CN113061890A - Method for constant-voltage electrodeposition of Ni-SiC composite coating on aluminum alloy surface - Google Patents
Method for constant-voltage electrodeposition of Ni-SiC composite coating on aluminum alloy surface Download PDFInfo
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Abstract
The invention belongs to the technical field of metal material surface modification, and particularly relates to a method for constant-voltage electrodeposition of a Ni-SiC composite coating on an aluminum alloy surface. Meanwhile, the silicon carbide powder in the electroplating solution has low concentration, and other large amounts of reagents are not added, so that the cost is reduced, and the pollution to the environment is reduced.
Description
Technical Field
The invention belongs to the technical field of surface modification of metal materials, and particularly relates to a method for performing constant-voltage electrodeposition on a Ni-SiC composite coating on an aluminum alloy surface.
Background
The marine resources are abundant in the ocean, in the exploration equipment of the marine resources, the marine riser is a connecting channel between a seabed wellhead and an offshore drilling platform, and compared with the traditional marine riser material, the aluminum alloy material has the advantages of low density, high strength, easiness in processing and the like, and is widely applied to the ocean exploitation process. However, in a severe marine environment, the uneven aluminum oxide film formed on the surface of the aluminum alloy can cause pitting corrosion on the surface of the aluminum alloy, which causes great economic loss. Therefore, the method has important significance for improving the corrosion resistance of the aluminum alloy in the marine environment so as to prolong the service life of the aluminum alloy and improve the application.
The aluminum alloy can be effectively protected from corrosion by depositing the alloy coating on the surface of the aluminum alloy by an electrodeposition method or chemical plating. The alloy coating obtained by electrodeposition can prevent the direct contact between the aluminum alloy and the ocean medium to form a protective barrier. Meanwhile, the alloy coating obtained by electrodeposition can improve the mechanical property of the aluminum alloy, so that the aluminum alloy can bear the continuous impact of seawater in the marine environment. Therefore, the alloy coating with good mechanical property and corrosion resistance is electrodeposited on the surface of the aluminum alloy, and the method has important research significance for improving the application range and prolonging the service life of the aluminum alloy.
Currently, the main electrodeposition processes are: Ni-SiC composite electroplating, chrome plating and the like. The chromium metal plating layer shows a plurality of excellent performances such as high corrosion resistance, high wear resistance, high hardness and the like, low oxidation rate and better strength retentivity at high temperature, solves the abrasion problem of the aluminum alloy in the use process and prolongs the service life of the aluminum alloy. However, the gas and waste liquid generated in the process of chromium electroplating can cause great harm to human body and environment, so a new green and healthy process needs to be found to replace chromium electroplating.
The Ni-SiC composite coating is a process for obtaining a composite material by co-depositing metal Ni and SiC particles by using an electrodeposition or chemical plating method. As a relatively new material surface treatment technology, the method has become an important method for improving the performances of wear resistance, hardness, corrosion resistance and the like of the material surface. Compared with chromium plating process, the Ni-SiC composite plating conforms to the national clean production concept, the process avoids pollutants for human body and environment, and the main performances of the Ni-SiC composite plating layer such as hardness, wear resistance, corrosion resistance and the like are equivalent to or superior to those of a chromium metal plating layer.
However, in the marine environment, the aluminum alloy marine riser not only faces the problem of corrosion, but also needs to bear the impact of seawater, and if the bonding force between the prepared coating and the substrate is not strong, the prepared coating can easily fall off, and the performance of the aluminum alloy surface is damaged, so that the preparation of the corrosion-resistant Ni-SiC composite coating with strong bonding force with the substrate has important significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for electrodepositing a Ni-SiC composite coating on the surface of an aluminum alloy in a constant-pressure mode, and the Ni-SiC composite coating which has stronger bonding force with a substrate and has anticorrosion performance is prepared on the surface of the aluminum alloy.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a method for electrodepositing a Ni-SiC composite coating on the surface of an aluminum alloy by constant voltage electrodeposition, which comprises the following steps:
s1, polishing the surface of the aluminum alloy to be smooth;
s2, putting the polished aluminum alloy into an alkali solution to remove grease on the surface of the aluminum alloy;
s3, placing the aluminum alloy into an acid solution, and removing an oxide film on the surface of the aluminum alloy;
s4, putting the aluminum alloy into a galvanizing solution to form a zinc replacement layer on the surface of the aluminum alloy;
s5, putting the aluminum alloy into an acid solution, and removing the zinc replacement layer on the surface of the aluminum alloy;
s6, putting the aluminum alloy into a galvanizing solution, and forming a zinc replacement layer on the surface of the aluminum alloy for the second time;
s7, configuring the powerPlating solution: 70g/L NiSO4·6H2O，115g/L Na3C6H5O7·2H2O，35g/L NH4Cl，0.1g/L C12H25O4NaS and SiC of which the concentration is not more than 0.5g/L, and carrying out ultrasonic treatment on the prepared electroplating solution to uniformly disperse SiC particles in the electroplating solution;
s8, putting the aluminum alloy obtained in the step S6 into electroplating solution, and performing constant-voltage electrodeposition by taking the aluminum alloy as a cathode and a graphite rod electrode as an anode to obtain the Ni-SiC composite coating by constant-voltage electrodeposition on the surface of the aluminum alloy.
The invention improves the composition of the electroplating solution, improves the pretreatment process of the aluminum alloy (degreasing, removing an oxide film, forming a zinc replacement layer for the first time, removing the zinc replacement layer, forming the zinc replacement layer for the second time and the like), and adopts the constant-pressure electrodeposition method to prepare the Ni-SiC composite coating which has corrosion resistance and stronger bonding force with the aluminum alloy substrate on the surface of the aluminum alloy, thereby having important significance for corrosion protection of maritime work equipment and accessories which are in direct contact with seawater in the marine environment. The principle of the invention is shown in figure 1, firstly, nickel ions are adsorbed on the surface of SiC nano particles to form ion cloud; then, the ion cloud formed under the action of the electric field moves to the cathode; finally, on the surface of the aluminum alloy substrate, nickel ions are reduced into metallic nickel, and SiC nano particles are coated in the metal coating at the same time.
In addition, the concentration of the silicon carbide powder in the electroplating solution is low and is controlled to be below 5g/L, compared with the electroplating solution in other electrodeposition methods, a large amount of other reagents are not added, so that the cost is reduced, and the environmental pollution is reduced.
Preferably, in the plating liquid of step S7, the amount of SiC used is 0.5 g/L.
Preferably, the time of the ultrasonic treatment in the step S7 is 1-3 h. Further, the time of the ultrasonic treatment was 1 h.
Preferably, the constant voltage of the constant voltage electrodeposition of step S8 is (-1) V- (-5) V. Further, the constant voltage of the constant voltage electrodeposition was-3V.
Preferably, the temperature of the constant voltage electrodeposition in step S8 is 30-50 ℃ for 10-30 min. Further, the temperature of the constant voltage electrodeposition was 35 ℃ for 10 min.
Preferably, mechanical stirring is used in the constant voltage electrodeposition process described in step S8, and the stirring speed is 200-300 rpm. Further, the stirring rate was 260 rpm.
Preferably, the SiC particles have a particle size of 20 to 50 nm. Further, the particle diameter of the SiC particles was 20 nm.
Preferably, 1000-sand 5000-mesh sand paper is used to polish the surface of the aluminum alloy to be smooth. Further, the aluminum alloy surface was polished to be smooth using 1000, 2000 and 3000 mesh sandpaper, respectively.
Preferably, step S2 is specifically: putting the polished aluminum alloy into 25g/L Na at 60 DEG C2CO3，25g/L Na3PO4And reacting in an aqueous alkali prepared by 80g/L NaOH for 2min to remove grease on the surface of the aluminum alloy, and then washing for 1min by using deionized water.
Preferably, step S3 is specifically: putting the aluminum alloy into a container filled with 300g/L HNO3And reacting in 200g/L HF acid solution at room temperature for 2min to remove the oxide film on the surface of the aluminum alloy, and then washing with deionized water for 1 min.
Preferably, step S4 is specifically: placing aluminum alloy into FeCl made of 10g/L3·6H2O，1g/L C4H4O6KNa·4H2Reacting in a zinc plating solution prepared by 80g/L ZnO and 500g/L NaOH at room temperature for 2min to form a zinc replacement layer on the surface of the aluminum alloy substrate, and then washing with deionized water for 1 min.
Preferably, step S5 is specifically: putting the aluminum alloy into a container filled with 300g/L HNO3And reacting in 200g/L HF acid solution at room temperature for 5min to remove the zinc replacement layer on the surface of the aluminum alloy, and then washing with deionized water for 1 min.
Preferably, step S6 is specifically: placing aluminum alloy into FeCl made of 10g/L3·6H2O，1g/L C4H4O6KNa·4H2Reacting in a zinc plating solution prepared by O, 90g/L ZnO and 500g/L NaOH at room temperature for 2minThe zinc displacement layer was formed on the surface of the aluminum alloy substrate for the second time, followed by rinsing with deionized water for 1 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for constant-voltage electrodeposition of a Ni-SiC composite coating on the surface of an aluminum alloy, which comprises the steps of applying certain pretreatment processes (degreasing, removing an oxidation film, forming a zinc replacement layer for the first time, removing the zinc replacement layer, forming the zinc replacement layer for the second time and the like) on the aluminum alloy, then carrying out constant-voltage electrodeposition in electroplating solution containing nickel ions and silicon carbide particles, and depositing on the surface of the aluminum alloy to obtain the Ni-SiC composite coating which has stronger bonding force with a substrate and has anti-corrosion performance. The invention has the following advantages:
(1) the Ni-SiC composite coating with the anti-corrosion performance can be prepared on the surface of the aluminum alloy;
(2) in the adopted electroplating solution, the concentration of the silicon carbide powder is lower and is controlled below 5g/L, compared with the electroplating solutions in other electrodeposition methods, a large amount of other reagents are not added, so that the cost is reduced on one hand, and the pollution to the environment is reduced on the other hand;
(3) c is added into the electroplating solution12H25O4NaS is used as a wetting agent, and ultrasonic treatment is carried out on the electroplating solution, so that the agglomeration of SiC particles is reduced;
(4) in the constant-voltage electric deposition process, SiC particles are prevented from agglomerating by continuous mechanical stirring, so that the deposition effect is improved;
(5) the aluminum alloy is subjected to secondary zinc dipping treatment, so that the binding force between the coating and the aluminum alloy substrate is improved;
(6) the prepared Ni-SiC composite coating not only has better corrosion resistance, but also has stronger binding force with a substrate, and can be applied to marine equipment and accessories which are in direct contact with seawater in marine environment.
Drawings
FIG. 1 is a schematic view of the principle of constant voltage electrodeposition of a Ni-SiC composite plating layer;
FIG. 2 is a microscopic surface topography of the Ni-SiC composite coating (example 1 for A, comparative example 1 for B, and comparative example 2 for C);
FIG. 3 is an EIS plot of the Ni-SiC composite coating (with the abscissa axis Zr being the real part of the impedance and the ordinate Zi being the imaginary part of the impedance).
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 method for preparing Ni-SiC composite coating by aluminum alloy surface constant voltage electrodeposition
Step 1: the aluminum alloy surface was polished smooth using 1000, 2000 and 3000 mesh sandpaper, respectively.
Step 2: putting the polished aluminum alloy into 25g/L Na at 60 DEG C2CO3，25g/L Na3PO4And reacting in an aqueous alkali prepared by 80g/L NaOH for 2min to remove grease on the surface of the aluminum alloy, and then washing for 1min by using deionized water.
And step 3: putting the aluminum alloy into a container filled with 300g/L HNO3And reacting in 200g/L HF acid solution at room temperature for 2min to remove the oxide film on the surface of the aluminum alloy, and then washing with deionized water for 1 min.
And 4, step 4: placing aluminum alloy into FeCl made of 10g/L3·6H2O，1g/L C4H4O6KNa·4H2Reacting in a zinc plating solution prepared by 80g/L ZnO and 500g/L NaOH at room temperature for 2min to form a zinc replacement layer on the surface of the aluminum alloy substrate, and then washing with deionized water for 1 min.
And 5: putting the aluminum alloy into a container filled with 300g/L HNO3200g/L HF acid solution, reacting at room temperature for 5min, removing the zinc replacement layer on the surface of the aluminum alloy, and washing with deionized water for 1min。
Step 6: placing aluminum alloy into FeCl made of 10g/L3·6H2O，1g/L C4H4O6KNa·4H2Reacting in a zinc plating solution prepared by 90g/L ZnO and 500g/L NaOH at room temperature for 2min to form a zinc replacement layer on the surface of the aluminum alloy substrate for the second time, and then washing with deionized water for 1 min.
And 7: the prepared electroplating solution has the composition of 70g/L NiSO4·6H2O，115g/L Na3C6H5O7·2H2O，35g/L NH4Cl，0.1g/L C12H25O4NaS and 0.5g/L SiC, wherein the particle size of SiC particles is 20nm, and the prepared electroplating solution is subjected to ultrasonic treatment for 1h by using a numerical control ultrasonic cleaner, so that silicon carbide particles can be uniformly dispersed in the electroplating solution.
And 8: and (2) putting the aluminum alloy into prepared electroplating solution for constant-voltage electrodeposition, taking the aluminum alloy substrate as a cathode and the graphite rod electrode as an anode, and performing constant-voltage electrodeposition at constant voltage of-3V, wherein the temperature is kept constant at 35 ℃ in the constant-voltage electrodeposition process for 10min, mechanical stirring is used in the constant-voltage electrodeposition process, and the stirring speed is 260rpm, so that the Ni-SiC composite coating can be obtained by constant-voltage electrodeposition on the surface of the aluminum alloy.
Comparative example 1 method for preparing Ni-SiC composite coating by constant-voltage electrodeposition on aluminum alloy surface
Steps 1 to 6 were the same as in example 1.
And 7: the prepared electroplating solution has the composition of 70g/L NiSO4·6H2O，115g/LNa3C6H5O7·2H2O，35g/LNH4Cl，0.1g/LC12H25O4NaS, 1.0g/L SiC, wherein the grain diameter of SiC grains is 20nm, and the prepared electroplating solution is subjected to ultrasonic treatment by using a numerical control ultrasonic cleaner for 1h, so that silicon carbide grains can be uniformly dispersed in the electroplating solution.
And 8, performing constant-voltage electrodeposition on the surface of the aluminum alloy to obtain the Ni-SiC composite coating as in the example 1.
Comparative example 2 method for preparing Ni-SiC composite coating by constant-voltage electrodeposition on aluminum alloy surface
Steps 1 to 6 were the same as in example 1.
And 7: the prepared electroplating solution has the composition of 70g/L NiSO4·6H2O，115g/L Na3C6H5O7·2H2O，35g/L NH4Cl，0.1g/L C12H25O4NaS, 1.5g/L SiC, wherein the particle size of SiC particles is 20nm, and the prepared electroplating solution is subjected to ultrasonic treatment for 1h by using a numerical control ultrasonic cleaner, so that silicon carbide particles can be uniformly dispersed in the electroplating solution.
And 8, performing constant-voltage electrodeposition on the surface of the aluminum alloy to obtain the Ni-SiC composite coating as in the example 1.
Experimental example 1 surface morphology observation and anticorrosion property test
The Ni-SiC composite coatings prepared in example 1 and comparative examples 1 to 2 were subjected to surface morphology observation and corrosion resistance test using a scanning electron microscope and an impedance spectroscopy test.
(1) Surface morphology of Ni-SiC composite coating
The surface morphology of the Ni-SiC composite plating layer was observed using a scanning electron microscope, and as shown in fig. 2, the Ni-SiC composite plating layers prepared using constant voltage electrodeposition in example 1 and comparative examples 1 to 2 of the present invention had a flat, uniform and dense surface morphology, and silicon carbide particles were uniformly distributed in the plating layer without significant agglomeration. The Ni-SiC composite coating prepared by the method has stronger binding force with the aluminum alloy substrate.
(2) Impedance spectrogram test
And testing the corrosion resistance of the Ni-SiC composite coating prepared by the experiment by using a Gamry electrochemical workstation. The test uses a three-electrode system, wherein the prepared aluminum alloy sample with the Ni-SiC composite coating is used as a working electrode, a platinum sheet electrode is used as a counter electrode, an Ag/AgCl electrode filled with saturated potassium chloride solution is used as a reference electrode, the test solution is 3.5 w.t.% of sodium chloride solution, the test frequency range is 100000-0.01Hz, 10mV alternating current disturbance is adopted in the test process, and the open-circuit voltage of the three-electrode system is required to be stable before the test.
As can be seen from FIG. 3, the Ni-SiC composite plating layer obtained in example 1 having a SiC concentration of 0.5g/L has excellent corrosion resistance, while the corrosion resistance is lowered as the concentration of silicon carbide is increased (comparative examples 1-2). Therefore, the silicon carbide particles with lower concentration can be more uniformly distributed in the Ni-SiC composite coating, so that the coating is more uniform and compact, and the corrosion resistance is improved.
The experimental results show that the Ni-SiC composite coating prepared by constant-voltage electrodeposition has uniform and compact surface appearance, silicon carbide particles are uniformly distributed in the coating, and the coating has excellent corrosion resistance.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A method for electrodepositing a Ni-SiC composite coating on the surface of an aluminum alloy at constant voltage is characterized by comprising the following steps:
s1, polishing the surface of the aluminum alloy to be smooth;
s2, putting the polished aluminum alloy into an alkali solution to remove grease on the surface of the aluminum alloy;
s3, placing the aluminum alloy into an acid solution, and removing an oxide film on the surface of the aluminum alloy;
s4, putting the aluminum alloy into a galvanizing solution to form a zinc replacement layer on the surface of the aluminum alloy;
s5, putting the aluminum alloy into an acid solution, and removing the zinc replacement layer on the surface of the aluminum alloy;
s6, putting the aluminum alloy into a galvanizing solution, and forming a zinc replacement layer on the surface of the aluminum alloy for the second time;
s7, preparing a plating solution: 70g/L NiSO4·6H2O，115g/L Na3C6H5O7·2H2O，35g/L NH4Cl，0.1g/L C12H25O4NaS, not largeCarrying out ultrasonic treatment on the prepared electroplating solution in 0.5g/L of SiC, so that SiC particles can be uniformly dispersed in the electroplating solution;
s8, putting the aluminum alloy obtained in the step S6 into electroplating solution, and performing constant-voltage electrodeposition by taking the aluminum alloy as a cathode and a graphite rod electrode as an anode to obtain the Ni-SiC composite coating by constant-voltage electrodeposition on the surface of the aluminum alloy.
2. The method for constant-pressure electrodeposition of a Ni-SiC composite coating on an aluminum alloy surface according to claim 1, wherein the ultrasonic treatment of the step S7 is carried out for 1-3 h.
3. The method for constant voltage electrodeposition of a Ni-SiC composite coating on an aluminum alloy surface according to claim 1, wherein the constant voltage of the constant voltage electrodeposition in the step S8 is (-1) V- (-5) V.
4. The method for constant voltage electrodeposition of a Ni-SiC composite coating on an aluminum alloy surface as recited in claim 1 in which the constant voltage electrodeposition of step S8 is carried out at a temperature of 30 to 50 ℃ for a period of 10 to 30 min.
5. The method for constant voltage electrodeposition of Ni-SiC composite coating on aluminum alloy surface as claimed in claim 1, wherein the step S8 is performed by mechanical stirring at 200-300 rpm.
6. The method for constant-pressure electrodeposition of a Ni-SiC composite coating on an aluminum alloy surface according to claim 1, wherein the SiC particles have a particle size of 20-50 nm.
7. The method for constant-voltage electrodeposition of the Ni-SiC composite coating on the surface of the aluminum alloy according to claim 1, wherein the step S3 is specifically as follows: putting the aluminum alloy into a container filled with 300g/L HNO3And reacting in 200g/L HF acid solution at room temperature for 2min to remove the oxide film on the surface of the aluminum alloy, and then washing with deionized water for 1 min.
8. The method for constant-voltage electrodeposition of the Ni-SiC composite coating on the surface of the aluminum alloy according to claim 1, wherein the step S4 is specifically as follows: placing aluminum alloy into FeCl made of 10g/L3·6H2O，1g/L C4H4O6KNa·4H2Reacting in a zinc plating solution prepared by 80g/L ZnO and 500g/L NaOH at room temperature for 2min to form a zinc replacement layer on the surface of the aluminum alloy substrate, and then washing with deionized water for 1 min.
9. The method for constant-voltage electrodeposition of the Ni-SiC composite coating on the surface of the aluminum alloy according to claim 1, wherein the step S5 is specifically as follows: putting the aluminum alloy into a container filled with 300g/L HNO3And reacting in 200g/L HF acid solution at room temperature for 5min to remove the zinc replacement layer on the surface of the aluminum alloy, and then washing with deionized water for 1 min.
10. The method for constant-voltage electrodeposition of the Ni-SiC composite coating on the surface of the aluminum alloy according to claim 1, wherein the step S6 is specifically as follows: placing aluminum alloy into FeCl made of 10g/L3·6H2O，1g/L C4H4O6KNa·4H2Reacting in a zinc plating solution prepared by 90g/L ZnO and 500g/L NaOH at room temperature for 2min to form a zinc replacement layer on the surface of the aluminum alloy substrate for the second time, and then washing with deionized water for 1 min.
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