WO2015010464A1 - Method for preparing super-hydrophobic surface by means of nanocomposite electro brush plating - Google Patents

Method for preparing super-hydrophobic surface by means of nanocomposite electro brush plating Download PDF

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WO2015010464A1
WO2015010464A1 PCT/CN2014/072214 CN2014072214W WO2015010464A1 WO 2015010464 A1 WO2015010464 A1 WO 2015010464A1 CN 2014072214 W CN2014072214 W CN 2014072214W WO 2015010464 A1 WO2015010464 A1 WO 2015010464A1
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concentration
nano
plating
activation
composite
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PCT/CN2014/072214
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French (fr)
Chinese (zh)
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刘洪涛
汪雪梅
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中国矿业大学
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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
    • C25D5/04—Electroplating with moving electrodes
    • C25D5/06—Brush or pad plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • 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

Definitions

  • the present invention relates to a method of preparing a hydrophobic surface, and more particularly to a method of preparing a superhydrophobic surface by nanocomposite brush plating.
  • Superhydrophobic surfaces have broad application prospects in many fields due to their many excellent properties, such as self-cleaning function, waterproofing, anti-icing, anti-corrosion and the like.
  • the most well-known superhydrophobic surface is the lotus leaf, which has excellent superhydrophobic properties and extraordinary self-cleaning properties.
  • the preparation and application of superhydrophobic surfaces have always been a research hotspot for scientists. The researchers concluded two methods for the preparation of superhydrophobic surfaces: one is to prepare micro-nano double rough structures on low surface energy materials, and the other is to prepare micro-nano double rough structures on materials with relatively high surface energy. It is then modified with a low surface energy material to reduce the surface energy of the rough structure.
  • the object of the present invention is to provide a method for preparing a superhydrophobic surface by nano composite brush plating, which solves the problem that the surface mechanical strength existing in the preparation process of the superhydrophobic surface is not high, the process is complicated, and the surface wear resistance is insufficient. It is difficult to achieve the problem of large-area preparation.
  • the object of the invention is achieved in that: The prepared superhydrophobic surface method is divided into two steps:
  • Step 1 Preparation of nanocomposite coating: Firstly, the carbon steel substrate is polished, the surface roughness is Ra0.8, and dried after washing; the electrocleaning liquid required for brush plating, the second activation liquid, the third activation liquid, the special nickel Solution, nano-C particle composite Ni plating solution, nano-Cu composite Ni plating solution;
  • Brush plating process parameters for each process electric net process, applied voltage +6V, time 30s, relative motion speed 4-8m/min; second activation process, applied voltage -6V, time 30s, relative motion speed 5_10m/min; The third activation process, applying voltage -8V, time 30s, relative motion speed 5 - lOm / min; plating process, applied voltage +10V, time 90s, relative motion speed 6_8m / min; plating nano C / Ni composite coating process, Applying voltage +15V, time 90s, relative motion speed 6-8m/min; plating nano-Cu/Ni composite plating process, applying voltage +15V, time 90s, relative motion speed 8-12m/min; The brushed sample is placed in alcohol, and washed in an ultrasonic cleaner for 30 minutes, and then placed in a 60 ° C drying oven for 1 hour;
  • the dried sample is placed in a prepared fluorosilane solution, and the mass ratio of tridecafluorooctyltrimethoxysilane to absolute ethanol in the fluorosilane solution is 1:49, soaked at 60 ° C for 40 minutes, and taken out. Dry in an oven at 10 CTC for 1 hour;
  • the electric cleaning liquid comprises: sodium hydroxide (NaOH), concentration 25.0 g / L, sodium carbonate (Na 2 C0 3 ), concentration 21.7 g / L, trisodium phosphate (Na 3 P0 4 ), concentration 50.0 g / L and sodium chloride (NaCI), concentration 2.4 g / L;
  • the second activation liquid comprises: hydrochloric acid (HCI), a concentration of 25.0 g / L and sodium chloride (NaCI), a concentration of 140.0 g / L;
  • the third activation liquid comprises: nickel chloride (NiCl 2 .6H 2 0 ), concentration 3.0 g/L, trisodium citrate (Na 3 C 6 H 5 0 7 .2H 2 0), concentration 142.2 g / L, citric acid (H 3 C 6 H 5 0 7 ), concentration 94.2 g / L and ammonium oxalate (NaCI), concentration 0.1 g / L;
  • the special nickel solution includes: NiS0 4 -7H20, concentration 400 g/L, NiCl 2 -6H 2 0, concentration 20 g/L, CH3COOH, concentration 68 g/L and HC1 (concentration 30%), concentration 20 g /L;
  • the nano-C particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ⁇ 3 ⁇ ⁇ 2 0 ( ⁇ 3 content 25% 28%), concentration 105 mIJL, (NH4) 3 C 6 H 5 0 7 , concentration 56g / L, CH3COONH4, concentration 23g / L, sodium lauryl sulfate (CH 3 (CH 2 ) 10 CH 2 OSO 3 Na), concentration 0.1g / L, ammonium oxalate (C 2 H 8 N 2 0 4 .H 2 0), concentration 0.1 g / L and nano carbon powder, concentration 15g / L;
  • the nano-Cu particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ⁇ 3 ⁇ ⁇ 2 0 ( ⁇ 3 content 25% 28%), concentration 105 mL/L, (NH 4 ) 3 C 6 H 5 0 7 , concentration 56g/L, CH 3 COONH 4 , concentration 23g/L, CH3COOH, concentration 56 g/L, sodium lauryl sulfate (CH 3 (CH 2 ) 1() CH 2 OS0 3 Na), concentration 0.1 g / L, ammonium oxalate (C 2 H 8 N 2 4 4 fl 2 0) concentration 0.1 g / L, nano copper powder, concentration 5g / L.
  • the nano-composite brush plating technology is used to prepare the super-hydrophobic surface, which is of great significance for the super-hydrophobic surface large-area preparation technology and its application.
  • the equipment Fully applied to the brush plating technology, the equipment has the advantages of light weight, flexible process, various coating layers, high bonding strength, high efficiency and large-area coating.
  • the nano-C/Ni is coated on the carbon steel substrate by suitable process conditions.
  • the super-hydrophobic surface can be prepared by nano-Cu/Ni two-layer composite coating.
  • the surface of the coating is micro-nano double-thickness structure, similar to the microstructure of the lotus leaf surface; when the working voltage is 15V, the plating speed is 8m/min, the concentration of nano-copper particles
  • the optimum process parameters are about 5g/L.
  • the contact angle of the coating is the largest, which can reach 155.5 ⁇ 0.9°, and the rolling angle is 5°.
  • the coating has better friction and corrosion resistance than the base carbon steel. It can protect the ship's surface and hull surface equipment. When the ship is running in water, its surface will be corroded by water and oxygen in the atmosphere. After plating the nano-plating layer, the surface will be super-hydrophobic, reducing the corrosion of water and oxygen on the substrate.
  • the problem that the surface mechanical strength existing in the preparation process of the superhydrophobic surface is not high, the process is complicated, the surface wear resistance is insufficient, and the large-area preparation is difficult to be solved.
  • the equipment is simple and reliable.
  • the brush plating equipment is only one brush plating power supply, which is small in size, light in weight, easy to move, easy to carry, and low in price;
  • the surface of the coating is a micro-nano double rough structure, similar to the microstructure of the lotus leaf surface, and the contact angle of the coating can reach 155.5 ⁇ 0.9. , the rolling angle is only 5 °, and the hydrophobic effect is good.
  • the coating has better friction and corrosion resistance than the base carbon steel, and has a long service life.
  • Example 1 The prepared superhydrophobic surface method was divided into two steps:
  • the Q345 carbon steel substrate was polished, and the surface roughness was Ra0.8, which was washed and dried.
  • the electrocleaning liquid required for brush plating Preparing the electrocleaning liquid required for brush plating, the second activation liquid, the third activation liquid, the special nickel solution, the nano C particle composite Ni plating solution, the nano Cu composite Ni plating solution;
  • Brush plating process parameters for each process electric net process, applied voltage +6V, time 30s, relative motion speed 4-8m/min; second activation process, applied voltage -6V, time 30s, relative motion speed 5_10m/min; The third activation process, applying voltage -8V, time 30s, relative motion speed 5 - lOm / min; plating process, applied voltage +10V, time 90s, relative motion speed 6_8m / min; plating nano C / Ni composite coating process, Applying voltage +15V, time 90s, relative motion speed 6-8m/min; plating nano-Cu/Ni composite plating process, applying voltage +15V, time 90s, relative motion speed 8-12m/min;
  • the brush-plated sample is placed in alcohol, and washed in an ultrasonic cleaner for 30 minutes, and then dried in a drying oven at 60 ° C for 1 hour;
  • the dried sample is placed in a prepared fluorosilane solution, and the mass ratio of tridecafluorooctyltrimethoxysilane to absolute ethanol in the fluorosilane solution is 1:49, soaked at 60 ° C for 40 minutes, and taken out. Dry in an oven at 10 CTC for 1 hour;
  • the electric cleaning liquid comprises: sodium hydroxide (NaOH), concentration 25.0 g / L, sodium carbonate (Na 2 C0 3 ), concentration 21.7 g / L, trisodium phosphate (Na 3 P0 4 ), concentration 50.0 g / L and sodium chloride (NaCI), concentration 2.4 g / L;
  • the second activation liquid comprises: hydrochloric acid (HCI), a concentration of 25.0 g / L and sodium chloride (NaCI), a concentration of 140.0 g / L;
  • the third activation liquid comprises: nickel chloride (NiCl 2 .6H 2 0 ), concentration 3.0 g/L, trisodium citrate (Na 3 C 6 H 5 0 7 .2H 2 0), concentration 142.2 g / L, citric acid (H 3 C 6 H 5 0 7 ), concentration 94.2 g / L and ammonium oxalate (NaCI), Concentration 0.1 g / L;
  • the special nickel solution includes: NiS0 4 -7H20, concentration 400 g/L, NiCl 2 -6H 2 0, concentration 20 g/L, CH3COOH, concentration 68 g/L and HC1 (concentration 30%), concentration 20 g /L;
  • the nano-C particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ⁇ 3 ⁇ ⁇ 2 0 ( ⁇ 3 content 25% 28%), concentration 105 mIJL, (NH4) 3 C 6 H 5 0 7 , concentration 56g / L, CH3COONH4, concentration 23g / L, sodium lauryl sulfate (CH 3 (CH 2 ) 10 CH 2 OSO 3 Na), concentration 0.1g / L, ammonium oxalate (C 2 H 8 N 2 0 4 .H 2 0), concentration 0.1 g / L and nano carbon powder, concentration 15g / L;
  • the nano-Cu particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ⁇ 3 ⁇ ⁇ 2 0 ( ⁇ 3 content 25% 28%), concentration 105 mL/L, (NH 4 ) 3 C 6 H 5 0 7 , concentration 56g/L, CH 3 COONH 4 , concentration 23g/L, CH3COOH, concentration 56 g/L, sodium lauryl sulfate (CH 3 (CH 2 ) 1() CH 2 OS0 3 Na), concentration 0.1 g / L, ammonium oxalate (C 2 H 8 N 2 4 4 fl 2 0) concentration 0.1 g / L, nano copper powder, concentration 5g / L.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

A method for preparing a super-hydrophobic surface by means of nanocomposite electro brush plating relates to a method for preparing a super-hydrophobic surface. The method comprises the steps: step 1: preparation of a plate: firstly, polishing a carbon steel substrate, the surface roughness Ra being 0.8, and then drying after cleaning; depositing to form a double-layered nanocomposite plate with a micro-nano double coarse structure on the carbon steel substrate according to a process order of electrocleaning, second activation, third activation, bottom layer plating, plating of a nanometer C/Ni composite plate and plating of a nanometer Cu/Ni composite plate, washing a sample by using deionized water after each step is finished, and then performing a next step; placing brush plated sample into alcohol, washing for 30 minutes in an ultrasonic cleaner, placing in a drying box at the temperature of 60 degrees centigrade to dry for 1 hour; and step 2: surface chemical modification: placing dried sample in a prepared fluoroalkyl silane solution, the mass ratio of Actyflon-G607 to absolute ethyl alcohol being 1:49 in the fluoroalkyl silane solution, soaking for 40 minutes at the temperature of 60 degrees centigrade, and taking out to dry for 1 hour at the temperature of 100 degrees centigrade in the drying box.

Description

一种纳米复合电刷镀制备超疏水表面的方法  Method for preparing superhydrophobic surface by nano composite brush plating
技术领域 Technical field
本发明涉及一种制备疏水表面的方法， 特别是一种纳米复合电刷镀制备超疏水表面 的方法。  The present invention relates to a method of preparing a hydrophobic surface, and more particularly to a method of preparing a superhydrophobic surface by nanocomposite brush plating.
背景技术 Background technique
超疏水表面由于有许多优异的性能， 比如自清洁功能、 防水、 抗结冰、 防腐蚀等等， 在许多领域都有广阔的应用前景。 最为熟知的超疏水表面就是荷叶， 荷叶具有优异的超 疏水性能和非凡的自清洁功能。 超疏水表面的制备和应用研究一直以来都是科学家的研 究热点。 研究人员总结出了制备超疏水表面的两个方法： 一种是在低表面能的材料上制 备微纳米双重粗糙结构，一种是在表面能比较高的材料上先制备出微纳米双重粗糙结构， 再用低表面能的物质对其进行修饰， 以降低粗糙结构表现得表面能。 对于光滑的固体材 料， 即使它具有最低的表面能， 它与水的接触角也最多能达到 120°， 因此在材料表面构 建微纳米双重粗糙结构是制备超疏水表面的关键。  Superhydrophobic surfaces have broad application prospects in many fields due to their many excellent properties, such as self-cleaning function, waterproofing, anti-icing, anti-corrosion and the like. The most well-known superhydrophobic surface is the lotus leaf, which has excellent superhydrophobic properties and extraordinary self-cleaning properties. The preparation and application of superhydrophobic surfaces have always been a research hotspot for scientists. The researchers concluded two methods for the preparation of superhydrophobic surfaces: one is to prepare micro-nano double rough structures on low surface energy materials, and the other is to prepare micro-nano double rough structures on materials with relatively high surface energy. It is then modified with a low surface energy material to reduce the surface energy of the rough structure. For a smooth solid material, even if it has the lowest surface energy, its contact angle with water can reach up to 120°. Therefore, constructing a micro-nano double roughness structure on the surface of the material is the key to preparing a superhydrophobic surface.
目前已有许多在金属表面制备超疏水表面的方法， 如溶液浸泡法、 电化学沉积法、 化学腐蚀法、 阳极氧化法、 化学沉积法等。 但是现有的技术还存在许多不足， 如表面机 械强度不高， 工艺过程比较复杂， 表面耐磨性持久性不足， 对设备的要求比较高， 难以 实现大范围的制备。 因此目前超疏水表面仍旧处于基础性研究阶段， 其规模化的实际应 用受到限制。  There are many methods for preparing superhydrophobic surfaces on metal surfaces, such as solution immersion, electrochemical deposition, chemical etching, anodization, and chemical deposition. However, the existing technology still has many shortcomings, such as low surface mechanical strength, complicated process, insufficient durability of surface abrasion resistance, high requirements on equipment, and difficulty in achieving a wide range of preparation. Therefore, the current superhydrophobic surface is still in the basic research stage, and its practical application of scale is limited.
发明内容： Summary of the invention:
本发明的目的是要提供一种纳米复合电刷镀制备超疏水表面的方法， 解决目前超疏 水表面制备过程中存在的表面机械强度不高， 工艺过程比较复杂， 表面耐磨性持久性不 足， 难以实现大面积制备的问题。  The object of the present invention is to provide a method for preparing a superhydrophobic surface by nano composite brush plating, which solves the problem that the surface mechanical strength existing in the preparation process of the superhydrophobic surface is not high, the process is complicated, and the surface wear resistance is insufficient. It is difficult to achieve the problem of large-area preparation.
本发明的目的是这样实现的： 制备的超疏水表面方法分两个步骤：  The object of the invention is achieved in that: The prepared superhydrophobic surface method is divided into two steps:
步骤 1、纳米复合镀层制备： 首先将碳钢基体抛光， 表面粗糙度 Ra0.8， 清洗后烘干; 配制电刷镀所需的电净液、 二号活化液、 三号活化液、 特殊镍溶液、 纳米 C颗粒复 合 Ni镀液、 纳米 Cu复合 Ni镀液；  Step 1. Preparation of nanocomposite coating: Firstly, the carbon steel substrate is polished, the surface roughness is Ra0.8, and dried after washing; the electrocleaning liquid required for brush plating, the second activation liquid, the third activation liquid, the special nickel Solution, nano-C particle composite Ni plating solution, nano-Cu composite Ni plating solution;
按照电净 -二号活化-三号活化-镀底层-镀纳米 C/Ni复合镀层-镀纳米 Cu/Ni复合镀层 的工序顺序在碳钢基体上沉积出具有微纳米双重粗糙结构的双层纳米复合镀层， 每一个 步骤完成后用去离子水冲洗试样， 然再进行下一个步骤；  According to the sequence of electricity-net-second activation-third activation-plating-plating-plated nano-C/Ni composite coating-plated nano-Cu/Ni composite coating, two-layer nano-layers with micro-nano double roughness structure are deposited on the carbon steel substrate. Composite coating, after each step is completed, rinse the sample with deionized water, and then proceed to the next step;
每一工序的刷镀工艺参数： 电净工序， 施加电压 +6V， 时间 30s， 相对运动速度 4— 8m/min; 二号活化工序， 施加电压 -6V, 时间 30s， 相对运动速度 5_10m/min; 三号 活化工序， 施加电压 -8V, 时间 30s， 相对运动速度 5— lOm/min; 镀底层工序， 施加电压 +10V, 时间 90s，相对运动速度 6_8m/min; 镀纳米 C/Ni复合镀层工序，施加电压 +15V, 时间 90s， 相对运动速度 6— 8m/min; 镀纳米 Cu/Ni复合镀层工序， 施加电压 +15V, 时间 90s, 相对运动速度 8— 12m/min; 将刷镀完的试样放入酒精中， 并在超声波清洗器中清洗 30分钟， 再放入 60°C烘干 箱中烘干 1小时； Brush plating process parameters for each process: electric net process, applied voltage +6V, time 30s, relative motion speed 4-8m/min; second activation process, applied voltage -6V, time 30s, relative motion speed 5_10m/min; The third activation process, applying voltage -8V, time 30s, relative motion speed 5 - lOm / min; plating process, applied voltage +10V, time 90s, relative motion speed 6_8m / min; plating nano C / Ni composite coating process, Applying voltage +15V, time 90s, relative motion speed 6-8m/min; plating nano-Cu/Ni composite plating process, applying voltage +15V, time 90s, relative motion speed 8-12m/min; The brushed sample is placed in alcohol, and washed in an ultrasonic cleaner for 30 minutes, and then placed in a 60 ° C drying oven for 1 hour;
步骤 2、 表面化学改性：  Step 2. Surface chemical modification:
将烘干的试样放入配制的氟硅烷溶液中， 氟硅烷溶液中十三氟辛基三甲氧基硅烷与 无水乙醇的质量比为 1 : 49， 在 60°C下浸泡 40分钟， 取出在 10CTC的烘箱中烘干 1小时， 即可；  The dried sample is placed in a prepared fluorosilane solution, and the mass ratio of tridecafluorooctyltrimethoxysilane to absolute ethanol in the fluorosilane solution is 1:49, soaked at 60 ° C for 40 minutes, and taken out. Dry in an oven at 10 CTC for 1 hour;
所述的电净液包括： 氢氧化钠（NaOH)，浓度 25.0 g/L、碳酸钠（Na2C03)，浓度 21.7 g/L、 磷酸三钠 （Na3P04)， 浓度 50.0 g/L和氯化钠 （NaCI)， 浓度 2.4 g/L; The electric cleaning liquid comprises: sodium hydroxide (NaOH), concentration 25.0 g / L, sodium carbonate (Na 2 C0 3 ), concentration 21.7 g / L, trisodium phosphate (Na 3 P0 4 ), concentration 50.0 g / L and sodium chloride (NaCI), concentration 2.4 g / L;
所述的二号活化液包括： 盐酸 （HCI)， 浓度 25.0 g/L和氯化钠 （NaCI)， 浓度 140.0 g/L;  The second activation liquid comprises: hydrochloric acid (HCI), a concentration of 25.0 g / L and sodium chloride (NaCI), a concentration of 140.0 g / L;
所述的三号活化液包括： 氯化镍 （ NiCl2.6H20 )， 浓度 3.0 g/L、 柠檬酸三钠 (Na3C6H507.2H20)，浓度 142.2 g/L、柠檬酸（H3C6H507)，浓度 94.2 g/L和草酸铵（NaCI)， 浓度 0.1 g/L; The third activation liquid comprises: nickel chloride (NiCl 2 .6H 2 0 ), concentration 3.0 g/L, trisodium citrate (Na 3 C 6 H 5 0 7 .2H 2 0), concentration 142.2 g / L, citric acid (H 3 C 6 H 5 0 7 ), concentration 94.2 g / L and ammonium oxalate (NaCI), concentration 0.1 g / L;
所述的特殊镍溶液包括： NiS04-7H20, 浓度 400 g/L、 NiCl2-6H20, 浓度 20 g/L、 CH3COOH, 浓度 68 g/L和 HC1 (浓度 30%)， 浓度 20 g/L; The special nickel solution includes: NiS0 4 -7H20, concentration 400 g/L, NiCl 2 -6H 2 0, concentration 20 g/L, CH3COOH, concentration 68 g/L and HC1 (concentration 30%), concentration 20 g /L;
所述的纳米 C颗粒复合 Ni镀液包括： NiS04.6H20， 浓度 254g/L、 ΝΗ3·Η20 (ΝΗ3 含量 25 % 28 % )，浓度 105mIJL、（NH4)3C6H507，浓度 56g/L、 CH3COONH4,浓度 23g/L、 十二烷基硫酸钠 （CH3(CH2)10CH2OSO3Na)， 浓度 0.1g/L、 草酸铵 （C2H8N204.H20)， 浓 度 0.1 g/L和纳米碳粉， 浓度 15g/L; The nano-C particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ΝΗ 3 · Η 2 0 (ΝΗ 3 content 25% 28%), concentration 105 mIJL, (NH4) 3 C 6 H 5 0 7 , concentration 56g / L, CH3COONH4, concentration 23g / L, sodium lauryl sulfate (CH 3 (CH 2 ) 10 CH 2 OSO 3 Na), concentration 0.1g / L, ammonium oxalate (C 2 H 8 N 2 0 4 .H 2 0), concentration 0.1 g / L and nano carbon powder, concentration 15g / L;
所述的纳米 Cu颗粒复合 Ni镀液包括： NiS04.6H20， 浓度 254g/L、 ΝΗ3·Η20 (ΝΗ3 含量 25 % 28 % )，浓度 105mL/L、（NH4)3C6H507，浓度 56g/L、 CH3COONH4、浓度 23g/L、 CH3COOH, 浓度 56 g/L、 十二烷基硫酸钠 （CH3(CH2)1()CH2OS03Na)， 浓度 0.1g/L、 草 酸铵 （C2H8N204fl20) 浓度 0.1 g/L、 纳米铜粉， 浓度 5g/L。 The nano-Cu particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ΝΗ 3 · Η 2 0 (ΝΗ 3 content 25% 28%), concentration 105 mL/L, (NH 4 ) 3 C 6 H 5 0 7 , concentration 56g/L, CH 3 COONH 4 , concentration 23g/L, CH3COOH, concentration 56 g/L, sodium lauryl sulfate (CH 3 (CH 2 ) 1() CH 2 OS0 3 Na), concentration 0.1 g / L, ammonium oxalate (C 2 H 8 N 2 4 4 fl 2 0) concentration 0.1 g / L, nano copper powder, concentration 5g / L.
有益效果， 由于采用了上述方案， 采用纳米复合电刷镀技术制备了超疏水表面， 对 超疏水表面大面积制备技术及其应用有重要意义。 充分应用了电刷镀技术具有的设备轻 便、 工艺灵活、 镀层种类多样、 镀层结合强度高、 高效及可制备大面积镀层优点， 采用 合适的工艺条件在碳钢基体上刷镀纳米 C/Ni和纳米 Cu/Ni二层复合镀层可以制备出超疏 水表面，镀层表面为微纳米双重粗糙结构，与荷叶表面微观结构相似；当工作电压为 15V, 刷镀速度为 8m/min，纳米铜颗粒浓度为 5g/L左右时为最佳工艺参数，镀层的接触角最大， 可以达到 155.5±0.9°， 滚动角为 5°; 镀层与基体碳钢相比有较好的摩擦性能和耐腐蚀性 能。 能对舰船表面及船体表面设备的保护。 舰船在水中运行， 其表面将会受到水和大气 中的氧的腐蚀， 镀覆纳米镀层后， 实现表面超疏水， 减小水和氧对基体的腐蚀。 解决了 目前超疏水表面制备过程中存在的表面机械强度不高， 工艺过程比较复杂， 表面耐磨性 持久性不足， 难以实现大面积制备的问题。 优点： The beneficial effects, due to the above scheme, the nano-composite brush plating technology is used to prepare the super-hydrophobic surface, which is of great significance for the super-hydrophobic surface large-area preparation technology and its application. Fully applied to the brush plating technology, the equipment has the advantages of light weight, flexible process, various coating layers, high bonding strength, high efficiency and large-area coating. The nano-C/Ni is coated on the carbon steel substrate by suitable process conditions. The super-hydrophobic surface can be prepared by nano-Cu/Ni two-layer composite coating. The surface of the coating is micro-nano double-thickness structure, similar to the microstructure of the lotus leaf surface; when the working voltage is 15V, the plating speed is 8m/min, the concentration of nano-copper particles The optimum process parameters are about 5g/L. The contact angle of the coating is the largest, which can reach 155.5±0.9°, and the rolling angle is 5°. The coating has better friction and corrosion resistance than the base carbon steel. It can protect the ship's surface and hull surface equipment. When the ship is running in water, its surface will be corroded by water and oxygen in the atmosphere. After plating the nano-plating layer, the surface will be super-hydrophobic, reducing the corrosion of water and oxygen on the substrate. The problem that the surface mechanical strength existing in the preparation process of the superhydrophobic surface is not high, the process is complicated, the surface wear resistance is insufficient, and the large-area preparation is difficult to be solved. advantage:
1、 可实现超疏水表面的大面积制备， 为超疏水表面的工业化应用提供了可行性； 1. It can realize large-area preparation of superhydrophobic surface, which provides feasibility for industrial application of superhydrophobic surface;
2、 设备简单可靠。 电刷镀设备仅为一台刷镀电源， 体积小， 重量轻， 易移动， 可便 携， 价格低； 2. The equipment is simple and reliable. The brush plating equipment is only one brush plating power supply, which is small in size, light in weight, easy to move, easy to carry, and low in price;
3、 镀层表面为微纳米双重粗糙结构， 与荷叶表面微观结构相似， 镀层的接触角可以 达到 155.5±0.9。， 滚动角仅为 5°， 疏水效果良好。  3. The surface of the coating is a micro-nano double rough structure, similar to the microstructure of the lotus leaf surface, and the contact angle of the coating can reach 155.5±0.9. , the rolling angle is only 5 °, and the hydrophobic effect is good.
4、 镀层与基体碳钢相比有较好的摩擦性能和耐腐蚀性能， 使用寿命长久。  4. The coating has better friction and corrosion resistance than the base carbon steel, and has a long service life.
具体实施方式 detailed description
实施例 1 : 制备的超疏水表面方法分两个步骤：  Example 1 : The prepared superhydrophobic surface method was divided into two steps:
步骤 1、 纳米复合镀层制备：  Step 1. Preparation of nanocomposite coating:
首先将 Q345碳钢基体抛光， 表面粗糙度 Ra0.8， 清洗后烘干。  First, the Q345 carbon steel substrate was polished, and the surface roughness was Ra0.8, which was washed and dried.
配制电刷镀所需的电净液、 二号活化液、 三号活化液、 特殊镍溶液、 纳米 C颗粒复 合 Ni镀液、 纳米 Cu复合 Ni镀液；  Preparing the electrocleaning liquid required for brush plating, the second activation liquid, the third activation liquid, the special nickel solution, the nano C particle composite Ni plating solution, the nano Cu composite Ni plating solution;
按照电净 -二号活化-三号活化-镀底层-镀纳米 C/Ni复合镀层-镀纳米 Cu/Ni复合镀层 的工序顺序在碳钢基体上沉积出具有微纳米双重粗糙结构的双层纳米复合镀层， 每一个 步骤完成后用去离子水冲洗试样， 然再进行下一个步骤；  According to the sequence of electricity-net-second activation-third activation-plating-plating-plated nano-C/Ni composite coating-plated nano-Cu/Ni composite coating, two-layer nano-layers with micro-nano double roughness structure are deposited on the carbon steel substrate. Composite coating, after each step is completed, rinse the sample with deionized water, and then proceed to the next step;
每一工序的刷镀工艺参数： 电净工序， 施加电压 +6V， 时间 30s， 相对运动速度 4— 8m/min; 二号活化工序， 施加电压 -6V, 时间 30s， 相对运动速度 5_10m/min; 三号 活化工序， 施加电压 -8V, 时间 30s， 相对运动速度 5— lOm/min; 镀底层工序， 施加电压 +10V, 时间 90s，相对运动速度 6_8m/min; 镀纳米 C/Ni复合镀层工序，施加电压 +15V, 时间 90s， 相对运动速度 6— 8m/min; 镀纳米 Cu/Ni复合镀层工序， 施加电压 +15V, 时间 90s, 相对运动速度 8— 12m/min;  Brush plating process parameters for each process: electric net process, applied voltage +6V, time 30s, relative motion speed 4-8m/min; second activation process, applied voltage -6V, time 30s, relative motion speed 5_10m/min; The third activation process, applying voltage -8V, time 30s, relative motion speed 5 - lOm / min; plating process, applied voltage +10V, time 90s, relative motion speed 6_8m / min; plating nano C / Ni composite coating process, Applying voltage +15V, time 90s, relative motion speed 6-8m/min; plating nano-Cu/Ni composite plating process, applying voltage +15V, time 90s, relative motion speed 8-12m/min;
将刷镀完的试样放入酒精中， 并在超声波清洗器中清洗 30分钟， 再放入 60°C烘干 箱中烘干 1小时；  The brush-plated sample is placed in alcohol, and washed in an ultrasonic cleaner for 30 minutes, and then dried in a drying oven at 60 ° C for 1 hour;
步骤 2、 表面化学改性：  Step 2. Surface chemical modification:
将烘干的试样放入配制的氟硅烷溶液中， 氟硅烷溶液中十三氟辛基三甲氧基硅烷与 无水乙醇的质量比为 1 : 49， 在 60°C下浸泡 40分钟， 取出在 10CTC的烘箱中烘干 1小时， 即可；  The dried sample is placed in a prepared fluorosilane solution, and the mass ratio of tridecafluorooctyltrimethoxysilane to absolute ethanol in the fluorosilane solution is 1:49, soaked at 60 ° C for 40 minutes, and taken out. Dry in an oven at 10 CTC for 1 hour;
所述的电净液包括： 氢氧化钠（NaOH)，浓度 25.0 g/L、碳酸钠（Na2C03)，浓度 21.7 g/L、 磷酸三钠 （Na3P04)， 浓度 50.0 g/L和氯化钠 （NaCI)， 浓度 2.4 g/L; The electric cleaning liquid comprises: sodium hydroxide (NaOH), concentration 25.0 g / L, sodium carbonate (Na 2 C0 3 ), concentration 21.7 g / L, trisodium phosphate (Na 3 P0 4 ), concentration 50.0 g / L and sodium chloride (NaCI), concentration 2.4 g / L;
所述的二号活化液包括： 盐酸 （HCI)， 浓度 25.0 g/L和氯化钠 （NaCI)， 浓度 140.0 g/L;  The second activation liquid comprises: hydrochloric acid (HCI), a concentration of 25.0 g / L and sodium chloride (NaCI), a concentration of 140.0 g / L;
所述的三号活化液包括： 氯化镍 （ NiCl2.6H20 )， 浓度 3.0 g/L、 柠檬酸三钠 (Na3C6H507.2H20)，浓度 142.2 g/L、柠檬酸（H3C6H507)，浓度 94.2 g/L和草酸铵（NaCI)， 浓度 0.1 g/L; The third activation liquid comprises: nickel chloride (NiCl 2 .6H 2 0 ), concentration 3.0 g/L, trisodium citrate (Na 3 C 6 H 5 0 7 .2H 2 0), concentration 142.2 g / L, citric acid (H 3 C 6 H 5 0 7 ), concentration 94.2 g / L and ammonium oxalate (NaCI), Concentration 0.1 g / L;
所述的特殊镍溶液包括： NiS04-7H20, 浓度 400 g/L、 NiCl2-6H20, 浓度 20 g/L、 CH3COOH, 浓度 68 g/L和 HC1 (浓度 30%)， 浓度 20 g/L; The special nickel solution includes: NiS0 4 -7H20, concentration 400 g/L, NiCl 2 -6H 2 0, concentration 20 g/L, CH3COOH, concentration 68 g/L and HC1 (concentration 30%), concentration 20 g /L;
所述的纳米 C颗粒复合 Ni镀液包括： NiS04.6H20， 浓度 254g/L、 ΝΗ3·Η20 (ΝΗ3 含量 25 % 28 % )，浓度 105mIJL、（NH4)3C6H507，浓度 56g/L、 CH3COONH4,浓度 23g/L、 十二烷基硫酸钠 （CH3(CH2)10CH2OSO3Na)， 浓度 0.1g/L、 草酸铵 （C2H8N204.H20)， 浓 度 0.1 g/L和纳米碳粉， 浓度 15g/L; The nano-C particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ΝΗ 3 · Η 2 0 (ΝΗ 3 content 25% 28%), concentration 105 mIJL, (NH4) 3 C 6 H 5 0 7 , concentration 56g / L, CH3COONH4, concentration 23g / L, sodium lauryl sulfate (CH 3 (CH 2 ) 10 CH 2 OSO 3 Na), concentration 0.1g / L, ammonium oxalate (C 2 H 8 N 2 0 4 .H 2 0), concentration 0.1 g / L and nano carbon powder, concentration 15g / L;
所述的纳米 Cu颗粒复合 Ni镀液包括： NiS04.6H20， 浓度 254g/L、 ΝΗ3·Η20 (ΝΗ3 含量 25 % 28 % )，浓度 105mL/L、（NH4)3C6H507，浓度 56g/L、 CH3COONH4、浓度 23g/L、 CH3COOH, 浓度 56 g/L、 十二烷基硫酸钠 （CH3(CH2)1()CH2OS03Na)， 浓度 0.1g/L、 草 酸铵 （C2H8N204fl20) 浓度 0.1 g/L、 纳米铜粉， 浓度 5g/L。 The nano-Cu particle composite Ni plating solution comprises: NiS0 4 .6H 2 0, concentration 254 g/L, ΝΗ 3 · Η 2 0 (ΝΗ 3 content 25% 28%), concentration 105 mL/L, (NH 4 ) 3 C 6 H 5 0 7 , concentration 56g/L, CH 3 COONH 4 , concentration 23g/L, CH3COOH, concentration 56 g/L, sodium lauryl sulfate (CH 3 (CH 2 ) 1() CH 2 OS0 3 Na), concentration 0.1 g / L, ammonium oxalate (C 2 H 8 N 2 4 4 fl 2 0) concentration 0.1 g / L, nano copper powder, concentration 5g / L.

Claims

权利要求书 Claim
1、 一种纳米复合电刷镀制备超疏水表面的方法， 其特征是： 制备的超疏水表面方法 分两个步骤： A method for preparing a superhydrophobic surface by nanocomposite brush plating, characterized in that: the prepared superhydrophobic surface method is divided into two steps:
步骤 1、 纳米复合镀层制备：  Step 1. Preparation of nanocomposite coating:
首先将 Q345碳钢基体抛光， 表面粗糙度 Ra0.8， 清洗后烘干；  Firstly, the Q345 carbon steel substrate is polished, the surface roughness is Ra0.8, and dried after washing;
配制电刷镀所需的电净液、 二号活化液、 三号活化液、 特殊镍溶液、 纳米 C颗粒复 合 Ni镀液、 纳米 Cu复合 Ni镀液；  Preparing the electrocleaning liquid required for brush plating, the second activation liquid, the third activation liquid, the special nickel solution, the nano C particle composite Ni plating solution, the nano Cu composite Ni plating solution;
按照电净 -二号活化-三号活化-镀底层-镀纳米 C/Ni 复合镀层-镀纳米 Cu/Ni 复合镀层 的工序顺序在碳钢基体上沉积出具有微纳米双重粗糙结构的双层纳米复合镀层， 每一个 步骤完成后用去离子水冲洗试样， 然再进行下一个步骤；  According to the sequence of electricity-net-second activation-third activation-plating-plating nano-C/Ni composite coating-plated nano-Cu/Ni composite coating, a double-layer nano-layer with nano-nano double roughness structure is deposited on the carbon steel substrate. Composite coating, after each step is completed, rinse the sample with deionized water, and then proceed to the next step;
每一工序的刷镀工艺参数： 电净工序， 施加电压 +6V, 时间 30s， 相对运动速度 4一 8m/min; 二号活化工序， 施加电压 -6V, 时间 30s， 相对运动速度 5_10m/min; 三号活化 工序， 施加电压 -8V， 时间 30s， 相对运动速度 5— 10m/min; 镀底层工序， 施加电压 +10V, 时间 90s， 相对运动速度 6— 8m/min; 镀纳米 C/Ni 复合镀层工序， 施加电压 +15V, 时间 90s， 相对运动速度 6— 8m/min; 镀纳米 Cu/Ni 复合镀层工序， 施加电压 +15V, 时间 90s， 相对运动速度 8— 12m/min;  Brush plating process parameters for each process: electric net process, applied voltage +6V, time 30s, relative motion speed 4-8m/min; second activation process, applied voltage -6V, time 30s, relative motion speed 5_10m/min; No. 3 activation process, applying voltage -8V, time 30s, relative motion speed 5-10m/min; plating process, applied voltage +10V, time 90s, relative motion speed 6-8m/min; plated nano C/Ni composite coating Process, applying voltage +15V, time 90s, relative motion speed 6-8m/min; plating nano-Cu/Ni composite plating process, applying voltage +15V, time 90s, relative motion speed 8-12m/min;
将刷镀完的试样放入酒精中， 并在超声波清洗器中清洗 30分钟， 再放入 60°C烘干箱 中烘干 1小时；  The brushed sample is placed in alcohol, and washed in an ultrasonic cleaner for 30 minutes, and then dried in a 60 ° C drying oven for 1 hour;
步骤 2、 表面化学改性：  Step 2. Surface chemical modification:
将烘干的试样放入配制的氟硅烷溶液中， 氟硅烷溶液中十三氟辛基三甲氧基硅烷与 无水乙醇的质量比为 1 : 49， 在 60°C下浸泡 40 分钟， 取出在 10CTC的烘箱中烘干 1 小 时， 即可；  The dried sample is placed in a prepared fluorosilane solution. The mass ratio of tridecafluorooctyltrimethoxysilane to absolute ethanol in the fluorosilane solution is 1:49, soaked at 60 ° C for 40 minutes, and taken out. Dry in an oven at 10 CTC for 1 hour;
所述的电净液包括： 浓度为 25.0 g/L的氢氧化钠 （NaOH)、 浓度为 21.7 g/L的碳酸钠 (Na2C03)、 浓度为 50.0 g/L的磷酸三钠 (Na3P04) 和浓度为 2.4 g/L的氯化钠 (NaCI); 所述的二号活化液包括： 浓度为 25.0 g/L的盐酸 （HCI) 和浓度为 140.0 g/L的氯化 钠 （NaCI); The electric cleaning liquid comprises: sodium hydroxide (NaOH) having a concentration of 25.0 g/L, sodium carbonate (Na 2 C0 3 ) having a concentration of 21.7 g/L, and trisodium phosphate (Na at a concentration of 50.0 g/L). 3 P0 4 ) and a concentration of 2.4 g/L of sodium chloride (NaCI); the second activation solution comprises: hydrochloric acid (HCI) at a concentration of 25.0 g/L and sodium chloride at a concentration of 140.0 g/L (NaCI);
所述的三号活化液包括： 浓度为 3.0 g/L 的氯化镍 （NiCl2.6H20)、 浓度为 142.2 g/L 柠檬酸三钠 （Na3C6H507.2H20)、 浓度为 94.2 g/L的柠檬酸 （H3C6H507) 和浓度为 0.1 g/L 的草酸铵 （NaCI); The third activation liquid comprises: nickel chloride (NiCl 2 .6H 2 0) having a concentration of 3.0 g/L, and a concentration of 142.2 g/L trisodium citrate (Na 3 C 6 H 5 0 7 .2H 2 ) 0), citrate (H 3 C 6 H 5 0 7 ) at a concentration of 94.2 g/L and ammonium oxalate (NaCI) at a concentration of 0.1 g/L;
所述的特殊镍溶液包括： 浓度为 400 g/L 的 NiS04.7H20、 浓度为 20 g/L 的 NiCl 6H20、 浓度为 68 g/L的 CH3COOH和浓度为 20 g/L的 HC1 (浓度 30%); The special nickel solution includes: NiS0 4 .7H20 at a concentration of 400 g/L, NiCl 6H 2 0 at a concentration of 20 g/L, CH 3 COOH at a concentration of 68 g/L, and a concentration of 20 g/L. HC1 (concentration 30%);
所述的纳米 C 颗粒复合 Ni 镀液包括： 浓度为 254g/L 的 NiS04.6H20、 浓度为 105mL/L 的 ΝΗ3·Η20 (ΝΗ3含量 25 — 28 ) 浓度为 56g/L 的 （NH4)3C6H507、 浓度 23g/L 的 CH3COONH4、 浓度为 O.lg/L 的十二烷基硫酸钠 （CH3(CH2)1()CH2OS03Na)、 浓 度为 0.1 g/L的草酸铵 （C2H8N204 H20) 和浓度为 15g/L的纳米碳粉； 所述的纳米 Cu 颗粒复合 Ni 镀液包括： 浓度为 254g/L 的 NiS( 6H20、 浓度为 105mL/L的 ΝΗ3·Η20 (ΝΗ3含量 25 % 28 % )、 浓度为 56g/L的 （NH4)3C6H507、 浓度为 23g/L 的 CH3COONH4、、 浓度为 56 g/L的 CH3COOH、 浓度为 0.1g/L的十二烷基硫酸钠 (CH3(CH2)ioCH2OS03Na), 浓度为 0.1 g/L的草酸铵 （C2H8N204.H20)、 浓度为 5g/L的纳 米铜粉。 The nano-C particle composite Ni plating solution comprises: NiS0 4 .6H 2 0 with a concentration of 254 g/L, ΝΗ 3 · Η 2 0 (ΝΗ 3 content 25-28) at a concentration of 105 mL/L, and a concentration of 56 g/L. (NH4) 3 C 6 H 5 0 7 , 23 g/L CH 3 COONH 4 , concentration of O.lg/L sodium lauryl sulfate (CH 3 (CH 2 ) 1() CH 2 OS0 3 Na), ammonium oxalate (C 2 H 8 N 2 0 4 H 2 0) having a concentration of 0.1 g/L, and nano carbon powder having a concentration of 15 g/L; The nano-Cu particle composite Ni plating solution comprises: NiS at a concentration of 254 g/L (6H 2 0, ΝΗ 3 · Η 2 0 at a concentration of 105 mL/L (ΝΗ 3 content 25% 28%), concentration 56 g/ L (NH 4 ) 3 C 6 H 5 0 7 , CH 3 COONH 4 at a concentration of 23 g/L, CH 3 COOH at a concentration of 56 g/L, sodium lauryl sulfate at a concentration of 0.1 g/L (CH 3 (CH 2 )ioCH 2 OS0 3 Na), ammonium oxalate (C 2 H 8 N 2 4 .H 2 0) having a concentration of 0.1 g/L, and a nano copper powder having a concentration of 5 g/L.
PCT/CN2014/072214 2013-07-26 2014-02-19 Method for preparing super-hydrophobic surface by means of nanocomposite electro brush plating WO2015010464A1 (en)

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