CN114790563A - Corrosion-resistant super-hydrophobic copper-nickel composite coating and preparation method and application thereof - Google Patents

Corrosion-resistant super-hydrophobic copper-nickel composite coating and preparation method and application thereof Download PDF

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CN114790563A
CN114790563A CN202210472508.6A CN202210472508A CN114790563A CN 114790563 A CN114790563 A CN 114790563A CN 202210472508 A CN202210472508 A CN 202210472508A CN 114790563 A CN114790563 A CN 114790563A
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solution
nickel
electroplating
copper
boron carbide
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赵雪
东书汉
杨阳
马瑞娜
范永哲
杜安
曹晓明
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Hebei University of Technology
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Hebei University of Technology
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
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Abstract

The invention provides a corrosion-resistant super-hydrophobic copper-nickel composite coating, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) carrying out oil and rust removal pretreatment on a metal matrix; (2) electroplating a copper coating on the surface of the metal substrate obtained in the step (1); (3) electroplating a nickel-boron carbide coating on the surface of the metal matrix obtained in the step (2); (4) modifying the surface of the metal matrix obtained in the step (3) to obtain a copper-nickel composite coating on the surface of the metal matrix; wherein, the nickel-boron carbide composite plating solution adopted by the electroplating in the step (3) contains micron-sized boron carbide particles. The water contact angle of the copper-nickel composite coating is not less than 150 degrees, and the rolling angle is not more than 10 degrees. The preparation method provided by the invention simplifies the preparation process, enhances the binding force between the coating and the metal matrix, improves the wear resistance and reduces the preparation cost.

Description

Corrosion-resistant super-hydrophobic copper-nickel composite coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal substrate surface anticorrosion treatment processes, relates to a composite coating, and particularly relates to a corrosion-resistant super-hydrophobic copper-nickel composite coating as well as a preparation method and application thereof.
Background
The steel surface coating is an effective protection measure for steel corrosion resistance, but most coatings need to be used for a long time in severe environments such as high humidity and heat, industrial atmosphere or marine atmosphere, and the like, and are difficult to provide effective protection for a steel matrix. For example: the hot dip galvanizing layer is low in price, but is difficult to apply to a humid environment; bright nickel or bright copper coatings, although having good shielding properties, are mostly hydrophilic and difficult to serve in a humid environment for a long time; particularly, the bright copper plating layer is easy to be corroded by a corrosive medium in a humid environment to form pitting holes, and once the plating layer is penetrated by the corrosive medium, the corrosion rate of the steel substrate is accelerated. Therefore, it is urgently needed to develop a coating which can resist the humid environment and expand the application range of the common steel materials in the humid environment.
The super-hydrophobic coating (the water contact angle is more than or equal to 150 degrees, the rolling angle is less than or equal to 10 degrees) is considered as an effective method for metal corrosion prevention, and the super-hydrophobic coating can efficiently prevent corrosion of a corrosive medium to a metal matrix. At present, a quick and convenient surface modification method is mostly adopted for a super-hydrophobic coating, and although the method is simple and convenient, the wear resistance of the coating is poor, and the problem of serious failure exists in the service process.
CN 109385630A discloses a one-step preparation process of a zinc-based super-hydrophobic functional surface, the invention utilizes the oxidation-reduction reaction between zinc and metal ions, simultaneously adds long chain fatty acid, and prepares a super-hydrophobic surface on galvanized steel by a one-step method, however, the corrosion resistance of a sample obtained by the preparation process is poor, and the further application and production of the super-hydrophobic surface are limited by the wear resistance and adhesive force of a coating.
CN 109183131A discloses a SiO 2 The invention relates to a preparation method of a base composite super-hydrophobic metal surface, which comprises the steps of firstly adopting composite sol to construct a silicon dioxide base micro-nano scale rough surface on the metal surface by an electrodeposition method, and then using a low surface energy substance to modify. However, the preparation method is complex in process and needs to be carried out with multiple times of ultrafiltration to realize the modification of the silicon dioxide. In order to solve the problems, a laser etching method is applied to the construction of the super-hydrophobic film layer, and the super-hydrophobic layer obtained by the laser etching method has good wear resistance, but is expensive in manufacturing cost and cannot be popularized and applied in practice.
Therefore, how to provide a corrosion-resistant super-hydrophobic coating, which can simplify the preparation process, enhance the binding force between the coating and the metal matrix, improve the wear resistance and reduce the preparation cost becomes a problem to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a corrosion-resistant super-hydrophobic copper-nickel composite coating, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a corrosion-resistant super-hydrophobic copper-nickel composite coating, which is characterized by comprising the following steps:
(1) carrying out oil and rust removal pretreatment on a metal matrix;
(2) electroplating a copper coating on the surface of the metal matrix obtained in the step (1);
(3) electroplating a nickel-boron carbide coating on the surface of the metal matrix obtained in the step (2);
(4) and (4) carrying out modification treatment on the surface of the metal matrix obtained in the step (3), namely preparing the copper-nickel composite coating on the surface of the metal matrix.
Wherein, the nickel-boron carbide composite plating solution adopted by the electroplating in the step (3) contains micron-sized boron carbide particles.
The invention replaces the nanometer particles in the composite plating solution adopted by the nanometer composite electroplating process which accounts for most of the current research with the micron particles, effectively solves the problem of particle agglomeration, and reduces the manufacturing cost and the plating process difficulty of the plating solution.
In addition, the existence of the micron-sized boron carbide particles promotes the preferential growth of nickel crystals, and the boron carbide particles impact and attach to the surface of a cathode plate in the electroplating process, so that heterogeneous nucleation sites are provided for the deposition of the nickel crystals, and the formation of a micro-nano structure of a coating is promoted; after the obtained coating with the micro-nano structure is modified, the surface energy of the coating is reduced, and the coating achieves super-hydrophobicity under the combined action of roughness and surface energy.
Particularly, a compact copper plating layer is plated below a nickel-boron carbide plating layer, the self-corrosion potential of the obtained super-hydrophobic copper-nickel composite plating layer is-0.2874V, which is higher than-0.3421V of an unmodified copper-nickel composite plating layer and-0.4488V of a pure nickel plating layer, and the increase of the corrosion potential shows that the corrosion activity of the plating layer is reduced; meanwhile, the super-hydrophobic copper-nickel composite coating also has the minimum corrosion current density of 1.87 multiplied by 10 -7 A/cm 2 Compared with the pure nickel coating layer of 7.05 multiplied by 10 -5 A/cm 2 The reduction is two orders of magnitude; the super-hydrophobic copper-nickel composite coating also prevents the nickel coating from generating a cathode effect after being damaged, and the compact copper layer still can play a shielding role after the nickel coating is damaged, so that a corrosion medium is prevented from being in direct contact with a metal matrix, and the corrosion resistance and the protective performance of the coating are enhanced.
Preferably, the metal matrix of steps (1) - (4) comprises a steel plate.
Preferably, the steel plate has any one of the models of Q235B, Q345B, 510L or 610L.
Preferably, the oil and rust removing pretreatment in the step (1) comprises oil removing treatment, rust removing treatment and flushing which are sequentially carried out.
Preferably, the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt.
Preferably, the sodium salt comprises any one of sodium hydroxide, sodium carbonate, sodium phosphate dodecahydrate or sodium silicate nonahydrate, or a combination of at least two thereof, and typical, but non-limiting combinations include a combination of sodium hydroxide and sodium carbonate, a combination of sodium carbonate and sodium phosphate dodecahydrate, a combination of sodium phosphate dodecahydrate and sodium silicate nonahydrate, a combination of sodium hydroxide, sodium carbonate and sodium phosphate dodecahydrate, a combination of sodium carbonate, sodium phosphate dodecahydrate and sodium silicate nonahydrate, or a combination of sodium hydroxide, sodium carbonate, sodium phosphate dodecahydrate and sodium silicate nonahydrate, and further preferably a combination of sodium hydroxide, sodium carbonate, sodium phosphate dodecahydrate and sodium silicate nonahydrate.
Preferably, the concentration of sodium hydroxide in the deoiling liquid is 40-60g/L, such as 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L, 56g/L, 58g/L or 60g/L, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the concentration of sodium carbonate in the degreasing liquid is 20-40g/L, for example 20g/L, 22g/L, 24g/L, 26g/L, 28g/L, 30g/L, 32g/L, 34g/L, 36g/L, 38g/L or 40g/L, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the concentration of sodium phosphate dodecahydrate in the deoiling liquid is 10-30g/L, for example, 10g/L, 12g/L, 14g/L, 16g/L, 18g/L, 20g/L, 22g/L, 24g/L, 26g/L, 28g/L or 30g/L, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the concentration of the sodium silicate nonahydrate in the degreasing fluid is 10-20g/L, for example, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L or 20g/L, but the concentration is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the degreasing temperature is 60-75 ℃, for example 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃ or 75 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the degreasing treatment is carried out for 10-30min, for example 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the rust removing liquid used in the rust removing treatment includes a hydrochloric acid solution.
Preferably, the concentration of the hydrochloric acid solution is 10-20 vt%, and may be, for example, 10 vt%, 11 vt%, 12 vt%, 13 vt%, 14 vt%, 15 vt%, 16 vt%, 17 vt%, 18 vt%, 19 vt% or 20 vt%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the rust removing treatment is 20 to 30 ℃, and may be, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the time for the rust removing treatment is 10 to 30min, and may be, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the rinsing solution used for rinsing comprises deionized water.
Preferably, the metal substrate is further soaked in the pre-soaking copper solution before the electroplating in step (2), so that a thin and uniform copper layer is plated on the surface of the metal substrate, and the metal substrate is protected from being corroded by the copper plating solution.
Before the metal matrix is soaked in the presoaked copper solution, the residual liquid drops on the surface of the metal matrix are removed by adopting compressed air so as to reduce errors and ensure that the concentration change of the subsequent solution is in an allowable range.
Preferably, the soaking time is 20 to 40s, for example, 20s, 22s, 24s, 26s, 28s, 30s, 32s, 34s, 36s, 38s or 40s, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the copper pre-soak solution comprises sulfuric acid, copper sulfate pentahydrate, and thiourea.
Preferably, the concentration of sulfuric acid in the copper pre-preg solution is 80-120g/L, for example 80g/L, 85g/L, 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g/L or 120g/L, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the concentration of copper sulfate pentahydrate in the pre-preg copper solution is 40-60g/L, such as 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L, 56g/L, 58g/L, or 60g/L, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the concentration of thiourea in the copper pre-preg solution is 0.1 to 0.3g/L, and may be, for example, 0.1g/L, 0.12g/L, 0.14g/L, 0.16g/L, 0.18g/L, 0.2g/L, 0.22g/L, 0.24g/L, 0.26g/L, 0.28g/L, or 0.3g/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, after the soaking, compressed air is used for removing residual liquid drops on the surface of the metal matrix.
Preferably, the electroplating copper solution used in the electroplating in step (2) comprises sulfuric acid, copper sulfate pentahydrate, sodium chloride and sodium dodecyl sulfate.
Preferably, the concentration of sulfuric acid in the electrolytic copper plating solution is 35 to 55g/L, for example, 35g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L or 55g/L, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the concentration of the copper sulfate pentahydrate in the copper electroplating solution is 200-280g/L, such as 200g/L, 210g/L, 220g/L, 230g/L, 240g/L, 250g/L, 260g/L, 270g/L or 280g/L, but the copper electroplating solution is not limited to the values listed, and other values not listed in the value range are also applicable.
Preferably, the concentration of sodium chloride in the electrolytic copper plating solution is 30 to 70ppm, and may be, for example, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, 55ppm, 60ppm, 65ppm or 70ppm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the concentration of sodium lauryl sulfate in the electrolytic copper plating solution is 0.1 to 0.3g/L, and may be, for example, 0.1g/L, 0.12g/L, 0.14g/L, 0.16g/L, 0.18g/L, 0.2g/L, 0.22g/L, 0.24g/L, 0.26g/L, 0.28g/L, or 0.3g/L, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the anode used for electroplating in the step (2) is a T2 copper plate.
Preferably, the current density of the electroplating in the step (2) is 1-2A/dm 2 It may be, for example, 1A/dm 2 、1.1A/dm 2 、1.2A/dm 2 、1.3A/dm 2 、1.4A/dm 2 、1.5A/dm 2 、1.6A/dm 2 、1.7A/dm 2 、1.8A/dm 2 、1.9A/dm 2 Or 2A/dm 2 However, the numerical values are not limited to the numerical values listed, and other numerical values not listed in the numerical range are also applicable.
Preferably, the pulse frequency of the electroplating in the step (2) is 200Hz and 500Hz, such as 200Hz, 250Hz, 300Hz, 350Hz, 400Hz, 450Hz or 500Hz, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the duty cycle of the electroplating in step (2) is 60% -80%, for example, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, or 80%, but not limited to the recited values, and other values in the range are also applicable.
Preferably, the stirring speed of the electroplating in step (2) is 200-500rpm, such as 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm or 500rpm, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the temperature of the electroplating in step (2) is 20-30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the electroplating time in step (2) is 8-15min, such as 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, after the electroplating in the step (2), deionized water is used for washing the surface of the metal substrate, and compressed air is used for removing residual liquid drops on the surface of the metal substrate.
Preferably, the nickel-boron carbide composite plating solution adopted in the electroplating in the step (3) is an aqueous solution of nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, saccharin, sodium dodecyl sulfate and micron-sized boron carbide particles.
Preferably, the concentration of nickel sulfate hexahydrate in the nickel-boron carbide composite plating solution is 230-270g/L, such as 230g/L, 235g/L, 240g/L, 245g/L, 250g/L, 255g/L, 260g/L, 265g/L or 270g/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the concentration of nickel chloride hexahydrate in the nickel-boron carbide composite plating solution is 35-55g/L, for example 35g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L or 55g/L, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the concentration of boric acid in the nickel-boron carbide composite plating solution is 30-70g/L, for example, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L or 70g/L, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the concentration of saccharin in the nickel-boron carbide composite plating solution is 1.5-3.5g/L, and can be, for example, 1.5g/L, 1.6g/L, 1.8g/L, 2g/L, 2.2g/L, 2.4g/L, 2.6g/L, 2.8g/L, 3g/L, 3.2g/L, 3.4g/L, or 3.5g/L, but is not limited to the recited values, and other values in the range are equally applicable.
Preferably, the concentration of sodium dodecyl sulfate in the nickel-boron carbide composite plating solution is 0.1-0.3g/L, such as 0.1g/L, 0.12g/L, 0.14g/L, 0.16g/L, 0.18g/L, 0.2g/L, 0.22g/L, 0.24g/L, 0.26g/L, 0.28g/L or 0.3g/L, but not limited to the enumerated values, and other non-enumerated values in the range of values are equally applicable.
Preferably, the concentration of micron-sized boron carbide particles in the nickel-boron carbide composite plating solution is 1-7g/L, for example, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/L, 6.5g/L or 7g/L, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the average particle size of the micron-sized boron carbide particles in the nickel-boron carbide composite plating solution is 1 to 10 μm, and may be, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the pH of the nickel-boron carbide composite plating solution used for electroplating in step (3) is 2-5.5, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5 or 5.5, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the adjusting solution of the pH value of the nickel-boron carbide composite plating solution adopted in the electroplating in the step (3) is a sodium hydroxide solution and/or a sulfuric acid solution.
Preferably, the concentration of the sodium hydroxide solution in the conditioning solution is 0.8 to 1.2mol/L, and may be, for example, 0.8mol/L, 0.85mol/L, 0.9mol/L, 0.95mol/L, 1mol/L, 1.05mol/L, 1.1mol/L, 1.15mol/L, or 1.2mol/L, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the concentration of the sulfuric acid solution in the conditioning solution is 8-12 vt%, and may be, for example, 8 vt%, 8.5 vt%, 9 vt%, 9.5 vt%, 10 vt%, 10.5 vt%, 11 vt%, 11.5 vt%, or 12 vt%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the anode used in the electroplating in the step (3) is a nickel plate.
Preferably, the current density of the electroplating in the step (3) is 2-4A/dm 2 For example, it may be 2A/dm 2 、2.2A/dm 2 、2.4A/dm 2 、2.6A/dm 2 、2.8A/dm 2 、3A/dm 2 、3.2A/dm 2 、3.4A/dm 2 、3.6A/dm 2 、3.8A/dm 2 Or 4A/dm 2 However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
Preferably, the pulse frequency of the electroplating in step (3) is 800-1200Hz, such as 800Hz, 850Hz, 900Hz, 950Hz, 1000Hz, 1050Hz, 1100Hz, 1150Hz or 1200Hz, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the duty cycle of the electroplating in step (3) is 40% -80%, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the stirring speed of the electroplating in step (3) is 150-450rpm, such as 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm or 450rpm, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the temperature of the electroplating in step (3) is 20-60 deg.C, such as 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C or 60 deg.C, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the electroplating time in step (3) is 25-35min, such as 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, after the electroplating in the step (3), deionized water is used for washing the surface of the metal matrix, compressed air is used for removing residual liquid drops on the surface of the metal matrix, and then absolute ethyl alcohol is used for washing the surface of the metal matrix.
Preferably, the modification treatment of step (4) comprises soaking the metal substrate in a modification solution.
Preferably, the soaking time is 8-24h, such as 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the modification solution comprises an ethanolic solution of a long chain fatty acid.
Preferably, the concentration of the long-chain fatty acid in the modification solution is 0.03 to 0.08mol/L, and may be, for example, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, or 0.08mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the long chain fatty acid comprises any one or a combination of at least two of dodecanoic acid, tetradecanoic acid, hexadecanoic acid or octadecanoic acid, typical but non-limiting combinations include a combination of dodecanoic acid and tetradecanoic acid, a combination of tetradecanoic acid and hexadecanoic acid, a combination of hexadecanoic acid and octadecanoic acid, a combination of dodecanoic acid, tetradecanoic acid and hexadecanoic acid, a combination of tetradecanoic acid, hexadecanoic acid and octadecanoic acid, or a combination of dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid.
Preferably, the surface of the metal substrate is washed with absolute ethanol after the modification treatment in the step (4), residual droplets on the surface of the metal substrate are removed by using compressed air, and the metal substrate is dried for at least 24 hours, such as 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours or 36 hours, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
As a preferred technical solution of the first aspect of the present invention, the preparation method comprises the steps of:
(1) sequentially carrying out oil removal treatment, rust removal treatment and washing on a metal matrix; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt comprises a combination of 40-60g/L sodium hydroxide, 20-40g/L sodium carbonate, 10-30g/L sodium phosphate dodecahydrate and 10-20g/L sodium silicate nonahydrate; the temperature of the oil removing treatment is 60-75 ℃, and the time is 10-30 min; the rust removing liquid adopted by the rust removing treatment comprises 10-20 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 20-30 ℃, and the time is 10-30 min; the flushing liquid adopted by flushing comprises deionized water;
(2) soaking the metal matrix obtained in the step (1) in a pre-copper-dipping solution for 20-40s, taking out, removing residual liquid drops on the surface by using compressed air, soaking the metal matrix in an electro-coppering solution to carry out electro-coppering coating, washing the surface of the metal matrix by using deionized water after electroplating, and removing residual liquid drops on the surface of the metal matrix by using compressed air; the copper pre-soaking solution comprises 80-120g/L sulfuric acid, 40-60g/L copper sulfate pentahydrate and 0.1-0.3g/L thiourea; the copper electroplating solution comprises 35-55g/L sulfuric acid, 200-280g/L copper sulfate pentahydrate, 30-70ppm sodium chloride and 0.1-0.3g/L sodium dodecyl sulfate; the anode used for electroplating is a T2 copper plate, the cathode is a metal matrix, and the current density is 1-2A/dm 2 The pulse frequency is 200-500Hz, the duty ratio is 60-80%, the stirring speed is 200-500rpm, the temperature is 20-30 ℃, and the time is 8-15 min;
(3) immersing the metal substrate obtained in the step (2) into a nickel-boron carbide composite plating solution to carry out nickel-boron carbide plating, washing the surface of the metal substrate by using deionized water after electroplating, removing residual liquid drops on the surface by using compressed air, and washing the surface of the metal substrate by using absolute ethyl alcohol; the nickel-boron carbide composite plating solution is 230-270g/L nickel sulfate hexahydrate, 35-55g/L nickel chloride hexahydrate, 30-70g/L boric acid, 1.5-3.5g/L saccharin, 0.1-0.3g/L sodium dodecyl sulfate and 1-7g/L micron-sized boron carbide particle waterThe solution, and the average grain diameter of the micron-sized boron carbide particles is 1-10 mu m; the pH value of the nickel-boron carbide composite plating solution is 2-5.5, and the adjusting solution of the pH value is 0.8-1.2mol/L sodium hydroxide solution and/or 8-12 vt% sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a metal matrix, and the current density is 2-4A/dm 2 The pulse frequency is 800-1200Hz, the duty ratio is 40-80%, the stirring speed is 150-450rpm, the temperature is 20-60 ℃, and the time is 25-35 min;
(4) soaking the metal matrix obtained in the step (3) in a modification solution for 8-24h for modification treatment, taking out the metal matrix, washing the surface of the metal matrix by using absolute ethyl alcohol, removing residual liquid drops on the surface by using compressed air, and airing for at least 24h to obtain a copper-nickel composite coating on the surface of the metal matrix; the modifying solution comprises 0.03-0.08mol/L ethanol solution of long-chain fatty acid, and the long-chain fatty acid comprises any one or combination of at least two of dodecanoic acid, tetradecanoic acid, hexadecanoic acid or octadecanoic acid.
Wherein, the metal matrix in the steps (1) to (4) comprises a steel plate, and the type of the steel plate is any one of Q235B, Q345B, 510L or 610L.
In a second aspect, the present invention provides a copper-nickel composite plating layer obtained by the preparation method according to the first aspect.
Preferably, the copper-nickel composite plating layer has a water contact angle of 150 ° or more, such as 150 °, 155 °, 160 °, 165 °, 170 ° or 175 °, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the copper-nickel composite coating has a roll angle of 10 ° or less, and may be, for example, 2 °, 4 °, 6 °, 8 °, or 10 °, but not limited to the values listed, and other values not listed in the range of values are also applicable.
In a third aspect, the invention provides a use of the copper-nickel composite plating layer according to the second aspect in the surface anticorrosion treatment of a metal substrate.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the nano-scale particles in the composite plating solution adopted by the nano-composite electroplating process which accounts for most of the current researches are replaced by the micron-scale particles, so that the problem of particle agglomeration is effectively solved, and the manufacturing cost and the plating process difficulty of the plating solution are reduced;
(2) the existence of the micron-sized boron carbide particles promotes the preferential growth of nickel crystals, the boron carbide particles impact and attach to the surface of a cathode plate in the electroplating process, heterogeneous nucleation sites are provided for the deposition of the nickel crystals, and the formation of a micro-nano structure of a coating is promoted; after the obtained coating with the micro-nano structure is subjected to modification treatment, the surface energy of the coating is reduced, and the coating achieves super-hydrophobicity under the combined action of roughness and surface energy;
(3) according to the invention, a compact copper plating layer is plated below the nickel-boron carbide plating layer, the self-corrosion potential of the obtained super-hydrophobic copper-nickel composite plating layer is-0.2874V, which is higher than-0.3421V of an unmodified copper-nickel composite plating layer and-0.4488V of a pure nickel plating layer, and the increase of the corrosion potential shows that the activity of the plating layer corrosion is reduced; meanwhile, the super-hydrophobic copper-nickel composite coating also has the minimum corrosion current density of 1.87 multiplied by 10 -7 A/cm 2 Compared with the pure nickel coating layer of 7.05 multiplied by 10 -5 A/cm 2 The reduction is two orders of magnitude; the super-hydrophobic copper-nickel composite coating also prevents the nickel coating from generating a cathode effect after being damaged, and the compact copper layer still can play a shielding role after the nickel coating is damaged, so that a corrosion medium is prevented from being in direct contact with a metal matrix, and the corrosion resistance and the protective performance of the coating are enhanced.
Drawings
FIG. 1 is a photograph of the water static contact angle of the surface of the copper-nickel composite plating layer provided in example 1;
fig. 2 is an SEM image of micron-sized boron carbide particles in the preparation method provided in example 1;
FIG. 3 is an SEM image of the surface morphology of the copper-nickel composite plating layer provided in example 1;
FIG. 4 is a polarization curve of the plating layer provided in example 1 and comparative examples 1-2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a corrosion-resistant super-hydrophobic copper-nickel composite plating layer and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) sequentially carrying out oil removal treatment, rust removal treatment and washing on the Q235B steel plate; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt is a combination of 50g/L sodium hydroxide, 30g/L sodium carbonate, 20g/L sodium phosphate dodecahydrate and 15g/L sodium silicate nonahydrate; the temperature of the oil removing treatment is 70 ℃, and the time is 20 min; the rust removing liquid adopted by the rust removing treatment is 15 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 25 ℃, and the time is 20 min; the flushing liquid adopted for flushing is deionized water;
(2) soaking the steel plate obtained in the step (1) in a pre-copper-soaking solution for 30s, taking out, removing residual liquid drops on the surface by using compressed air, soaking the steel plate in an electro-coppering solution for electro-coppering, washing the surface of the steel plate by using deionized water after electroplating, and removing the residual liquid drops on the surface of the steel plate by using compressed air; the copper pre-soaking solution is formed by mixing 100g/L sulfuric acid, 50g/L copper sulfate pentahydrate and 0.2g/L thiourea; the electrolytic copper plating solution is formed by mixing 45g/L sulfuric acid, 240g/L copper sulfate pentahydrate, 50ppm sodium chloride and 0.2g/L lauryl sodium sulfate; the anode used for electroplating is a T2 copper plate, the cathode is a steel plate, and the current density is 1.5A/dm 2 The pulse frequency is 350Hz, the duty ratio is 70%, the stirring speed is 350rpm, the temperature is 25 ℃, and the time is 10 min;
(3) immersing the steel plate obtained in the step (2) into a nickel-boron carbide composite plating solution to carry out nickel-boron carbide plating, washing the surface of the steel plate by using deionized water after electroplating, removing residual liquid drops on the surface by using compressed air, and washing the surface of the steel plate by using absolute ethyl alcohol; the nickel-boron carbide composite plating solution is an aqueous solution of 250g/L nickel sulfate hexahydrate, 45g/L nickel chloride hexahydrate, 50g/L boric acid, 2.5g/L saccharin, 0.2g/L sodium dodecyl sulfate and 4g/L micron-sized boron carbide particles, and the average particles of the micron-sized boron carbide particlesThe diameter is 5 mu m; the pH value of the nickel-boron carbide composite plating solution is 3.5, and the adjusting solution of the pH value is 1mol/L sodium hydroxide solution and 10 vt% sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a steel plate, and the current density is 3A/dm 2 The pulse frequency is 1000Hz, the duty ratio is 60%, the stirring speed is 300rpm, the temperature is 40 ℃, and the time is 30 min;
(4) soaking the steel plate obtained in the step (3) in a modification solution for 16h for modification treatment, taking out, washing the surface of the steel plate by absolute ethyl alcohol, removing residual liquid drops on the surface by using compressed air, and airing for more than 24h to obtain a copper-nickel composite coating on the surface of the steel plate; the modified solution is 0.05mol/L ethanol solution of octadecanoic acid.
FIG. 1 is a photograph showing the water static contact angle of the surface of the copper-nickel composite plating layer obtained in this example.
As can be seen from fig. 1: the water drop is approximately spherical on the surface of the plating layer, the water contact angle is as high as 161.5 +/-2 degrees, and the rolling angle is less than 10 degrees.
Fig. 2 is an SEM image of micron-sized boron carbide particles in the preparation method provided in this example.
As can be seen from fig. 2: compared with the nano particles, the micron-sized boron carbide particles selected in the embodiment have smaller surface energy and are easier to disperse in the electrolyte, so that the plating process flow is simplified.
FIG. 3 is an SEM image of the surface morphology of the Cu-Ni composite plating layer obtained in the present example.
As can be seen from fig. 3: the surface of the coating is in the shape of cauliflower protrusions, and when the coating is in contact with a corrosive medium, the air film stored in the gaps of the protrusions isolates the base body from the corrosive medium, so that the steel plate has more excellent corrosion resistance.
Example 2
The embodiment provides a corrosion-resistant super-hydrophobic copper-nickel composite plating layer and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) sequentially carrying out oil removal treatment, rust removal treatment and washing on the Q345B steel plate; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt is a combination of 40g/L sodium hydroxide, 20g/L sodium carbonate, 10g/L sodium phosphate dodecahydrate and 10g/L sodium silicate nonahydrate; the temperature of the oil removing treatment is 60 ℃, and the time is 30 min; the rust removing liquid adopted by the rust removing treatment is 10 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 20 ℃, and the time is 30 min; the flushing liquid adopted for flushing is deionized water;
(2) soaking the steel plate obtained in the step (1) in a pre-copper-dipping solution for 40s, taking out the steel plate, removing residual liquid drops on the surface by using compressed air, soaking the steel plate in an electro-coppering solution to carry out electro-coppering coating, washing the surface of the steel plate by using deionized water after electroplating, and removing the residual liquid drops on the surface of the steel plate by using compressed air; the copper pre-soaking solution is formed by mixing 80g/L sulfuric acid, 40g/L copper sulfate pentahydrate and 0.1g/L thiourea; the electrolytic copper plating solution is formed by mixing 35g/L sulfuric acid, 200g/L copper sulfate pentahydrate, 30ppm sodium chloride and 0.1g/L lauryl sodium sulfate; the anode used for electroplating is a T2 copper plate, the cathode is a steel plate, and the current density is 1A/dm 2 The pulse frequency is 200Hz, the duty ratio is 60%, the stirring speed is 200rpm, the temperature is 20 ℃, and the time is 15 min;
(3) immersing the steel plate obtained in the step (2) into a nickel-boron carbide composite plating solution to carry out nickel-boron carbide plating, washing the surface of the steel plate by using deionized water after electroplating, removing residual liquid drops on the surface by using compressed air, and washing the surface of the steel plate by using absolute ethyl alcohol; the nickel-boron carbide composite plating solution is 230g/L nickel sulfate hexahydrate, 35g/L nickel chloride hexahydrate, 30g/L boric acid, 1.5g/L saccharin, 0.1g/L sodium dodecyl sulfate and 1g/L aqueous solution of micron-sized boron carbide particles, and the average particle size of the micron-sized boron carbide particles is 1 mu m; the pH value of the nickel-boron carbide composite plating solution is 2, and the adjusting solution of the pH value is 0.8mol/L sodium hydroxide solution and 8 vt% sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a steel plate, and the current density is 2A/dm 2 The pulse frequency is 800Hz, the duty ratio is 40%, the stirring speed is 150rpm, the temperature is 20 ℃, and the time is 35 min;
(4) soaking the steel plate obtained in the step (3) in a modification solution for 24h for modification treatment, taking out the steel plate, washing the surface of the steel plate by using absolute ethyl alcohol, removing residual liquid drops on the surface by using compressed air, and airing for more than 24h to obtain a copper-nickel composite coating on the surface of the steel plate; the modified solution is 0.03mol/L ethanol solution of hexadecanoic acid.
The photograph of the water static contact angle of the surface of the copper-nickel composite plating layer obtained in this embodiment is similar to that of embodiment 1, and therefore, the details thereof are not repeated herein.
The water contact angle of the copper-nickel composite plating layer obtained in the embodiment is 159.5 degrees +/-2 degrees, and the rolling angle is less than 10 degrees.
Example 3
The embodiment provides a corrosion-resistant super-hydrophobic copper-nickel composite plating layer and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) carrying out oil removal treatment, rust removal treatment and flushing on a 610L steel plate in sequence; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt is a combination of 60g/L sodium hydroxide, 40g/L sodium carbonate, 30g/L sodium phosphate dodecahydrate and 20g/L sodium silicate nonahydrate; the temperature of the oil removing treatment is 75 ℃, and the time is 10 min; the rust removing liquid adopted by the rust removing treatment is 20 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 30 ℃, and the time is 10 min; the flushing liquid adopted for flushing is deionized water;
(2) soaking the steel plate obtained in the step (1) in a pre-copper-dipping solution for 20s, taking out the steel plate, removing residual liquid drops on the surface by using compressed air, soaking the steel plate in an electro-coppering solution to carry out electro-coppering coating, washing the surface of the steel plate by using deionized water after electroplating, and removing the residual liquid drops on the surface of the steel plate by using compressed air; the copper pre-soaking solution is formed by mixing 120g/L sulfuric acid, 60g/L copper sulfate pentahydrate and 0.3g/L thiourea; the electrolytic copper plating solution is formed by mixing 55g/L sulfuric acid, 280g/L copper sulfate pentahydrate, 70ppm sodium chloride and 0.3g/L lauryl sodium sulfate; the anode used for electroplating is a T2 copper plate, the cathode is a steel plate, and the current density is 2A/dm 2 The pulse frequency is 500Hz, the duty ratio is 80%, the stirring speed is 500rpm, the temperature is 30 ℃, and the time is 8 min;
(3) immersing the steel plate obtained in the step (2) into a nickel-boron carbide composite plating solution to carry out nickel-boron carbide plating, flushing the surface of the steel plate by using deionized water after electroplating, removing residual liquid drops on the surface by using compressed air, and then adoptingWashing the surface of the steel plate by absolute ethyl alcohol; the nickel-boron carbide composite plating solution is 270g/L nickel sulfate hexahydrate, 55g/L nickel chloride hexahydrate, 70g/L boric acid, 3.5g/L saccharin, 0.3g/L sodium dodecyl sulfate and 7g/L aqueous solution of micron-sized boron carbide particles, and the average particle size of the micron-sized boron carbide particles is 10 mu m; the pH value of the nickel-boron carbide composite plating solution is 5.5, and the adjusting solution of the pH value is 1.2mol/L sodium hydroxide solution and 12vt percent sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a steel plate, and the current density is 4A/dm 2 The pulse frequency is 1200Hz, the duty ratio is 80%, the stirring speed is 450rpm, the temperature is 60 ℃, and the time is 25 min;
(4) soaking the steel plate obtained in the step (3) in a modification solution for 8h for modification treatment, taking out the steel plate, washing the surface of the steel plate by using absolute ethyl alcohol, removing residual liquid drops on the surface by using compressed air, and airing for more than 24h to obtain a copper-nickel composite coating on the surface of the steel plate; the modified solution is 0.08mol/L ethanol solution of myristic acid.
The photograph of the water static contact angle of the surface of the copper-nickel composite plating layer obtained in this embodiment is similar to that of embodiment 1, and therefore, the description thereof is omitted here.
The water contact angle of the copper-nickel composite plating layer obtained in the embodiment is 156 degrees +/-2 degrees, and the rolling angle is less than 10 degrees.
Comparative example 1
The present comparative example provides a pure nickel plating layer and a method for preparing the same, the method comprising the steps of:
(1) sequentially carrying out oil removal treatment, rust removal treatment and washing on the Q235B steel plate; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt is a combination of 50g/L sodium hydroxide, 30g/L sodium carbonate, 20g/L sodium phosphate dodecahydrate and 15g/L sodium silicate nonahydrate; the temperature of the oil removing treatment is 70 ℃, and the time is 20 min; the rust removing liquid adopted by the rust removing treatment is 15 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 25 ℃, and the time is 20 min; the flushing liquid adopted for flushing is deionized water;
(2) immersing the steel plate obtained in the step (1) into an electroplating nickel solution to electroplate a pure nickel coating, flushing the surface of the steel plate with deionized water after electroplating, andremoving residual liquid drops on the surface by adopting compressed air, and then washing the surface of the steel plate by adopting absolute ethyl alcohol; the nickel electroplating solution is an aqueous solution of 250g/L nickel sulfate hexahydrate, 45g/L nickel chloride hexahydrate, 50g/L boric acid, 2.5g/L saccharin and 0.2g/L sodium dodecyl sulfate; the pH value of the nickel electroplating solution is 3.5, and the adjusting solution of the pH value is 1mol/L sodium hydroxide solution and 10 vt% sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a steel plate, and the current density is 3A/dm 2 The pulse frequency is 1000Hz, the duty ratio is 60%, the stirring speed is 300rpm, the temperature is 40 ℃, and the time is 30 min;
(3) soaking the steel plate obtained in the step (2) in a modification solution for 16h for modification treatment, taking out the steel plate, washing the surface of the steel plate by using absolute ethyl alcohol, removing residual liquid drops on the surface by using compressed air, and airing for more than 24h to obtain a pure nickel coating on the surface of the steel plate; the modified solution is 0.05mol/L ethanol solution of octadecanoic acid.
Comparative example 2
The present comparative example provides a copper-nickel composite plating layer and a method for preparing the same, the method comprising the steps of:
(1) sequentially carrying out oil removal treatment, rust removal treatment and washing on the Q235B steel plate; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt is a combination of 50g/L sodium hydroxide, 30g/L sodium carbonate, 20g/L sodium phosphate dodecahydrate and 15g/L sodium silicate nonahydrate; the temperature of the oil removing treatment is 70 ℃, and the time is 20 min; the rust removing liquid adopted by the rust removing treatment is 15 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 25 ℃, and the time is 20 min; the flushing liquid adopted for flushing is deionized water;
(2) soaking the steel plate obtained in the step (1) in a pre-copper-dipping solution for 30s, taking out the steel plate, removing residual liquid drops on the surface by using compressed air, soaking the steel plate in an electro-coppering solution to carry out electro-coppering coating, washing the surface of the steel plate by using deionized water after electroplating, and removing the residual liquid drops on the surface of the steel plate by using compressed air; the copper pre-soaking solution is formed by mixing 100g/L sulfuric acid, 50g/L copper sulfate pentahydrate and 0.2g/L thiourea; the electrolytic copper plating solution consists of 45g/L sulfuric acid, 240g/L copper sulfate pentahydrate, 50ppm sodium chloride and0.2g/L of lauryl sodium sulfate; the anode used for electroplating is a T2 copper plate, the cathode is a steel plate, and the current density is 1.5A/dm 2 The pulse frequency is 350Hz, the duty ratio is 70%, the stirring speed is 350rpm, the temperature is 25 ℃, and the time is 10 min;
(3) immersing the steel plate obtained in the step (2) into a nickel-boron carbide composite plating solution to carry out nickel-boron carbide plating, washing the surface of the steel plate by using deionized water after electroplating, removing residual liquid drops on the surface by using compressed air, washing the surface of the steel plate by using absolute ethyl alcohol, and drying in the air to obtain a copper-nickel composite plating layer on the surface of the steel plate; the nickel-boron carbide composite plating solution is 250g/L nickel sulfate hexahydrate, 45g/L nickel chloride hexahydrate, 50g/L boric acid, 2.5g/L saccharin, 0.2g/L sodium dodecyl sulfate and 4g/L aqueous solution of micron-sized boron carbide particles, and the average particle size of the micron-sized boron carbide particles is 5 mu m; the pH value of the nickel-boron carbide composite plating solution is 3.5, and the adjusting solution of the pH value is 1mol/L sodium hydroxide solution and 10vt percent sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a steel plate, and the current density is 3A/dm 2 The pulse frequency is 1000Hz, the duty ratio is 60%, the stirring speed is 300rpm, the temperature is 40 ℃, and the time is 30 min.
FIG. 4 is a polarization curve of the plating provided in example 1 and comparative examples 1-2.
As can be seen from fig. 4: the self-corrosion potential of the copper-nickel composite plating layer obtained in the example 1 is-0.2874V, which is higher than that of the pure nickel plating layer obtained in the comparative example 1, namely-0.4488V, and the corrosion current density is 1.87 multiplied by 10 -7 A/cm 2 But much less than that of pure nickel plating layer -5 A/cm 2 And is reduced by more than two orders of magnitude. In addition, the copper-nickel composite plating layer without the modification of the low surface energy substance obtained in the comparative example 2 has the self-corrosion potential of-0.3421V, which is still higher than the corrosion potential of the pure nickel plating layer, and the corrosion current density is also lower than that of the pure nickel plating layer.
Therefore, the invention replaces the nanometer particles in the composite plating solution adopted by the nanometer composite electroplating process which accounts for most of the current researches with the micron particles, effectively solves the problem of particle agglomeration, and reduces the manufacturing cost of the plating solution and the plating processDifficulty; in addition, the existence of the micron-sized boron carbide particles promotes the preferential growth of nickel crystals, and the boron carbide particles impact and attach to the surface of a cathode plate in the electroplating process, so that heterogeneous nucleation sites are provided for the deposition of the nickel crystals, and the formation of a micro-nano structure of a coating is promoted; after the obtained coating with the micro-nano structure is modified, the surface energy of the coating is reduced, and the coating achieves super-hydrophobicity under the combined action of roughness and surface energy; particularly, a compact copper plating layer is plated below a nickel-boron carbide plating layer, the self-corrosion potential of the obtained super-hydrophobic copper-nickel composite plating layer is-0.2874V, which is higher than-0.3421V of an unmodified copper-nickel composite plating layer and-0.4488V of a pure nickel plating layer, and the increase of the corrosion potential shows that the corrosion activity of the plating layer is reduced; meanwhile, the super-hydrophobic copper-nickel composite coating also has the minimum corrosion current density of 1.87 multiplied by 10 -7 A/cm 2 Compared with the pure nickel coating layer of 7.05 multiplied by 10 -5 A/cm 2 The reduction is two orders of magnitude; the super-hydrophobic copper-nickel composite coating also prevents the cathode effect generated after the nickel coating is damaged, and the compact copper layer still can play a shielding role after the nickel coating is damaged, so that a corrosion medium is prevented from being in direct contact with a metal matrix, and the corrosion resistance and the protection performance of the coating are enhanced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The preparation method of the corrosion-resistant super-hydrophobic copper-nickel composite coating is characterized by comprising the following steps of:
(1) carrying out oil and rust removal pretreatment on a metal matrix;
(2) electroplating a copper coating on the surface of the metal matrix obtained in the step (1);
(3) electroplating a nickel-boron carbide coating on the surface of the metal matrix obtained in the step (2);
(4) modifying the surface of the metal matrix obtained in the step (3), namely preparing a copper-nickel composite coating on the surface of the metal matrix;
wherein, the nickel-boron carbide composite plating solution adopted by the electroplating in the step (3) contains micron-sized boron carbide particles.
2. The method of claim 1, wherein the metal matrix of steps (1) - (4) comprises a steel plate;
preferably, the steel plate has any one of the models of Q235B, Q345B, 510L or 610L;
preferably, the oil and rust removing pretreatment in the step (1) comprises oil removing treatment, rust removing treatment and flushing which are sequentially carried out.
3. The preparation method according to claim 2, wherein the deoiling liquid used in the deoiling treatment is an aqueous solution of sodium salt;
preferably, the sodium salt comprises any one or combination of at least two of sodium hydroxide, sodium carbonate, sodium phosphate dodecahydrate or sodium silicate nonahydrate, and is further preferably a combination of sodium hydroxide, sodium carbonate, sodium phosphate dodecahydrate and sodium silicate nonahydrate;
preferably, the concentration of the sodium hydroxide in the deoiling liquid is 40-60 g/L;
preferably, the concentration of sodium carbonate in the deoiling liquid is 20-40 g/L;
preferably, the concentration of the sodium phosphate dodecahydrate in the deoiling liquid is 10-30 g/L;
preferably, the concentration of the sodium silicate nonahydrate in the deoiling liquid is 10-20 g/L;
preferably, the temperature of the oil removing treatment is 60-75 ℃;
preferably, the time of the degreasing treatment is 10-30 min.
4. A production method according to claim 2 or 3, wherein the rust removing liquid used in the rust removing treatment includes a hydrochloric acid solution;
preferably, the concentration of the hydrochloric acid solution is 10-20 vt%;
preferably, the temperature of the rust removal treatment is 20-30 ℃;
preferably, the time of the rust removal treatment is 10-30 min;
preferably, the rinsing solution used for rinsing comprises deionized water.
5. The method according to any one of claims 1 to 4, wherein the metal substrate is further immersed in a copper pre-immersion solution before the electroplating in step (2);
preferably, the soaking time is 20-40 s;
preferably, the copper pre-soak solution comprises sulfuric acid, copper sulfate pentahydrate, and thiourea;
preferably, the concentration of the sulfuric acid in the copper presoaking solution is 80-120 g/L;
preferably, the concentration of the copper sulfate pentahydrate in the copper pre-soaking solution is 40-60 g/L;
preferably, the concentration of thiourea in the copper pre-soaking solution is 0.1-0.3 g/L;
preferably, after the soaking, the residual liquid drops on the surface of the metal matrix are removed by adopting compressed air;
preferably, the electrolytic copper plating solution adopted in the step (2) comprises sulfuric acid, copper sulfate pentahydrate, sodium chloride and sodium dodecyl sulfate;
preferably, the concentration of sulfuric acid in the electrolytic copper plating solution is 35-55 g/L;
preferably, the concentration of the copper sulfate pentahydrate in the copper electroplating solution is 200-280 g/L;
preferably, the concentration of sodium chloride in the electrolytic copper plating solution is 30-70 ppm;
preferably, the concentration of the sodium dodecyl sulfate in the electrolytic copper plating solution is 0.1-0.3 g/L;
preferably, the anode used in the electroplating in the step (2) is a T2 copper plate;
preferably, the current density of the electroplating in the step (2) is 1-2A/dm 2 ；
Preferably, the pulse frequency of the electroplating in the step (2) is 200-500 Hz;
preferably, the duty ratio of the electroplating in the step (2) is 60% -80%;
preferably, the stirring speed of the electroplating in the step (2) is 200-500 rpm;
preferably, the temperature of the electroplating in the step (2) is 20-30 ℃;
preferably, the electroplating time in the step (2) is 8-15 min;
preferably, after the electroplating in the step (2), deionized water is used for washing the surface of the metal substrate, and compressed air is used for removing residual liquid drops on the surface of the metal substrate.
6. The preparation method according to any one of claims 1 to 5, wherein the nickel-boron carbide composite plating solution adopted in the electroplating in the step (3) is an aqueous solution of nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, saccharin, sodium dodecyl sulfate and micron-sized boron carbide particles;
preferably, the concentration of nickel sulfate hexahydrate in the nickel-boron carbide composite plating solution is 230-270 g/L;
preferably, the concentration of nickel chloride hexahydrate in the nickel-boron carbide composite plating solution is 35-55 g/L;
preferably, the concentration of the boric acid in the nickel-boron carbide composite plating solution is 30-70 g/L;
preferably, the concentration of saccharin in the nickel-boron carbide composite plating solution is 1.5-3.5 g/L;
preferably, the concentration of the sodium dodecyl sulfate in the nickel-boron carbide composite plating solution is 0.1-0.3 g/L;
preferably, the concentration of micron-sized boron carbide particles in the nickel-boron carbide composite plating solution is 1-7 g/L;
preferably, the average grain diameter of micron-sized boron carbide particles in the nickel-boron carbide composite plating solution is 1-10 mu m;
preferably, the pH value of the nickel-boron carbide composite plating solution adopted in the electroplating in the step (3) is 2-5.5;
preferably, the pH value adjusting solution of the nickel-boron carbide composite plating solution adopted in the electroplating in the step (3) is a sodium hydroxide solution and/or a sulfuric acid solution;
preferably, the concentration of the sodium hydroxide solution in the adjusting solution is 0.8-1.2 mol/L;
preferably, the concentration of sulfuric acid solution in the adjusting solution is 8-12 vt%;
preferably, the anode used in the electroplating in the step (3) is a nickel plate;
preferably, the current density of the electroplating in the step (3) is 2-4A/dm 2 ；
Preferably, the pulse frequency of the electroplating in the step (3) is 800-1200 Hz;
preferably, the duty ratio of the electroplating in the step (3) is 40-80%;
preferably, the stirring speed of the electroplating in the step (3) is 150-450 rpm;
preferably, the temperature of the electroplating in the step (3) is 20-60 ℃;
preferably, the electroplating time in the step (3) is 25-35 min;
preferably, after the electroplating in the step (3), deionized water is used for washing the surface of the metal substrate, compressed air is used for removing residual liquid drops on the surface of the metal substrate, and then absolute ethyl alcohol is used for washing the surface of the metal substrate.
7. The production method according to any one of claims 1 to 6, wherein the modification treatment in step (4) comprises immersing the metal substrate in a modification solution;
preferably, the soaking time is 8-24 h;
preferably, the modifying solution comprises an ethanolic solution of a long chain fatty acid;
preferably, the concentration of the long-chain fatty acid in the modification solution is 0.03-0.08 mol/L;
preferably, the long chain fatty acid comprises any one of dodecanoic acid, tetradecanoic acid, hexadecanoic acid or octadecanoic acid or a combination of at least two thereof;
preferably, after the modification treatment in the step (4), absolute ethyl alcohol is used for washing the surface of the metal matrix, compressed air is used for removing residual liquid drops on the surface of the metal matrix, and then the metal matrix is dried for at least 24 hours.
8. The method for preparing a composite material according to any one of claims 1 to 7, wherein the method for preparing a composite material comprises the steps of:
(1) sequentially carrying out oil removal treatment, rust removal treatment and washing on a metal matrix; the deoiling liquid adopted in the deoiling treatment is an aqueous solution of sodium salt, and the sodium salt comprises the combination of 40-60g/L of sodium hydroxide, 20-40g/L of sodium carbonate, 10-30g/L of sodium phosphate dodecahydrate and 10-20g/L of sodium silicate nonahydrate; the temperature of the oil removing treatment is 60-75 ℃, and the time is 10-30 min; the rust removing liquid adopted by the rust removing treatment comprises 10-20 vt% hydrochloric acid solution, the temperature of the rust removing treatment is 20-30 ℃, and the time is 10-30 min; the flushing liquid adopted by flushing comprises deionized water;
(2) soaking the metal substrate obtained in the step (1) in a pre-copper-soaking solution for 20-40s, taking out, removing residual liquid drops on the surface by using compressed air, soaking the metal substrate in an electro-coppering solution for electro-coppering coating, washing the surface of the metal substrate by using deionized water after electroplating, and removing residual liquid drops on the surface of the metal substrate by using compressed air; the copper pre-soaking solution comprises 80-120g/L sulfuric acid, 40-60g/L copper sulfate pentahydrate and 0.1-0.3g/L thiourea; the electrolytic copper plating solution comprises 35-55g/L sulfuric acid, 200-280g/L copper sulfate pentahydrate, 30-70ppm sodium chloride and 0.1-0.3g/L sodium dodecyl sulfate; the anode used for electroplating is a T2 copper plate, the cathode is a metal matrix, and the current density is 1-2A/dm 2 The pulse frequency is 200-500Hz, the duty ratio is 60-80%, the stirring speed is 200-500rpm, the temperature is 20-30 ℃, and the time is 8-15 min;
(3) immersing the metal substrate obtained in the step (2) into a nickel-boron carbide composite plating solution to carry out nickel-boron carbide plating, washing the surface of the metal substrate by using deionized water after electroplating, removing residual liquid drops on the surface by using compressed air, and washing the surface of the metal substrate by using absolute ethyl alcohol; the nickel-boron carbide composite plating solution is an aqueous solution of 230-270g/L nickel sulfate hexahydrate, 35-55g/L nickel chloride hexahydrate, 30-70g/L boric acid, 1.5-3.5g/L saccharin, 0.1-0.3g/L sodium dodecyl sulfate and 1-7g/L micron-sized boron carbide particles, and the average particle size of the micron-sized boron carbide particles is 1-10 mu m; the nickel-boron carbide complexThe pH value of the combined plating solution is 2-5.5, and the adjusting solution of the pH value is 0.8-1.2mol/L sodium hydroxide solution and/or 8-12 vt% sulfuric acid solution; the anode used for electroplating is a nickel plate, the cathode is a metal matrix, and the current density is 2-4A/dm 2 The pulse frequency is 800-1200Hz, the duty ratio is 40-80%, the stirring speed is 150-450rpm, the temperature is 20-60 ℃, and the time is 25-35 min;
(4) soaking the metal matrix obtained in the step (3) in a modification solution for 8-24h for modification treatment, taking out the metal matrix, washing the surface of the metal matrix by absolute ethyl alcohol, removing residual liquid drops on the surface by using compressed air, and airing for at least 24h to obtain a copper-nickel composite coating on the surface of the metal matrix; the modification solution comprises 0.03-0.08mol/L ethanol solution of long-chain fatty acid, and the long-chain fatty acid comprises any one or combination of at least two of dodecanoic acid, tetradecanoic acid, hexadecanoic acid or octadecanoic acid;
the metal matrix in the steps (1) - (4) comprises a steel plate, and the type of the steel plate is any one of Q235B, Q345B, 510L or 610L.
9. The copper-nickel composite plating layer obtained by the preparation method according to any one of claims 1 to 8, wherein the water contact angle of the copper-nickel composite plating layer is not less than 150 degrees, and the rolling angle is not more than 10 degrees.
10. Use of the copper-nickel composite coating according to claim 9 for the surface corrosion protection of a metal substrate.
CN202210472508.6A 2022-04-29 2022-04-29 Corrosion-resistant super-hydrophobic copper-nickel composite coating and preparation method and application thereof Pending CN114790563A (en)

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