阅读说明：本技术 微纳米复合镀层表面浸渍覆膜和恒温处理的表面改性方法 (Surface modification method for micro-nano composite coating surface impregnation coating and constant temperature treatment ) 是由 张胜健 王峰 于 2020-04-26 设计创作，主要内容包括：本发明公开了微纳米复合镀层表面浸渍覆膜和恒温处理的表面改性方法,在瓦特型电沉积液中,通过调节主盐溶度,活化剂浓度,改变纳米二氧化硅的含量和改变工艺参数等,制备出Ni-Co-SiO<Sub>2</Sub>纳米复合涂层。将制备出的纳米复合涂层,放置在覆膜溶液中,一定时间后取出,放置在恒温干燥箱中,恒温一定时间,即可制备出浸渍覆膜恒温处理的Ni-Co-SiO<Sub>2</Sub>涂层,获得处理后涂层,其表面粗糙度显著降低,不会改变Ni-Co-SiO<Sub>2</Sub>纳米复合涂层的微结构,但是不改变Ni-Co-SiO<Sub>2</Sub>纳米复合涂层的厚度,膜层的在海水中的稳定性较好,改性后的涂层具有较高的耐蚀性,延长了Ni-Co-SiO<Sub>2</Sub>纳米复合涂层的防护寿命。(The invention discloses a surface modification method for surface impregnation coating and constant temperature treatment of a micro-nano composite coating, which prepares Ni-Co-SiO in watt-type electrodeposition liquid by adjusting the solubility of main salt and the concentration of an activating agent, changing the content of nano silicon dioxide, changing process parameters and the like 2 And (3) nano composite coating. Placing the prepared nano composite coating in a coating solution, taking out after a certain time, placing in a constant-temperature drying box, keeping the temperature for a certain time to prepare Ni-Co-SiO subjected to constant-temperature treatment of the impregnated coating 2 Coating, resulting in a treated coating, having a significantly reduced surface roughness without altering Ni-Co-SiO 2 Microstructure of nanocomposite coatings, howeverWithout changing Ni-Co-SiO 2 The thickness of the nano composite coating and the stability of the film layer in seawater are better, the modified coating has higher corrosion resistance, and the Ni-Co-SiO is prolonged 2 The protective life of the nanocomposite coating.)

1. The surface modification method for the surface impregnation coating and constant temperature treatment of the micro-nano composite coating is characterized by comprising the following steps: comprises the following steps of (a) carrying out,

s1: accurately weighing main salt, an activating agent and a buffering agent according to the mass ratio of 22:1:4:3, 22:2:4:3, 22:4:4:3, 18:1:4:3, 18:2:4:3, 18:3:4:3, 18:4:4:3, 20:1:4:3, 20:2:4:3, 20:3:4:3 and 20:4:4:3, adding deionized water to prepare a solution with a certain concentration, then adding 0-2 g of nano SiO2 particles, and dispersing the nano particles through magnetic stirring, ultrasonic oscillation and a cell disruptor. The carbon steel is polished by water sand paper and washed by ethanol, acetone and deionized water in sequence. During electrodeposition, continuously stirring the electrodeposition solution by using a magnetic stirrer, controlling the temperature to be 25-65 ℃, controlling the current to be 5-95 mA, controlling the pH to be 3.8-4.2, and controlling the thickness of a deposited composite coating to be 30 +/-mu m;

s2: the prepared composite coating is firstly ultrasonically cleaned by deionized water and dried for later use. Preparing a single dipping coating solution, wherein the mass ratio of solute to solvent in the solution can be 1:10, 1:5, 3:7, 4:6 and 1:1, and the dipping time is 10-90 min; preparing two or more than two kinds of dipping solutions, wherein the mass ratio of solute to solvent in the two kinds of film-coating dipping solutions is 1:1:10, 1:2:10, 1:3:10, 1:4:10, 1:5:10, 5:1:10, 5:2:10, 5:3:10, 5:4:10, 5:5:10, and the dipping time is 10-90 min;

s3: after the dipping treatment, the constant temperature is 40 ℃ to 160 ℃, the chemical reaction is carried out under the constant temperature condition, and the constant temperature treatment time is 1h to 14 h.

2. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in step S1, the main salt is an electrodepositable metal salt, including but not limited to nickel sulfate, cobalt sulfate, or one of nickel sulfamate and nickel chloride.

3. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in step S1, the activator is nickel chloride.

4. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in step S1, the buffer is boric acid.

5. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in the step S1, the composite coating is deposited as a nano or micro composite coating, including but not limited to Ni-Co-SiO₂、Ni-SiO₂、Ni-SiC、Zn-Co-SiO₂And Ni-Co-SiC.

6. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in step S2, the solute in the film coating solution is an oily substance, including but not limited to one of tung oil, castor oil, and oleic acid.

7. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in step S2, the solvent is an organic solvent including, but not limited to, acetone, ethanol, or diethyl ether.

8. The surface modification method for the surface impregnation coating and the constant temperature treatment of the micro-nano composite coating according to claim 1, characterized in that: in step S3, the film molecules may form a dense film layer by addition polymerization of molecules or oxidation at a certain temperature.

Technical Field

The invention relates to the technical field of chemistry, nanotechnology, electrodeposition of micro-nano composite coatings and film modification, and relates to preparation of macromolecule and nanoparticle polymers formed by addition polymerization of organic molecules, electrodeposition of micro-nano composite coatings, supporting and skeleton effects of micro-nano composites on films, in particular to a surface modification method for surface impregnation coating and constant temperature treatment of micro-nano composite coatings.

Background

Carbon steel is an important component of steel materials, and is widely used in various machine manufacturing industries such as buildings, railways, ships and the like due to its excellent performance. With the continuous deep development of oceans, carbon steel is also used in large quantity, but carbon steel is extremely easy to corrode in corrosive media such as oceanic atmosphere and seawater, the maintenance cost for steel corrosion is high, and the economic loss caused by oceanic corrosion is huge every year. Therefore, the surface treatment of the carbon steel to improve the corrosion resistance has important significance, wherein the metal alloy coating and the micro-nano composite coating are one of important means for ocean protection.

Ni-Co alloy coatings were first developed in 1936 and are widely used due to their good physical, chemical and mechanical properties, such as high hardness, wear and corrosion resistance. In order to further improve the performance of the Ni-Co alloy coating, doping micro-nano particles in the electrodeposition process is one of important means, for example, adding nano SiO into the electrodeposition solution₂Nano Si₃N₄Nano SiC and nano TiO₂Nano Al₂O₃And the performance of the Ni-Co metal-based alloy coating can be greatly improved. The nano silicon dioxide is an important oxide for enhancing the Ni-Co alloy coating, and compared with a pure alloy coating, the metal composite coating doped with the nano silicon dioxide has higher hardness, higher wear resistance and higher corrosion resistance. The particle size of the doped nano particles in the electrodeposition composite coating reported in the current research is about 50 nm. Atuanya et al prepared Ni-Co-SiO on the surface of carbon steel by Co-deposition₂The composite coatings can obviously influence the grain size and hardness of the alloy coating by doping the nano silicon dioxide with the grain diameter of 55nm, and realize effective corrosion prevention in pipelines. The method for depositing Ni-Co-SiO on the copper matrix by using the electrodeposition method is adopted by the King Heju et al₂Composite coating, comparativeThe addition of the Ni-Co coating with the nano-silica with the particle size of 30nm finds that the corrosion resistance and the tribology performance of the alloy coating can be improved by the addition of the nano-silica particles. Slavashimanian and the like change direct current deposition into pulse electrodeposition and research the deposition parameter pair Ni-Co-SiO of the pulse electrodeposition₂The influence of the composite coating is discovered by comparing direct current deposition and pulse electrodeposition of Ni-Co-SiO₂Has a smoother surface and smaller grain size. However, no matter which kind of electrodeposition is used, no matter which kind of nano particles are doped in the metal alloy coating, the surface at the end of the composite electrodeposition always has defects such as gaps, and in practical application, the gap positions are corroded firstly, so that the service life of the metal alloy coating is reduced.

Based on the method, the invention designs a surface modification method of the micro-nano composite plating layer surface impregnation coating and constant temperature treatment, so as to solve the problems.

Disclosure of Invention

The invention provides a surface modification method applied to surface impregnation coating and constant temperature treatment of a micro-nano composite coating, aiming at the problem that after composite electrodeposition is finished, the electrodeposition surface has defects such as gaps and the like, which are easy to cause corrosion. Firstly, preparing Ni-Co-SiO on a carbon steel substrate by constant current₂The nano composite coating is made to have different roughness by adjusting the current density and the content of nano silicon dioxide, then a sample is soaked in a solution of a coating substance, molecules of the coating substance reach the clearance of the composite coating through osmosis and are adsorbed at the clearance, finally, the coating substance is subjected to chemical reaction on the surface through constant temperature to generate a film with a net structure to cover the surface of the composite coating, and meanwhile, Ni-Co-SiO on the surface of the composite coating is coated₂The compound is used for strengthening and supporting, and the corrosion resistance of the compound plating layer is greatly improved. The method provides a new idea for further improving the corrosion resistance of the composite plating layer.

The technical scheme of the invention is as follows: in watt type electrodeposition liquid, the content of nano silicon dioxide is changed and the process is changed by adjusting the solubility of main salt and the concentration of an activating agentParameters and the like to prepare Ni-Co-SiO₂And (3) nano composite coating. Placing the prepared nano composite coating in a coating solution, taking out after a certain time, placing in a constant-temperature drying box, keeping the temperature for a certain time to prepare Ni-Co-SiO subjected to constant-temperature treatment of the impregnated coating₂And (4) coating.

The invention relates to a surface modification method applied to surface impregnation coating and constant temperature treatment of a micro-nano composite coating, which comprises the following steps: the Ni-Co-SiO is prepared by proper preparation of the electro-deposition solution and selection of proper electro-deposition parameters in a constant current mode₂A nanocomposite coating; selecting a film forming material and preparing a dipping film coating solution; the surface is treated at constant temperature, and the single molecules are polymerized into reticular macromolecules to form a film layer.

In order to achieve the purpose, the invention provides a surface modification method applied to surface impregnation coating and constant temperature treatment of a micro-nano composite coating, which comprises the following specific operation steps:

(1) accurately weighing main salt, an activating agent and a buffering agent according to the mass ratio of 22:1:4:3, 22:2:4:3, 22:4:4:3, 18:1:4:3, 18:2:4:3, 18:3:4:3, 18:4:4:3, 20:1:4:3, 20:2:4:3, 20:3:4:3 and 20:4:4:3, adding deionized water to prepare a solution with a certain concentration, then adding 0-2 g of nano SiO2 particles, and dispersing the nano particles through magnetic stirring, ultrasonic oscillation and a cell disruptor. The carbon steel is polished by water sand paper and washed by ethanol, acetone and deionized water in sequence. During electrodeposition, continuously stirring the electrodeposition solution by using a magnetic stirrer, controlling the temperature to be 25-65 ℃, controlling the current to be 5-95 mA, controlling the pH to be 3.8-4.2, and controlling the thickness of a deposited composite coating to be 30 +/-mu m;

(2) the prepared composite coating is firstly ultrasonically cleaned by deionized water and dried for later use. Preparing a single dipping coating solution, wherein the mass ratio of solute to solvent in the solution can be 1:10, 1:5, 3:7, 4:6 and 1:1, and the dipping time is 10-90 min; preparing two or more than two kinds of dipping solutions, wherein the mass ratio of solute to solvent in the two kinds of film-coating dipping solutions is 1:1:10, 1:2:10, 1:3:10, 1:4:10, 1:5:10, 5:1:10, 5:2:10, 5:3:10, 5:4:10, 5:5:10, and the dipping time is 10-90 min;

(3) after the dipping treatment, the constant temperature is 40 ℃ to 160 ℃, the chemical reaction is carried out under the constant temperature condition, and the constant temperature treatment time is 1h to 14 h.

Preferably, in step S1, the main salt is an electrodepositable metal salt, including but not limited to nickel sulfate, cobalt sulfate, nickel sulfamate, and nickel chloride.

Preferably, in step S1, the activator is nickel chloride, but the activator in the electrodeposition bath may be one of other substances that can activate the cathode.

Preferably, in step S1, the buffer is boric acid, and the particle size of the self-made nano-silica is about 60 nm. Three means are adopted for dispersing the nano particles: magnetic stirring, ultrasonic oscillation and cell disruption instrument.

Preferably, in the step S1, the composite coating is not limited to Ni-Co-SiO₂Composite coating also comprising Ni-SiO₂，Ni-SiC，Zn-Co-SiO₂Ni-Co-SiC and other nano or micron composite coatings.

Preferably, in step S2, the solute in the coating solution is an oily substance, including but not limited to tung oil, castor oil, and oleic acid, which have unsaturated double bonds and can be oxidized, added, and polymerized to form a network-like macromolecule, and the formed film is dense and has a good water-proof effect or a combination of multiple substances.

Preferably, in step S2, the solvent is an organic solvent including but not limited to acetone, ethanol, and ethyl ether, which can dissolve the coating material.

Preferably, in step S3, the film molecules may form a dense film layer by a polyaddition reaction of the molecules or by a chemical reaction such as an oxidation reaction at a suitable temperature.

Compared with the prior art, the invention has the beneficial effects that: successfully preparing Ni-Co-SiO on the surface of carbon steel₂The nano composite coating is dipped in the coating solution and then is continuously processed at constant temperature to obtain the processed coating, the surface roughness of the coating is obviously reduced, and Ni-Co-SiO is not changed₂The microstructure of the nanocomposite coating, but without altering Ni-Co-SiO₂The thickness of the nano composite coating and the stability of the film layer in seawater are better, the modified coating has higher corrosion resistance, and the Ni-Co-SiO is prolonged₂The protective life of the nanocomposite coating.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a SEM schematic diagram of a Ni-Co-SiO2 nanocomposite coating before dip coating treatment according to the present invention;

FIG. 2 is an SEM image of a Ni-Co-SiO2 coating after a dip coating treatment according to the present invention;

FIG. 3 is a map scan of the Si element of the Ni-Co-SiO2 nanocomposite coating of the invention;

FIG. 4 is a graph of the EDS composition of the sweep after Ni-Co-SiO2 dip coating treatment in accordance with the present invention;

FIG. 5 is an XRD pattern of a sample after the dipping coating treatment of Q235B, Ni-Co-SiO2 and Ni-Co-SiO2 according to the present invention;

FIG. 6 shows Tafel polarization patterns of samples treated with Q235B, Ni-Co-SiO2 and Ni-Co-SiO2 dipping films according to the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.