CN115110125B - A nanometer Y-containing material2O3Particle corrosion-resistant super-hydrophobic composite material and preparation method thereof - Google Patents
A nanometer Y-containing material2O3Particle corrosion-resistant super-hydrophobic composite material and preparation method thereof Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 61
- 238000005260 corrosion Methods 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000004070 electrodeposition Methods 0.000 claims abstract description 72
- 238000000576 coating method Methods 0.000 claims abstract description 71
- 239000011248 coating agent Substances 0.000 claims abstract description 70
- 239000011159 matrix material Substances 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 60
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 54
- 239000010959 steel Substances 0.000 claims abstract description 54
- 229910020514 Co—Y Inorganic materials 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002114 nanocomposite Substances 0.000 claims abstract description 17
- 210000001595 mastoid Anatomy 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000002715 modification method Methods 0.000 claims abstract description 6
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract 5
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract 5
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract 5
- 239000000243 solution Substances 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000000956 alloy Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 20
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 19
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 19
- 230000003213 activating effect Effects 0.000 claims description 18
- 238000005238 degreasing Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 15
- 235000021355 Stearic acid Nutrition 0.000 claims description 14
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008117 stearic acid Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 229940085605 saccharin sodium Drugs 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 241000080590 Niso Species 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- 239000006185 dispersion Substances 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
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 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
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 229960004106 citric acid Drugs 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- 238000007517 polishing process Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 29
- 238000007747 plating Methods 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
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- 239000000758 substrate Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 238000012876 topography Methods 0.000 description 8
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 4
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- 238000002604 ultrasonography Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
- C25D3/12—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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- C—CHEMISTRY; METALLURGY
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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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)
- Automation & Control Theory (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles and a preparation method thereof, wherein the preparation method comprises the following steps: performing electrodeposition by taking an X100 steel matrix as a cathode, taking a pure nickel plate as an anode and adopting Ni-Co-Y 2O3 electrodeposition solution to obtain a Ni-Co-Y 2O3 nano composite coating with mastoid protrusions on the surface of the steel matrix; and then using a low surface energy modification method to enable the Ni-Co-Y 2O3 nano composite coating to have superhydrophobicity, and finally drying to obtain the corrosion-resistant superhydrophobic composite material containing nano Y 2O3 particles. The invention can obviously improve the corrosion resistance of the Ni-Co coating, has higher hydrophobicity, and the surface of the obtained coating has a micro-nano mastoid-shaped protrusion structure. When the corrosive medium contacts with the nano composite coating, double protection of the surface super-hydrophobic film and the nano composite coating prevents corrosive ions from immersing into the coating, so that the corrosion resistance of the coating is improved, and a new thought is provided for the prepared novel composite coating to be widely applied in a soil corrosion environment.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment and modification, and particularly relates to a corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles and a preparation method thereof.
Background
Pipeline transportation is the main transportation mode in the oil and gas industry at present. In the oil gas development and transportation process, pipeline steel is in long-term service in different soil media, such as acid soil, saline-alkali soil and the like, a large amount of aqueous mixture is contained in the soil environment, the surface energy of the pipeline steel is large, so that water drops are easily spread on the surface of the pipeline steel, the contact area between water (or corrosive substances) and the surface of the pipeline steel is increased, and corrosion is increased. Soil corrosion is a major cause of threatening the safe operation of oil and gas, leading to corrosion perforation of pipelines. The nickel-cobalt (Ni-Co) alloy coating has higher corrosion resistance, hardness and good wear resistance, becomes a main stream material of a surface coating, and still cannot meet the current severe soil corrosion environment.
The superhydrophobic surface means that the water contact angle is greater than 150 degrees and the rolling angle is less than 10 degrees. In general, superhydrophobic surfaces can be achieved by a combination of micro-nanostructures and surface modification of low surface energy materials. The low surface energy material often needs fluorosilane and the like to reduce the surface energy, but the materials are expensive, pollute the environment and have great harm to human bodies, and how to prepare the super-hydrophobic Ni-Co alloy coating without using the fluorine-containing material is a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the problem that the existing Ni-Co alloy coating can not meet the modern requirements under severe working conditions, the invention provides the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles and the preparation method thereof, and the invention provides the super-hydrophobic composite coating with good hydrophobic performance and excellent corrosion resistance by adopting a low surface energy modification technology on the basis of adding second-phase nano particles Y 2O3 into the existing Ni-Co coating to strengthen the corrosion resistance of the Ni-Co coating, so that the composite material with the super-hydrophobic composite coating can be widely applied in soil corrosion environment.
The technical scheme adopted by the invention is as follows:
A preparation method of a corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles comprises the following steps:
The steel matrix is used as a cathode, a pure nickel plate is used as an anode, and Ni-Co-Y 2O3 electrodeposition solution is used for electrodeposition on the surface of the steel matrix to obtain a Ni-Co-Y 2O3 nano composite coating with mastoid protrusions; and then using a low surface energy modification method to enable the Ni-Co-Y 2O3 nano composite coating to have superhydrophobicity, and finally drying to obtain the corrosion-resistant superhydrophobic composite material containing nano Y 2O3 particles.
Preferably, the composition of the Ni-Co-Y 2O3 electrodeposition solution is as follows:
The concentration of NiSO 4·6H2 O is 150-300 g/L; the concentration of CoSO 4·7H2 O is 10-25 g/L; the concentration of NiCl 2·6H2 O is 15-30 g/L; the concentration of H 3BO3 is 15-30 g/L; the concentration of the citric acid is 60-90 g/L; the concentration of saccharin sodium is 0.5-1g/L; the concentration of the sodium dodecyl benzene sulfonate is 0.05-0.10 g/L; the concentration of the 1, 4-butynediol is 0.3-0.6g/L; the concentration of thiourea is 0.01-0.04g/L; the concentration of nanometer Y 2O3 is 5-20g/L.
Preferably, the Ni-Co-Y 2O3 electrodeposition solution is prepared by mixing a Ni-Co alloy electrodeposition solution and a nano Y 2O3 dispersion liquid, and the Ni-Co alloy electrodeposition solution is prepared by mixing and dissolving nickel sulfate, cobalt sulfate, boric acid, nickel chloride, citric acid, saccharin sodium, sodium dodecyl benzene sulfonate, 1, 4-butynediol, thiourea and deionized water.
Preferably, the preparation process of the nano Y 2O3 dispersion liquid comprises the following steps: adding nano Y 2O3 particles into deionized water, performing ultrasonic dispersion for 15-30min, standing and wetting for 21-24h to obtain nano Y 2O3 particle suspension, and performing ultrasonic dispersion again on the nano Y 2O3 particle suspension for 20-35min to obtain nano Y 2O3 dispersion.
Preferably, the preparation process of the Ni-Co alloy electrodeposition solution comprises the following steps:
Mixing NiSO 4·6H2O、CoSO4·7H2 O and NiCl 2·6H2 O with deionized water, and fully stirring for dissolution to obtain a main salt solution;
Mixing H 3BO3 with deionized water, heating until boiling, and maintaining for 5-8 min to obtain H 3BO3 solution;
dropwise adding the H 3BO3 solution into the main salt solution to obtain a solution A;
Mixing citric acid, saccharin sodium, sodium dodecyl benzene sulfonate, 1, 4-butynediol, thiourea and deionized water, and stirring for dissolving to obtain a solution B;
And adding the solution B into the solution A to obtain the Ni-Co alloy electrodeposition solution.
Preferably, the steel matrix after pretreatment is adopted for electrodeposition, and the pretreatment process of the steel matrix comprises polishing, cleaning, activating and washing, wherein the polishing process removes an oxide layer on the surface of the steel matrix, the cleaning process removes greasy dirt on the surface of the steel matrix, the activating is activated by dilute hydrochloric acid, and deionized water is adopted for washing.
Preferably, the cleaning process adopts alkali liquor for degreasing, wherein the alkali liquor contains 30-45 g/LNaOH and 20-35 g/LNa 3PO4、10～25g/LNa2CO3; the degreasing process is carried out at room temperature, and the degreasing time is 10-25min; the mass fraction of the dilute hydrochloric acid is 8-11% during activation.
Preferably, when the Ni-Co-Y 2O3 nano composite coating has superhydrophobicity by using a low surface energy modification method, the low surface energy modification solution is ethanol solution of stearic acid, the mass fraction of stearic acid is 1% -4%, and the low surface energy modification time is 60-90 min;
And when the drying treatment is carried out, the drying temperature is 80-110 ℃ and the drying time is 90-120 min.
Preferably, in the electrodeposition process, the deposition time is 90-120 min, the distance between the cathode and the anode is 3-4.5 cm, the area ratio of the cathode to the anode is (1:3) - (1:6), the temperature is 45-60 ℃, the current density is 4-7A/dm 2, the electrodeposition solution is continuously stirred, and the rotating speed is controlled at 400-550 rpm.
The invention also provides a corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, and the composite material is prepared by adopting the preparation method disclosed by the invention.
The invention has the following beneficial effects:
The invention relates to a preparation method of a corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, which is characterized in that a composite electrodeposition method which takes nano Y 2O3 particles as second phase particles and Ni and Co as main elements of a coating is combined by adopting direct current deposition to prepare a Ni-Co-Y 2O3 nano composite coating with micro-nano mastoid protrusions, and the rare earth Y 2O3 nano particles can be used for eliminating hot shortness, refining grains, improving the hardness and other performances of the coating, and reducing the defects of micropores and the like on the surface of the coating, thereby improving the corrosion resistance of the coating. And then carrying out low surface energy modification on the Ni-Co-Y 2O3 composite coating to obtain the Ni-Co-Y 2O3 corrosion-resistant super-hydrophobic composite coating. The invention can obviously improve the corrosion resistance of the Ni-Co alloy plating layer. When the corrosive medium reaches the surface of the coating, the corrosive ions are difficult to infiltrate into the inside due to the double protection of the surface hydrophobic layer and the nano composite coating, so that the corrosion resistance of the coating is improved, and a new thought is provided for preparing the novel metal composite coating. The preparation method provided by the invention is simple, efficient, easy to control, mild in reaction condition and capable of realizing large-area preparation.
Drawings
FIG. 1 (a) is a surface topography diagram of a composite material of a corrosion-resistant super-hydrophobic composite coating containing Ni-Co-Y 2O3 with nano Y 2O3 particles prepared in the embodiment 1 of the invention; FIG. 1 (b) is a schematic diagram showing the static water contact angle of the surface of the Ni-Co-Y 2O3 superhydrophobic composite coating containing nano Y 2O3 particles prepared in example 1 of the present invention.
FIG. 2 (a) is a surface topography diagram of a composite material of a corrosion-resistant super-hydrophobic composite coating containing Ni-Co-Y 2O3 with nano Y 2O3 particles prepared in example 2 of the present invention; FIG. 2 (b) is a schematic diagram showing the static water contact angle of the surface of the Ni-Co-Y 2O3 superhydrophobic composite coating containing nano Y 2O3 particles prepared in example 2 of the present invention.
FIG. 3 (a) is a surface topography diagram of a corrosion-resistant superhydrophobic composite coating containing nano Y 2O3 particles prepared in example 3 of the invention; FIG. 3 (b) is a schematic diagram showing the static water contact angle of the surface of the Ni-Co-Y 2O3 superhydrophobic composite coating containing nano Y 2O3 particles prepared in example 3 of the present invention.
FIG. 4 (a) is a surface topography diagram of a corrosion-resistant super-hydrophobic composite coating containing Ni-Co-Y 2O3 nano Y 2O3 particles prepared in example 4 of the present invention; FIG. 4 (b) is a schematic diagram showing the static water contact angle of the surface of the Ni-Co-Y 2O3 superhydrophobic composite coating containing nano Y 2O3 particles prepared in example 4 of the present invention.
FIG. 5 is an AC impedance diagram of the corrosion-resistant super-hydrophobic composite coating of X100 steel, the Ni-Co-Y 2O3 containing nano Y 2O3 particles prepared in the examples 1,2,3 and 4.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples.
Aiming at the defect of low corrosion resistance of the Ni-Co plating layer in the prior art, the invention can fill the defects of micropores and the like on the surface of the alloy plating layer by virtue of the rare earth nanometer Y 2O3, refine grains and the like; meanwhile, the superhydrophobic performance effectively reduces the contact area between the substrate and the corrosive medium, and multiple protection is carried out on the substrate, so that the corrosion resistance of the composite coating is improved. The specific scheme of the invention is as follows:
The invention relates to a preparation method of a corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, which comprises the following steps:
Electrodepositing by using a substrate (such as a pipeline steel substrate) as a cathode, a pure nickel plate as an anode and a Ni-Co-Y 2O3 electrodepositing solution, and preparing a Ni-Co-Y 2O3 composite coating with mastoid protrusions on the surface of the substrate; and then, endowing the Ni-Co-Y 2O3 composite coating with superhydrophobicity by using a low-surface energy substance modification method, and finally, drying to obtain the corrosion-resistant superhydrophobic composite material containing nano Y 2O3 particles.
Specifically, the Ni-Co-Y 2O3 electrodeposition solution adopted by the invention is formed by mixing the Ni-Co alloy electrodeposition solution and nano Y 2O3 dispersion liquid. The Ni-Co alloy electrodepositing solution is prepared by fully stirring and dissolving nickel sulfate, cobalt sulfate, boric acid, nickel chloride, citric acid, saccharin sodium, sodium dodecyl benzene sulfonate, 1, 4-butynediol, thiourea and deionized water. The concentrations of the components in the Ni-Co-Y 2O3 electrodeposition solution were as follows: the concentration of NiSO 4·6H2 O is 150-300 g/L; the concentration of CoSO 4·7H2 O is 10-25 g/L; the concentration of NiCl 2·6H2 O is 15-30 g/L; the concentration of H 3BO3 is 15-30 g/L; the concentration of the citric acid is 60-90 g/L; the concentration of saccharin sodium is 0.5-1g/L; the concentration of SDBS is 0.05-0.10 g/L; the concentration of the 1, 4-butynediol is 0.3-0.6g/L; the concentration of thiourea is 0.01-0.04g/L; the concentration of nanometer Y 2O3 is 5-20g/L. Nickel sulfate (NiSO 4·6H2 O) to provide nickel ions for the electrodeposition process; cobalt sulfate (CoSO 4·6H2 O) provides cobalt ions for the electrodeposition process; nickel chloride (NiCl 2·6H2 O) prevents anode passivation; boric acid (H 3BO3) is a pH buffering agent, so that the stability of the pH value of the plating solution is maintained; citric Acid (CITRICACID) is used as a complexing agent to ensure the stable operation of the electrodeposition reaction process; sodium Dodecyl Benzene Sulfonate (SDBS) is used as a surfactant to improve the suspension amount of nano Y 2O3 particles in the plating solution; 1, 4-butynediol and sodium saccharin (SodiumSaccharin) act as brightening agents for the solution, the main purpose of which is to planarize the surface of the formed coating and to fine the grains during electrodeposition.
When preparing the Ni-Co alloy electrodeposition solution, the method comprises the following steps:
1) Weighing 75-150 gNiSO 4·6H2O、5～12.5gCoSO4·7H2 O and 7.5-15 gNiCl 2·6H2 O, putting into a 500ml beaker, adding 300ml deionized water, and fully stirring and dissolving to prepare a main salt solution;
2) Weighing 7.5-15 g of H 3BO3, putting into a 100ml beaker, adding 50ml of deionized water, heating until boiling, and maintaining for 5-8 min to obtain H 3BO3 solution;
3) Slowly dripping the H 3BO3 solution into the main salt solution;
4) Weighing 30-45 g of citric acid and 0.25-0.5 g of saccharin sodium; 0.025-0.05 g of sodium dodecyl benzene sulfonate; 0.15-0.3 g of 1, 4-butynediol and 0.005-0.02 g of thiourea are put into a 100ml beaker, 75ml of deionized water is added, and stirring and dissolving are carried out;
5) Slowly adding the solution prepared in the step 4) into the solution obtained in the step 3), and finally obtaining the Ni-Co alloy electrodepositing solution.
The nanometer Y 2O3 dispersion is prepared by putting nanometer Y 2O3 particles into proper deionized water, performing ultrasonic dispersion for 15-30min, standing and wetting for 21-24h, then performing ultrasonic dispersion for 20-35min again on the wetted nanometer Y 2O3 particle suspension, and finally adding the nanoparticle dispersion into the prepared Ni-Co alloy electrodeposition solution to obtain Ni-Co-Y 2O3 electrodeposition solution, fixing the volume, and fully stirring for standby.
When the Ni-Co-Y 2O3 nano composite coating with mastoid-shaped protrusions is subjected to low surface energy modification, the used low surface energy modification solution is ethanol solution of stearic acid, the mass fraction of stearic acid is 1% -4%, and the low surface energy modification time is 60-90 min. And (3) drying the Ni-Co-Y 2O3 super-hydrophobic nano composite coating subjected to low surface energy modification, wherein the drying temperature is 80-110 ℃ and the drying time is 90-120 min.
In the electrodeposition process, the deposition time is 90-120 min, the cathode-anode distance is 3-4.5 cm, the cathode-anode area ratio is (1:3) - (1:6), the temperature is 45-60 ℃, the current density is 4-7A/dm 2, the electrodeposition solution is continuously stirred, and the rotating speed is controlled at 400-550 rpm.
In the technical scheme of the invention, the electrodeposition process is carried out by adopting the pretreated substrate, and the pretreatment process of the substrate comprises polishing, cleaning, activating and washing. The polishing adopts mechanical polishing, wherein the mechanical polishing is sand paper polishing, ultrasonic alkali liquor is used for degreasing and hot water washing are used for cleaning, dilute hydrochloric acid is used for activating, and deionized water washing is performed. In the alkali liquor deoiling process, the alkali liquor formula is 30-45 g/LNaOH, 20-35 g/LNa 3PO4、10～25g/LNa2CO3; the degreasing process is carried out at room temperature, and the degreasing time is 10-25min; the mass fraction of the dilute hydrochloric acid is 8-11% during activation.
The invention can fill micropores on the surface of the alloy plating layer, refine grains, reduce hydrogen embrittlement and pinholes by means of the intrinsic hydrophobicity of the rare earth nanometer Y 2O3; meanwhile, the superhydrophobic performance effectively reduces the contact area between the substrate and the corrosive medium, and multiple protection is carried out on the substrate, so that the corrosion resistance of the composite coating is improved. Therefore, the corrosion-resistant super-hydrophobic composite material containing the nano Y 2O3 particles has excellent corrosion resistance and hydrophobicity.
Example 1:
the preparation method of the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles in the embodiment adopts an X100 steel matrix as the matrix, and comprises the following steps:
(1) Pretreatment of a matrix:
a. And (3) sample packaging: cutting the matrix into cubes with the diameter of 10mm and the diameter of 3mm, welding one end of a wire with a sample, and encapsulating with epoxy resin to prepare the working electrode with the working area of 1cm 2.
B. Mechanical polishing: sequentially polishing the working surface of the matrix by using No. 180, no. 400, no. 600, no. 800, no. 1200 and No. 1500 abrasive paper to remove the oxide layer of the X100 steel matrix; and then cleaning by acetone and ethanol, and drying for later use.
C. Deoiling with alkali liquor: the degreasing solution adopted comprises the following components: 30g/L NaOH, 20g/L Na 3PO4、10g/L Na2CO3; the degreasing process is carried out in ultrasound at 25 ℃ for 10min.
D. Activating: the activating solution is diluted hydrochloric acid with mass fraction of 8%, and the activating time is 1min.
After each procedure is completed, deionized water is used for ultrasonic cleaning and drying is carried out for standby.
(2) Preparing an Ni-Co electrodeposition solution:
75g of nickel sulfate (NiSO 4·6H2 O), 5g of cobalt sulfate (CoSO 4·6H2 O), 7.5g of nickel chloride (NiCl 2·6H2 O), 7.5g of boric acid (H 3BO3), 30g of citric acid (CITRIC ACID), 0.25g of saccharin sodium (Sodium Saccharin), 0.15g of 1, 4-butynediol, 0.005g of thiourea and 0.025g of Sodium Dodecyl Benzene Sulfonate (SDBS) are respectively weighed by an electronic day, slowly added into a beaker with a proper amount of deionized water, and uniformly stirred to obtain an Ni-Co alloy electrodeposition solution for later use. 2.5g of Y 2O3 particles with the particle size not exceeding 40nm are weighed by an electronic balance, placed into a proper amount of deionized water for ultrasonic dispersion for 15min and standing for 21h, then the wetted nanoparticle suspension is subjected to ultrasonic dispersion again for 20min, finally the dispersed nanoparticle suspension is added into the prepared Ni-Co alloy electrodeposition solution to obtain Ni-Co-Y 2O3 electrodeposition solution, the volume is fixed to 500mL, and standing is carried out for standby.
(3) Electrodeposition
During electrodeposition, the positive electrode of the power supply is connected with a pure nickel plate, the negative electrode is connected with an X100 steel matrix, the distance between the positive electrode and the negative electrode is 3cm, and the current density is set to be 4A/dm 2; heating the Ni-Co electrodeposition solution in the beaker by using a constant-temperature water bath kettle, setting the electrodeposition time to be 90min and the temperature to be 45 ℃; the mechanical stirring speed was 400rpm. The electrodeposited sample was rinsed with deionized water.
(4) Low surface energy modification:
preparing a low surface energy modification solution of stearic acid with the mass fraction of 1% and absolute ethyl alcohol with the mass fraction of 99%, and uniformly stirring for later use. And immersing the X100 steel matrix with the surface provided with the coating with the micro-nano coarse structure after electrodeposition in an ethanol solution of stearic acid for 60min.
(5) Drying treatment
And drying the X100 steel matrix with the modified low surface energy, and putting the X100 steel matrix into an oven at the temperature of 80 ℃ for 90min. And finally, packaging the X100 steel matrix with a sample bag, and then placing the packaged X100 steel matrix into a drying oven for subsequent testing of various performances.
The surface topography of the Ni-Co-Y 2O3 corrosion-resistant super-hydrophobic composite coating containing nano Y 2O3 particles prepared in this example is shown in FIG. 1 (a), and the mastoid protrusions on the surface of the coating are substantially uniform.
Example 2:
the preparation method of the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles in the embodiment adopts an X100 steel matrix as the matrix, and comprises the following steps:
(1) Pretreatment of a matrix:
a. And (3) sample packaging: cutting the matrix into cubes with the diameter of 10mm and the diameter of 3mm, welding one end of a wire with a sample, and encapsulating with epoxy resin to prepare the working electrode with the working area of 1cm 2.
B. Mechanical polishing: sequentially polishing the working surface of the matrix by using No. 180, no. 400, no. 600, no. 800, no. 1200 and No. 1500 abrasive paper to remove the oxide layer of the X100 steel matrix; and then cleaning by acetone and ethanol, and drying for later use.
C. Deoiling with alkali liquor: the degreasing solution adopted comprises the following components: 35g/L NaOH, 25g/L Na 3PO4、15g/L Na2CO3; the degreasing process is carried out in ultrasound at 25 ℃ for 15min.
D. Activating: the activating solution is diluted hydrochloric acid with the mass fraction of 9%, and the activating time is 1min.
After each procedure is completed, deionized water is used for ultrasonic cleaning and drying is carried out for standby.
(2) Preparation of Ni-Co-Y 2O3 electrodeposition solution:
100g of nickel sulfate (NiSO 4·6H2 O), 7.5g of cobalt sulfate (CoSO 4·6H2 O), 10g of nickel chloride (NiCl 2·6H2 O), 10g of boric acid (H 3BO3), 35g of citric acid (CITRIC ACID), 0.3g of saccharin sodium (Sodium Saccharin), 0.20g of 1, 4-butynediol, 0.01g of thiourea and 0.03g of Sodium Dodecyl Benzene Sulfonate (SDBS) are respectively weighed by an electronic day, and slowly added into a beaker filled with a proper amount of deionized water, and uniformly stirred to obtain an Ni-Co alloy electrodeposition solution; weighing 5g of Y 2O3 particles with the particle size not exceeding 40nm by using an electronic balance, putting into a proper amount of deionized water, performing ultrasonic dispersion for 20min, standing for 22h, performing ultrasonic dispersion on the wetted nanoparticle suspension again for 25min, adding the dispersed nanoparticle suspension into the prepared Ni-Co alloy electrodeposition solution to obtain Ni-Co-Y 2O3 electrodeposition solution, fixing the volume to 500mL, and standing for later use.
(3) Electrodeposition:
during electrodeposition, the positive electrode of the power supply is connected with a pure nickel plate, the negative electrode is connected with an X100 steel matrix, the distance between the positive electrode and the negative electrode is 3.5cm, and the current density is set to be 5A/dm 2; heating Ni-Co-Y 2O3 electrodeposition solution in a beaker by using a constant-temperature water bath, setting the electrodeposition time to be 100min and the temperature to be 50 ℃; the mechanical stirring speed was 450rpm. The electrodeposited sample was rinsed with deionized water.
(4) Low surface energy modification:
Preparing a low surface energy modification solution of stearic acid with the mass fraction of 2% and absolute ethyl alcohol with the mass fraction of 98%, and uniformly stirring for later use. And immersing the X100 steel matrix with the surface provided with the coating with the micro-nano coarse structure after electrodeposition in ethanol solution of stearic acid for 65min.
(5) And (3) drying:
and drying the X100 steel matrix with the modified low surface energy, and putting the X100 steel matrix into an oven at the temperature of 90 ℃ for 100min. And finally, packaging the X100 steel matrix with a sample bag, and then placing the packaged X100 steel matrix into a drying oven for subsequent testing of various performances.
The surface topography of the Ni-Co-Y 2O3 corrosion-resistant super-hydrophobic composite coating containing nano Y 2O3 particles prepared in the embodiment is shown in figure 2 (a), mastoid protrusions are uniformly distributed on the surface of the coating, and the coating is complete and compact.
Example 3:
the preparation method of the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles in the embodiment adopts an X100 steel matrix as the matrix, and comprises the following steps:
(1) Pretreatment of a matrix:
a. And (3) sample packaging: cutting the matrix into cubes with the diameter of 10mm and the diameter of 3mm, welding one end of a wire with a sample, and encapsulating with epoxy resin to prepare the working electrode with the working area of 1cm 2.
B. Mechanical polishing: sequentially polishing the working surface of the matrix by using No. 180, no. 400, no. 600, no. 800, no. 1200 and No. 1500 abrasive paper to remove the oxide layer of the X100 steel matrix; and then cleaning by acetone and ethanol, and drying for later use.
C. deoiling with alkali liquor: the degreasing solution adopted comprises the following components: 40g/L NaOH, 30g/L Na 3PO4、20g/L Na2CO3; the degreasing process is carried out in ultrasound at 25 ℃ for 20min.
D. Activating: the activating solution is diluted hydrochloric acid with the mass fraction of 10%, and the activating time is 1min.
After each procedure is completed, deionized water is used for ultrasonic cleaning and drying is carried out for standby.
(2) Preparation of Ni-Co-Y 2O3 electrodeposition solution:
125g of nickel sulfate (NiSO 4·6H2 O), 10g of cobalt sulfate (CoSO 4·6H2 O), 12.5g of nickel chloride (NiCl 2·6H2 O), 12.5g of boric acid (H 3BO3), 40g of citric acid (CITRIC ACID), 0.4g of saccharin sodium (Sodium Saccharin), 0.25g of 1, 4-butynediol, 0.015g of thiourea and 0.04g of Sodium Dodecyl Benzene Sulfonate (SDBS) are respectively weighed by an electronic day, slowly added into a beaker filled with a proper amount of deionized water, and uniformly stirred to obtain an Ni-Co alloy electrodeposition solution; and weighing 7.5g of Y 2O3 particles with the particle size not exceeding 40nm by using an electronic balance, putting into a proper amount of deionized water, performing ultrasonic dispersion for 25min, standing for 23h, performing ultrasonic dispersion on the wetted nanoparticle suspension again for 30min, adding the dispersed nanoparticle suspension into the prepared Ni-Co alloy electrodeposition solution to obtain Ni-Co-Y 2O3 electrodeposition solution, fixing the volume to 500mL, and standing for later use.
(3) Electrodeposition:
During electrodeposition, the positive electrode of the power supply is connected with a pure nickel plate, the negative electrode is connected with an X100 steel matrix, the distance between the positive electrode and the negative electrode is 4cm, and the current density is set to be 6A/dm 2; heating the Ni-Co-Y 2O3 plating solution in the beaker by using a constant-temperature water bath, setting the electrodeposition time to be 110min and the temperature to be 55 ℃; the mechanical stirring speed was 500rpm. The electrodeposited sample was rinsed with deionized water.
(4) Low surface energy modification:
Preparing a low surface energy modification solution of stearic acid with the mass fraction of 3% and absolute ethyl alcohol with the mass fraction of 97%, and uniformly stirring for later use. And immersing the X100 steel matrix with the surface provided with the coating with the micro-nano coarse structure after electrodeposition in ethanol solution of stearic acid for 80min.
(5) And (3) drying:
And drying the X100 steel matrix with the modified low surface energy, and putting the X100 steel matrix into an oven at the temperature of 100 ℃ for 110min. And finally, packaging the X100 steel matrix with a sample bag, and then placing the packaged X100 steel matrix into a drying oven for subsequent testing of various performances.
The surface topography of the Ni-Co-Y 2O3 corrosion-resistant super-hydrophobic composite coating containing nano Y 2O3 particles prepared in the embodiment is shown in figure 3 (a), the coating surface is uniform, flat and compact, and the grains become smaller.
Example 4:
the preparation method of the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles in the embodiment adopts an X100 steel matrix as the matrix, and comprises the following steps:
(1) Pretreatment of a matrix:
a. And (3) sample packaging: cutting the matrix into cubes with the diameter of 10mm and the diameter of 3mm, welding one end of a wire with a sample, and encapsulating with epoxy resin to prepare the working electrode with the working area of 1cm 2.
B. Mechanical polishing: sequentially polishing the working surface of the matrix by using No. 180, no. 400, no. 600, no. 800, no. 1200 and No. 1500 abrasive paper to remove the oxide layer of the X100 steel matrix; and then cleaning by acetone and ethanol, and drying for later use.
C. Deoiling with alkali liquor: the degreasing solution adopted comprises the following components: 45g/L NaOH and 35g/L Na 3PO4、25g/L Na2CO3; the degreasing process is carried out in ultrasound at 25 ℃ for 25min.
D. Activating: the activating solution is diluted hydrochloric acid with the mass fraction of 11%, and the activating time is 1min.
After each procedure is completed, deionized water is used for ultrasonic cleaning and drying is carried out for standby.
(2) Preparation of Ni-Co-Y 2O3 electrodeposition solution:
150g of nickel sulfate (NiSO 4·6H2 O), 12.5g of cobalt sulfate (CoSO 4·6H2 O), 15g of nickel chloride (NiCl 2·6H2 O), 15g of boric acid (H 3BO3), 45g of citric acid (CITRIC ACID), 0.4g of saccharin sodium (Sodium Saccharin), 0.3g of 1, 4-butynediol, 0.020g of thiourea and 0.04g of Sodium Dodecyl Benzene Sulfonate (SDBS) are respectively weighed by an electronic day, and slowly added into a beaker filled with a proper amount of deionized water, and uniformly stirred to obtain an Ni-Co alloy electrodeposition solution; weighing 10.0g of Y 2O3 particles with the particle size not exceeding 40nm by using an electronic balance, putting into a proper amount of deionized water, performing ultrasonic dispersion for 30min, standing for 24h, performing ultrasonic dispersion on the wetted nanoparticle suspension again for 35min, adding the dispersed nanoparticle suspension into the prepared Ni-Co alloy electrodeposition solution to obtain Ni-Co-Y 2O3 electrodeposition solution, fixing the volume to 500mL, and standing for later use.
(3) Electrodeposition:
during electrodeposition, the positive electrode of the power supply is connected with a pure nickel plate, the negative electrode is connected with an X100 steel matrix, the distance between the positive electrode and the negative electrode is 4.5cm, and the current density is set to be 7A/dm 2; heating the Ni-Co-Y 2O3 plating solution in the beaker by using a constant-temperature water bath, setting the electrodeposition time to be 120min and the temperature to be 60 ℃; the mechanical stirring speed was 550rpm. The electrodeposited sample was rinsed with deionized water.
(4) Low surface energy modification:
Preparing a low surface energy modification solution of stearic acid with the mass fraction of 4% and absolute ethyl alcohol with the mass fraction of 96%, and uniformly stirring for later use. And immersing the X100 steel matrix with the surface provided with the coating with the micro-nano coarse structure after electrodeposition in an ethanol solution of stearic acid for 90min.
(5) And (3) drying:
And drying the X100 steel matrix with the modified low surface energy, and putting the X100 steel matrix into an oven at the temperature of 110 ℃ for 120min. And finally, packaging the X100 steel matrix with a sample bag, and then placing the packaged X100 steel matrix into a drying oven for subsequent testing of various performances.
The surface topography of the Ni-Co-Y 2O3 corrosion-resistant super-hydrophobic composite coating containing nano Y 2O3 particles prepared in this example is shown in FIG. 4 (a), the coating is uniform and compact, and mastoid protrusions are also uniformly distributed.
Contact angle measurements were performed on the composite materials with the corrosion-resistant superhydrophobic composite coatings of Ni-Co-Y 2O3 prepared in examples 1 to 4 of the present invention, and the results are shown in table 1:
TABLE 1
As can be obtained from table 1, fig. 1 (b), fig. 2 (b), fig. 3 (b) and fig. 4 (b), the contact angle of the Ni-Co-Y 2O3 nano composite coating prepared on the surface of the X100 steel by adopting the method is more than 150 degrees, and the super-hydrophobic state is achieved. The surface morphology of the super-hydrophobic composite plating layer prepared on the X100 steel surface in the embodiment 1 to the embodiment 4 of the invention is characterized, and the result is that the mastoid protrusions on the surface of the super-hydrophobic composite plating layer containing nano Y 2O3 particles obtained in the embodiment of the invention are uniformly distributed and compact in structure as shown in the figures 1 (a), 2 (a), 3 (a) and4 (a) and can be obtained by referring to the figures. As can be obtained from FIG. 5, the prepared Ni-Co-Y 2O3 super-hydrophobic composite coating has excellent corrosion resistance. The double protection effect of the super-hydrophobic film and the Ni-Co-Y 2O3 nano-coating on the matrix can obviously improve the corrosion resistance. On the other hand, the mastoid-shaped protrusions on the surface of the plating layer construct a stable Cassie state, and air trapping in the mastoid-shaped protrusions is ensured. The air which is retained has a buffer function, and the adsorption of water on the surface of the plating layer is prevented. In addition, the addition of Y 2O3 particles has a tendency to fill in defects of the Ni-Co plating; can also be used as a physical barrier, and can obviously prolong the penetration and diffusion of corrosive ions to the surface of the matrix.
From the above, the invention can obviously improve the corrosion resistance of the Ni-Co plating layer, has higher hydrophobicity, and the surface of the obtained plating layer has a micro-nano mastoid protuberance structure. When the corrosive medium contacts with the nano composite coating, double protection of the surface super-hydrophobic film and the nano composite coating prevents corrosive ions from immersing into the coating, so that the corrosion resistance of the coating is improved, and a new thought is provided for the prepared novel composite coating to be widely applied in a soil corrosion environment.
Claims (8)
1. The preparation method of the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles is characterized by comprising the following steps:
The steel matrix is used as a cathode, a pure nickel plate is used as an anode, and Ni-Co-Y 2O3 electrodeposition solution is used for electrodeposition on the surface of the steel matrix to obtain a Ni-Co-Y 2O3 nano composite coating with mastoid protrusions; then using a low surface energy modification method to enable the Ni-Co-Y 2O3 nano composite coating to have superhydrophobicity, and finally drying to obtain the corrosion-resistant superhydrophobic composite material containing nano Y 2O3 particles;
The composition of the Ni-Co-Y 2O3 electrodeposition solution is as follows:
The concentration of NiSO 4·6H2 O is 150-300 g/L; the concentration of CoSO 4·7H2 O is 10-25 g/L; the concentration of NiCl 2·6H2 O is 15-30 g/L; the concentration of H 3BO3 is 15-30 g/L; the concentration of the citric acid is 60-90 g/L; the concentration of saccharin sodium is 0.5-1g/L; the concentration of the sodium dodecyl benzene sulfonate is 0.05-0.10 g/L; the concentration of the 1, 4-butynediol is 0.3-0.6g/L; the concentration of thiourea is 0.01-0.04g/L; the concentration of the nanometer Y 2O3 is 5-20g/L;
In the electrodeposition process, the deposition time is 90-120 min, the distance between the cathode and the anode is 3-4.5 cm, the area ratio of the cathode to the anode is (1:3) - (1:6), the temperature is 45-60 ℃, the current density is 4-7A/dm 2, the electrodeposition solution is continuously stirred, and the rotating speed is controlled to be 400-550 rpm.
2. The method for preparing the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, which is disclosed in claim 1, is characterized in that the Ni-Co-Y 2O3 electrodeposition solution is prepared by mixing a Ni-Co alloy electrodeposition solution and nano Y 2O3 dispersion liquid, and the Ni-Co alloy electrodeposition solution is prepared by mixing and dissolving nickel sulfate, cobalt sulfate, boric acid, nickel chloride, citric acid, saccharin sodium, sodium dodecyl benzene sulfonate, 1, 4-butynediol, thiourea and deionized water.
3. The method for preparing the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles according to claim 2, wherein the preparation process of the nano Y 2O3 dispersion liquid comprises the following steps: adding nano Y 2O3 particles into deionized water, performing ultrasonic dispersion for 15-30min, standing and wetting for 21-24h to obtain nano Y 2O3 particle suspension, and performing ultrasonic dispersion again on the nano Y 2O3 particle suspension for 20-35min to obtain nano Y 2O3 dispersion.
4. The method for preparing the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles according to claim 2, wherein the preparation process of the Ni-Co alloy electrodeposition solution comprises the following steps:
Mixing NiSO 4·6H2O、CoSO4·7H2 O and NiCl 2·6H2 O with deionized water, and fully stirring for dissolution to obtain a main salt solution;
Mixing H 3BO3 with deionized water, heating until boiling, and maintaining for 5-8 min to obtain H 3BO3 solution;
dropwise adding the H 3BO3 solution into the main salt solution to obtain a solution A;
Mixing citric acid, saccharin sodium, sodium dodecyl benzene sulfonate, 1, 4-butynediol, thiourea and deionized water, and stirring for dissolving to obtain a solution B;
And adding the solution B into the solution A to obtain the Ni-Co alloy electrodeposition solution.
5. The method for preparing the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, which is characterized in that the pre-treated steel matrix is adopted for electrodeposition, the pre-treatment process of the steel matrix comprises polishing, cleaning, activating and washing, wherein the polishing process removes an oxide layer on the surface of the steel matrix, the cleaning process removes greasy dirt on the surface of the steel matrix, the activating is activated by dilute hydrochloric acid, and the washing is performed by deionized water.
6. The method for preparing the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, which is characterized in that alkali liquor is used for degreasing in the cleaning process, wherein the alkali liquor contains 30-45 g/L NaOH and 20-35 g/L Na 3PO4、10~25g/L Na2CO3; the degreasing process is carried out at room temperature, and the degreasing time is 10-25min; the mass fraction of the dilute hydrochloric acid during activation is 8% -11%.
7. The preparation method of the corrosion-resistant super-hydrophobic composite material containing nano Y 2O3 particles, which is characterized in that when the Ni-Co-Y 2O3 nano composite coating has super-hydrophobicity by using a low surface energy modification method, the used low surface energy modification solution is ethanol solution of stearic acid, the mass fraction of stearic acid is 1% -4%, and the low surface energy modification time is 60-90 min;
And when the drying treatment is carried out, the drying temperature is 80-110 ℃ and the drying time is 90-120 min.
8. The corrosion-resistant superhydrophobic composite containing nano Y 2O3 particles prepared by the method for preparing the corrosion-resistant superhydrophobic composite containing nano Y 2O3 particles according to any one of claims 1-7.
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