniform, the roughness of the surface is increased by adding the nano particles, the contact angle reaches 155-160 degrees, the rolling angle is close to 0 degree, and the prepared Co-TiO-based composite material is prepared by the method2The super-hydrophobic nano composite coating can meet the special requirements of the industry on meeting the requirements of both hydrophobic property and antibacterial property, and has certain practical application value.
Drawings
FIG. 1a and FIG. 1b show Co-TiO2SEM image of the super-hydrophobic nano composite coating.
FIG. 2a to FIG. 2d are Co-TiO2Contact angle diagram of super-hydrophobic nano composite coating.
Fig. 3 is a schematic diagram of the degradation of organic matter (sterilization).
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1
Firstly, polishing 99.9% brass sheets by using 800-mesh and 400-mesh sand paper, shearing the brass sheets by using scissors to form a length of 5 multiplied by 3cm, then ultrasonically cleaning the brass sheets by using sodium dodecyl benzene sulfonate for 10min, cleaning the brass sheets by using acetone for 20min, cleaning the brass sheets by using 0.5mol/l dilute sulfuric acid for 60s, finally, washing the brass sheets by using distilled water, and drying the brass sheets for later use.
Accurately weighing 2.6g of cobalt dichloride, 8.50g of stearic acid, 10g of 25nm titanium dioxide, 0.02g of sodium dodecyl benzene sulfonate and 4g of sodium citrate by using a tray balance, putting the weighed materials into a beaker, measuring 100ml of absolute ethyl alcohol by using a measuring cylinder, pouring the absolute ethyl alcohol into the beaker, firstly carrying out ultrasonic treatment for 10min by using an ultrasonic instrument with the power of 300W, and then stirring for 30min by using a magnetic stirrer with the power of 500r/min to obtain the uniformly dispersed electroplating solution.
And (3) electroplating the cleaned brass sheet serving as a cathode and the pure platinum sheet serving as an anode in the prepared electroplating solution, controlling the voltage to be 15V, electroplating for 30min, maintaining the temperature of the electroplating solution at 30 ℃, and keeping the electroplating solution under 500r/min magnetic stirring in the electroplating process.
Taking out the workpiece to be plated, washing the workpiece with ethanol, drying the workpiece, and measuring a contact angle of 155 degrees and a rolling angle of 1 degree by using a contact angle measuring instrument, as shown in figure 2 a. The scanning electron micrographs of the coating are shown in FIGS. 1a and 1b, from which the TiO clearly appears2The coating is uniformly dispersed in the coating, and the coating is uniformly dispersed. FIG. 3 depicts a schematic of titanium dioxide sterilization on a coating.
Example 2
Polishing stainless steel with 800-mesh and 400-mesh sand paper, shearing with scissors to 5 × 3cm, ultrasonically cleaning with sodium dodecyl benzene sulfonate for 15min, cleaning with acetone for 10min, cleaning with 0.5mol/l dilute sulfuric acid for 1min, rinsing with distilled water, and blow-drying.
Accurately weighing 0.650g of cobalt dichloride, 1.420g of myristic acid, 15g of 25nm titanium dioxide, 0.04g of sodium dodecyl benzene sulfonate and 7g of ammonium gluconate by using a tray balance, putting the weighed materials into a beaker, weighing 100ml of absolute ethyl alcohol by using a measuring cylinder, pouring the absolute ethyl alcohol into the beaker, firstly carrying out ultrasonic treatment for 10min by using an ultrasonic instrument with the power of 300W, and then stirring for 30min by using a magnetic stirrer with the power of 400r/min to obtain the uniformly dispersed electroplating solution.
And (3) electroplating the cleaned brass sheet serving as a cathode and the pure platinum sheet serving as an anode in the prepared electroplating solution, controlling the voltage to be 30V, electroplating for 5min, maintaining the temperature of the electroplating solution at 30 ℃, and keeping the electroplating solution under the magnetic stirring at 800r/min all the time in the electroplating process.
And taking out the workpiece to be plated, washing the workpiece with ethanol, drying the workpiece, and measuring a contact angle of 160 degrees and a rolling angle of 3 degrees by using a contact angle measuring instrument, as shown in figure 2 b.
Example 3
Grinding brass sheet with 800-mesh and 400-mesh sand paper, shearing with scissors to 5 × 3cm, ultrasonically cleaning with sodium dodecyl sulfate for 10min, cleaning with acetone for 15min, cleaning with 2mol/l dilute sulfuric acid for 30s, cleaning with distilled water, and blow-drying.
Accurately weighing 2.60g of cobalt dichloride, 8.50g of octadecanoic acid, 20g of 10nm titanium dioxide, 0.04g of sodium dodecyl benzene sulfonate and 10g of sodium citrate by using a tray balance, putting the weighed materials into a beaker, measuring 100ml of absolute ethyl alcohol by using a measuring cylinder, pouring the absolute ethyl alcohol into the beaker, firstly carrying out ultrasonic treatment for 10min by using an ultrasonic instrument with the power of 500W, and then stirring for 30min by using a magnetic stirrer with the power of 500r/min to obtain the uniformly dispersed electroplating solution.
And (3) electroplating the cleaned brass sheet serving as a cathode and the pure platinum sheet serving as an anode in the prepared electroplating solution, controlling the voltage to be 22.5V, electroplating for 17.5min, maintaining the temperature of the electroplating solution at 30 ℃, and keeping the electroplating solution under 400r/min magnetic stirring in the electroplating process.
And taking out the workpiece to be plated, washing the workpiece with ethanol, drying the workpiece, and measuring a contact angle of 158 degrees and a rolling angle of 1 degree by using a contact angle measuring instrument, as shown in figure 2 c.
Example 4
Polishing an aluminum sheet with the purity of 99.9% by using sand paper of 800 meshes and 400 meshes, shearing the aluminum sheet into 5 multiplied by 3cm, ultrasonically cleaning the aluminum sheet for 15min by using sodium dodecyl sulfate, cleaning the aluminum sheet for 15min by using acetone, cleaning the aluminum sheet for 30s by using 0.5mol/l dilute sulfuric acid, finally cleaning the aluminum sheet by using distilled water, and drying the aluminum sheet for later use.
1.63g of cobalt dichloride, 4.90g of stearic acid, 10g of 100nm titanium dioxide, 0.02g of sodium dodecyl benzene sulfonate and 4g of sodium citrate are accurately weighed by a tray balance, put into a beaker, then 100ml of absolute ethyl alcohol is measured by a measuring cylinder, poured into the beaker, firstly treated by ultrasonic for 10min by an ultrasonic instrument with the power of 300W, and then stirred for 30min by a magnetic stirrer with the power of 300r/min to obtain the uniformly dispersed electroplating solution.
And (3) electroplating the cleaned aluminum sheet serving as a cathode and the pure platinum sheet serving as an anode in the prepared electroplating solution, controlling the voltage to be 20V, electroplating for 15min, maintaining the temperature of the electroplating solution at 30 ℃, and keeping the electroplating solution under 400r/min magnetic stirring in the electroplating process.
And taking out the workpiece to be plated, washing the workpiece with ethanol, drying the workpiece, and measuring a contact angle of 157 degrees and a rolling angle of 4 degrees by using a contact angle measuring instrument, as shown in figure 2 d.
Claims (10)
1. Preparation of Co-TiO on metal surface2The method for preparing the super-hydrophobic nano composite coating is characterized by comprising the following steps of:
(1) pretreatment of the metal surface: firstly, polishing the metal surface by using sand paper, then carrying out ultrasonic cleaning by using a surfactant, then carrying out ultrasonic cleaning by using acetone, finally cleaning by using dilute sulfuric acid, and drying for later use;
(2) preparing electroplating solution; mixing metal cobalt salt, long-branched alkanoic acid, complexing agent, surfactant and nano-grade TiO2Adding the solution into ethanol, magnetically stirring, and then ultrasonically shaking uniformly to obtain an electroplating solution;
(3) taking the metal workpiece to be plated obtained in the step (1) as a cathode, taking a platinum sheet or carbon as an anode, electroplating in the electroplating solution prepared in the step (2), then washing the cathode with ethanol, and drying to obtain Co-TiO on the metal surface2A super-hydrophobic nano composite coating;
the long-branched alkanoic acid in the step (2) is stearic acid, myristic acid or octadecanoic acid;
the complexing agent in the step (2) is sodium citrate, sodium gluconate or ammonium citrate;
the surfactant in the step (2) is one or two of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
2. The method of claim 1, wherein the sandpaper in step (1) is 800 mesh and 400 mesh; the metal is stainless steel and brass conductive metal material; the surfactant is sodium dodecyl benzene sulfonate; the concentration of the dilute sulfuric acid is 0.5-2 mol/l; the ultrasonic cleaning time is 10-20 min; the time for cleaning with dilute sulfuric acid is 30-60 s.
3. The method according to claim 1, wherein the metallic cobalt salt in step (2) is cobalt chloride or cobalt sulfate; CoCl in the electroplating solution2The concentration of (b) is 0.05-0.2 mol/l.
4. The method as claimed in claim 1, wherein the concentration of stearic acid or stearic acid in the plating solution in the step (2) is 0.05 to 0.3 mol/l.
5. The method as set forth in claim 1, wherein the complexing agent is contained in the plating solution in the step (2) in a concentration of 40 to 100 g/l.
6. The method as claimed in claim 1, wherein the concentration of the surfactant in the plating solution in the step (2) is 0.01 to 0.2 g/l.
7. The method of claim 1, wherein the TiO in step (2)2Is anatase type with the specification of 10 nm-100 nm; TiO in the electroplating solution2The concentration of (b) is 10g/l to 20 g/l.
8. The method as claimed in claim 1, wherein the ultrasonic instrument with power of 200W-500W is used for ultrasonic treatment for 10-20 min in step (2), and the magnetic stirrer with power of 200-800r/min is used for stirring for 10-40 min.
9. The method as claimed in claim 1, wherein the power supply for the electroplating in step (3) is an alternating current power supply, the voltage is set to be 15-30V, the electroplating time is 5-30 min, the temperature of the electroplating solution is room temperature, and the electroplating solution is stirred under a magnetic stirrer all the time during the electroplating process to ensure that the electroplating solution is uniformly dispersed.
10. Co-TiO obtainable by a process according to any one of claims 1 to 92And (3) a super-hydrophobic nano composite coating.
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| CN102140659A (en) * | 2011-02-24 | 2011-08-03 | 西北工业大学 | Method for preparing superhydrophobic film |
| CN102677132A (en) * | 2012-05-28 | 2012-09-19 | 大连理工大学 | Method for preparing super-hydrophobic coating of metallic matrix |
| CN103382564A (en) * | 2013-07-18 | 2013-11-06 | 华南理工大学 | Super-hydrophobic cobalt plating of metal surface and preparation method for super-hydrophobic cobalt plating |
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| CN102140659A (en) * | 2011-02-24 | 2011-08-03 | 西北工业大学 | Method for preparing superhydrophobic film |
| CN102677132A (en) * | 2012-05-28 | 2012-09-19 | 大连理工大学 | Method for preparing super-hydrophobic coating of metallic matrix |
| CN103382564A (en) * | 2013-07-18 | 2013-11-06 | 华南理工大学 | Super-hydrophobic cobalt plating of metal surface and preparation method for super-hydrophobic cobalt plating |
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