CN106906498A - A kind of graphene oxide zinc composite plating solution and its preparation method and application - Google Patents

Abstract

A kind of graphene oxide zinc composite electroplating solution, calculated by every liter of electroplating solution, by 50-300 mg graphene oxide, 30-40g zinc chloride, 150-170g ammonium chloride, 16g hexamethylenetetramine, 12g lemon Sodium acid, 2g of compound additives and the rest of distilled water; the compound additives are composed of saccharin, benzoic acetone and pingjia, and the mass ratio of saccharin, bianchacetone and pingjia is 1:2:15. Also provided is the preparation method of the above-mentioned electroplating solution, adding zinc chloride, ammonium chloride, hexamethylenetetramine, trisodium citrate and composite additives into distilled water to dissolve in sequence, and adding graphene oxide under stirring conditions, and then Adjust the pH value to 4.5-5.0, and finally ultrasonicate at an ultrasonic power of 100W to obtain a graphene oxide-zinc composite electroplating solution. The graphene oxide-zinc composite electroplating solution of the invention is used for electroplating on the surface of steel alloys, that is, to form a graphene oxide composite coating with good corrosion resistance.

Description

A kind of graphene oxide zinc composite electroplating solution and its preparation method and application

technical field

The invention belongs to the field of materials science, and relates to an electroplating solution, in particular to a graphene oxide-zinc composite electroplating solution and a preparation method and application thereof.

Background technique

Since zinc is easily passivated in the atmosphere and has a negative potential than iron, it is widely used as a sacrificial anode protective coating on steel products. Zinc coatings have a good cathodic protection effect on steel products in the atmospheric environment, but their corrosion resistance in salt water or humid marine atmospheric environments is not ideal, which limits the practical application of zinc coatings and related steel products.

Composite coating is currently the main means to improve the protective performance of zinc coating. That is, in the process of applying zinc coating, zinc-based composite coatings are formed by incorporating a small amount of heterogeneous elements or second-phase particles, and relying on the incorporation of heterogeneous elements and second-phase particles to change the structure and properties of the zinc coating to achieve the zinc coating. Influence of layer anticorrosion performance. The heterogeneous alloy elements reported to be doped mainly include Ni, Fe, Co, Al, Cd, Mg, Mn, Si, P, etc.; the second phase particles are mainly metal oxides, carbides, and nitrides. Based on existing studies, it has been shown that although the addition of these elements and the second phase improves the protective performance of zinc coatings to some extent, the increase in corrosion resistance is not significant. Therefore, it is urgent to develop new and efficient zinc-based composite anti-corrosion coatings.

Graphene oxide is a derivative of graphene, a new type of carbon material that is exfoliated from graphite oxide to form a single atomic layer thickness. Because graphene oxide not only has a special two-dimensional structure similar to graphene, high specific surface area, excellent permeability resistance, high thermal stability and chemical stability, but also contains rich oxygen-containing functional groups, making it a It is well dispersed in most polar solvents and easily compounded with other materials, so it has great application potential in the field of building composite coatings for metal anticorrosion.

At present, the reports on the composite anticorrosion coating of graphene oxide and other materials mainly focus on the research of integrating graphene oxide into polymer materials to form composite anticorrosion coating. Such as polyvinylidene fluoride, alkyd resin, polyurethane acrylate, epoxy resin and other polymer materials. No studies have been done on graphene oxide zinc composite coatings.

Due to its simple process, low cost, parameter control and dense coating, electrodeposition technology has become a kind of anti-corrosion, wear-resistant and decorative metal coatings such as Sn, Zn, Ni, Cr, Cu, etc. on the surface of steel products. Typical preparation process. Therefore, the use of electrodeposition technology to prepare a composite coating of metal and graphene on the surface of steel products is of great significance for improving the corrosion resistance of steel products and its application.

Contents of the invention

For the above-mentioned technical problems in the prior art, the invention provides a kind of graphene oxide zinc composite electroplating solution and its preparation method and application, described this graphene oxide zinc composite electroplating solution and its preparation method and application to solve The corrosion resistance of the zinc coating in the prior art is not ideal in salt water or humid marine atmosphere environment.

The invention provides a kind of graphene oxide zinc composite electroplating solution, calculated by every liter of graphene oxide zinc composite electroplating solution, its composition and content are as follows:

The compound additive is composed of saccharin, benzacetone and pecaid, and the mass ratio of the said saccharin, benzacetone and pepina is 1:2:15.

The present invention also provides the preparation method of above-mentioned a kind of graphene oxide zinc composite electroplating solution, weigh graphene oxide, zinc chloride, chloride Ammonium, hexamethylenetetramine, trisodium citrate, composite additives and distilled water, zinc chloride, ammonium chloride, hexamethylenetetramine, trisodium citrate and composite additives were added in turn to dissolve in distilled water, and in Graphene oxide is added under the condition of stirring, then the pH value is adjusted to 4.5-5.0 with hydrochloric acid solution, and finally the plating solution is ultrasonicated for 1-3 hours to obtain a graphene oxide-zinc composite plating solution with good dispersion.

The present invention also provides the above-mentioned graphene oxide zinc electroplating solution for forming a zinc-graphene oxide graphene zinc composite coating on the surface of a steel workpiece.

Further, the above-mentioned graphene oxide electroplating solution forms the method for graphene oxide zinc composite coating on the steel workpiece surface, comprises the following steps:

1) a step of pretreating the surface of a steel alloy workpiece;

The surface of the iron and steel alloy workpiece is polished with 280#, 800# and 1500# sandpaper successively, and then rinsed with deionized water to remove the residual matrix wear stripping and sandpaper abrasive grains on the steel surface, and then polished with 0.5# diamond abrasive paste, and then Soak in 20% sodium hydroxide aqueous solution at a temperature of 70-80°C for 10-15 minutes, degrease and remove oil, then rinse with tap water and distilled water in order to obtain a smooth and pollution-free surface;

Finally, pickling with 10% hydrochloric acid aqueous solution for surface activation for 30-60s, then rinsing the surface acid solution with tap water and distilled water successively, and then immersing the steel workpiece treated above in distilled water for standby;

2) a step of preparing a graphene oxide zinc composite coating on the surface of a steel alloy workpiece;

Put the iron and steel alloy workpiece and pure zinc material treated in step 1) into the graphene oxide zinc composite electroplating solution, and connect them to the negative pole and positive pole of the DC stabilized current power supply respectively, at a current density of 5A/dm ² , The temperature of the electroplating solution is 30°C and deposited under continuous mechanical stirring conditions. After taking it out, wash it with tap water and distilled water in turn, and dry it with a hair dryer or dry it in the shade in a dry environment, and then you can get a steel alloy coated with graphene oxide zinc composite coating on the surface. artifact.

The graphene oxide zinc composite coating on the iron and steel workpiece whose surface is coated with the graphene oxide zinc composite coating obtained above, that is, through the process of electrodepositing zinc, the graphene oxide particles are co-deposited into the zinc coating along with the zinc atom deposition A graphene oxide-zinc composite coating is formed, and the surface of the formed graphene oxide-zinc composite coating presents a rice-like cluster structure.

A kind of graphene oxide zinc composite electroplating solution of the present invention, owing to added chemically inert graphene oxide in the pure zinc electroplating solution, therefore when applying this graphene oxide zinc composite electroplating solution on the steel alloy workpiece surface plating, formed The graphene oxide zinc composite coating with dense, nanoscale structure and high anti-corrosion performance solves the problem of poor corrosion resistance of traditional pure zinc coatings in salt water and humid marine atmosphere environments.

Compared with the prior art, the technical progress of the present invention is remarkable. The high-corrosion-resistant graphene oxide zinc composite coating prepared by the present invention has low cost, low environmental impact, and low equipment requirements, so the preparation and application of the graphene oxide zinc composite electroplating solution of the present invention meet the needs of industrial production .

Description of drawings

Fig. 1 is the scanning electron micrograph of the coating surface of the iron and steel alloy coating piece that the surface of comparative example 1 gained is coated with pure zinc coating;

Fig. 2 is the scanning electron micrograph of the coating surface of the iron and steel alloy plated part that the surface of embodiment 1 gained is coated with graphene-zinc composite coating;

Fig. 3 is the scanning electron micrograph of the coating surface of the iron and steel alloy plated part that the surface of embodiment 2 gained is coated with graphene-zinc composite coating;

Fig. 4 is the scanning electron micrograph of the coating surface of the steel alloy plated part that the surface of embodiment 3 gained is coated with graphene-zinc composite coating;

Fig. 5 is the scanning electron micrograph of the coating surface of the iron and steel alloy plated part that the surface of embodiment 4 gained is coated with graphene-zinc composite coating;

Fig. 6 is the iron and steel alloy plated piece that the surface of comparative example 1 gained is coated with pure zinc coating and above-mentioned embodiment 1,2,3,4, the steel alloy plated piece that the surface of above-mentioned embodiment 1,2,3,4,5 gained is coated with graphene zinc composite coating Potentiodynamic polarization curve of 3.5% (mass fraction) NaCl solution.

detailed description

The present invention will be further described below in conjunction with specific examples. It should be pointed out that the following examples are intended to understand the present invention, but do not limit it in any way.

Comparative Example 1

The present embodiment is the comparative example of following embodiment 1, embodiment 2, embodiment 3, embodiment 4

In the present embodiment, a kind of zinc electroplating solution without adding graphene oxide, calculated by every liter of zinc plating solution, its composition and content are as follows:

Above-mentioned a kind of zinc electroplating solution is prepared by the method of following steps:

Zinc chloride, ammonium chloride, benzylidene acetone, hexamethylenetetramine, trisodium citrate, and sodium citrate were sequentially added to distilled water for dissolution, and then the pH value was adjusted to 4.5- 5.0, the zinc composite electroplating solution is obtained.

Application Comparative Example 1

The zinc electroplating solution that comparative example 1 gained is applied to the surface of steel alloy to form the method for zinc coating, specifically comprises the steps:

(1) Surface pretreatment of steel and alloy workpieces

The surface of the steel alloy workpiece is polished with 280#, 800# and 1500# sandpaper in sequence, and then rinsed with deionized water to remove the residual matrix wear stripping and sandpaper abrasive grains on the steel surface, then polished with 0.5# diamond abrasive paste, and then used The sodium hydroxide aqueous solution with a mass percentage concentration of 20% is soaked at a temperature of 70-80° C. for 10-15 minutes to degrease and degrease, and then washed with tap water and distilled water in order to obtain a smooth and pollution-free surface;

Then, pickle with 10% hydrochloric acid aqueous solution for surface activation for 30-60s, then rinse the surface acid solution with tap water and distilled water successively, and finally soak the steel workpiece treated above in distilled water for later use.

(2), the preparation of zinc coating on the surface of steel alloy workpiece

Put the iron and steel alloy workpiece and pure zinc material processed in step ( ¹ ) into the zinc electroplating solution, and connect them to the negative and positive poles of the DC stabilized current power supply respectively. Deposit at 30°C and continuous mechanical stirring for 10 minutes, take it out, rinse with tap water and distilled water in turn, and blow dry with a hair dryer or dry in the shade in a dry environment to obtain a zinc-coated steel alloy workpiece.

Above-mentioned gained surface is coated with the coating surface of the iron and steel alloy plated part of zinc coating, scans the figure that gains with scanning electron microscope as shown in 1, as can be seen from Figure 1, the zinc coating that forms on the steel alloy workpiece surface presents smoothness Flat surface structure.

The linear polarization curve measurement is carried out on the iron and steel alloy plated piece with zinc coating on the surface obtained above. Measuring method: the electrolyte is a mass concentration of 3.5wt% NaCl solution, using a three-electrode method, wherein the reference electrode is a calomel electrode, the counter electrode is a platinum electrode, and the working electrode is the steel that is coated with a zinc coating on the surface obtained in Comparative Example 1 For alloy plated parts, the scan rate is 50mV/s. The obtained polarization curve test results are shown in Figure 6. From Figure 6, it can be seen that the corrosion potential of the steel workpiece with the zinc coating formed on the surface of the steel alloy workpiece is -1.292V, and its corrosion current is 1.063A.cm ^-2 .

Example 1

A kind of graphene oxide zinc composite plating solution, calculated by every liter of graphene oxide zinc composite plating solution, its composition and content are as follows:

The compound additive is composed of saccharin, benzacetone and pecaid, and the mass ratio of the said saccharin, benzacetone and pepina is 1:2:15.

Above-mentioned a kind of graphene oxide zinc composite plating solution is prepared by the method of following steps:

Zinc chloride, ammonium chloride, hexamethylenetetramine, trisodium citrate, and composite additives were sequentially added to distilled water to dissolve, and then graphene oxide was added under stirring conditions, and then 10% hydrochloric acid solution was used to The pH value was adjusted to 4.5-5.0, and finally the plating solution was ultrasonicated for 2 hours at an ultrasonic power of 100W to obtain a graphene oxide-zinc composite plating solution with good dispersion.

Application Example 1

The graphene oxide composite electroplating solution of embodiment 1 gained is applied to the surface of iron and steel alloy to form the method for graphene oxide zinc composite coating coating, specifically comprises the steps:

(1) Surface pretreatment of steel and alloy workpieces

The surface of the steel alloy workpiece is polished with 280#, 800# and 1500# sandpaper in sequence, and then rinsed with deionized water to remove the residual matrix wear stripping and sandpaper abrasive grains on the steel surface, then polished with 0.5# diamond abrasive paste, and then used The sodium hydroxide aqueous solution with a mass percentage concentration of 20% is soaked at a temperature of 70-80° C. for 10-15 minutes to degrease and degrease, and then washed with tap water and distilled water in order to obtain a smooth and pollution-free surface;

Then, pickle with 10% hydrochloric acid aqueous solution for surface activation for 30-60s, then rinse the surface acid solution with tap water and distilled water successively, and finally soak the steel workpiece treated above in distilled water for later use.

(2), preparation of graphene oxide zinc composite coating on the surface of iron and steel alloy workpiece

Put the iron and steel alloy workpiece and pure zinc material processed in step (1) into the graphene oxide zinc composite electroplating solution, and connect them to the negative pole and positive pole of the DC stabilized current power supply respectively, at a current density of 5A/dm ² , The temperature of the electroplating solution is 30°C and the condition of continuous mechanical stirring is deposited for 10 minutes, taken out, rinsed with tap water and distilled water in turn, and dried with a hair dryer or dried in the shade in a dry environment, and the steel coated with graphene oxide zinc composite coating on the surface is obtained alloy workpiece.

Above-mentioned gained surface is coated with the coating surface of the iron and steel alloy plated part of graphene oxide zinc composite coating, scans the figure that gains with scanning electron microscope as shown in 2, as can be seen from Figure 2, is different from comparative example 1 The morphology characteristics of the pure zinc coating formed on the surface of the obtained iron and steel alloy workpiece, and the surface morphology of the graphene oxide zinc composite coating formed on the surface of the iron and steel alloy workpiece present a rice grain cluster structure.

Carry out linear polarization curve measurement to the iron and steel alloy plated piece that the above-mentioned obtained surface is plated with graphene oxide zinc coating. Measuring method: the electrolyte is a mass concentration of 3.5wt% NaCl solution, using a three-electrode method, wherein the reference electrode is a calomel electrode, the counter electrode is a platinum electrode, and the working electrode is the graphene oxide zinc coating on the surface obtained in Example 1 Steel alloy plated parts, the scan rate is 50mV/s. Gained polarization curve test results are as shown in Figure 6, as can be seen from Figure 6 compared with the iron and steel workpiece of the zinc coating formed on the surface of Comparative Example 1 gained, the surface gained through Example 1 is coated with graphene oxide zinc The corrosion current of steel alloy plated parts with composite coating decreased by an order of magnitude, about 2.088×10 ^-5 A.cm ^-2 ; the corrosion potential increased by 33mv, reaching -1.259V. The reduction of corrosion current and the increase of corrosion potential fully demonstrate that the graphene oxide-zinc composite coating obtained in Example 1 can provide better corrosion resistance for steel alloy workpieces.

Example 2

A kind of graphene oxide zinc composite plating solution, calculated by every liter of graphene oxide zinc composite plating solution, its composition and content are as follows:

The compound additive is composed of saccharin, benzacetone and pecaid, and the mass ratio of the said saccharin, benzacetone and pepina is 1:2:15.

Above-mentioned a kind of graphene oxide zinc composite plating solution is prepared by the method of following steps:

Zinc chloride, ammonium chloride, hexamethylenetetramine, trisodium citrate, and composite additives were sequentially added to distilled water to dissolve, and then graphene oxide was added under stirring conditions, and then 10% hydrochloric acid solution was used to The pH value was adjusted to 4.5-5.0, and finally the plating solution was ultrasonicated for 2 hours at an ultrasonic power of 100W to obtain a graphene oxide-zinc composite plating solution with good dispersion.

Application Example 2

The graphene oxide composite electroplating solution of embodiment 2 gained is applied to the surface of iron and steel alloy to form the method for graphene oxide zinc composite coating coating, specifically comprises the steps:

(1) Surface pretreatment of steel and alloy workpieces

The surface of the steel alloy workpiece is polished with 280#, 800# and 1500# sandpaper in sequence, and then rinsed with deionized water to remove the residual matrix wear stripping and sandpaper abrasive grains on the steel surface, then polished with 0.5# diamond abrasive paste, and then used The sodium hydroxide aqueous solution with a mass percentage concentration of 20% is soaked at a temperature of 70-80° C. for 10-15 minutes to degrease and degrease, and then washed with tap water and distilled water in order to obtain a smooth and pollution-free surface;

Then, pickle with 10% hydrochloric acid aqueous solution for surface activation for 30-60s, then rinse the surface acid solution with tap water and distilled water successively, and finally soak the steel workpiece treated above in distilled water for later use.

(2), preparation of graphene oxide zinc composite coating on the surface of iron and steel alloy workpiece

Put the iron and steel alloy workpiece and pure zinc material processed in step (1) into the graphene oxide zinc composite electroplating solution, and connect them to the negative pole and positive pole of the DC stabilized current power supply respectively, at a current density of 5A/dm ² , The temperature of the electroplating solution is 30°C and the condition of continuous mechanical stirring is deposited for 10 minutes, taken out, rinsed with tap water and distilled water in turn, and dried with a hair dryer or dried in the shade in a dry environment, and the steel coated with graphene oxide zinc composite coating on the surface is obtained alloy workpiece.

Above-mentioned gained surface is coated with the coating surface of the iron and steel alloy plated part of graphene oxide zinc composite coating, scans the figure that gains with scanning electron microscope as shown in 2, as can be seen from Figure 2, is different from comparative example 1 The morphology characteristics of the pure zinc coating formed on the surface of the obtained iron and steel alloy workpiece, and the surface morphology of the graphene oxide zinc composite coating formed on the surface of the iron and steel alloy workpiece present a rice grain cluster structure.

Carry out linear polarization curve measurement to the iron and steel alloy plated piece that the above-mentioned obtained surface is plated with graphene oxide zinc coating. Measuring method: the electrolyte is a mass concentration of 3.5wt% NaCl solution, using a three-electrode method, wherein the reference electrode is a calomel electrode, the counter electrode is a platinum electrode, and the working electrode is coated with graphene oxide zinc coating on the surface obtained in Example 4 Steel alloy plated parts, the scan rate is 50mV/s. Gained polarization curve test result is as shown in Figure 6, as can be seen from Figure 6 compared with the iron and steel workpiece of the zinc coating formed on the surface of Comparative Example 1 gained, the surface gained through Example 2 is coated with graphene oxide zinc The corrosion current of steel alloy plated parts with composite coating decreased by nearly three orders of magnitude, about 2.980×10 ^-7 A.cm ^-2 ; the corrosion potential increased by 45mV, reaching -1.249V. The reduction of corrosion current and the increase of corrosion potential fully demonstrate that the graphene oxide zinc composite coating obtained in Example 2 can provide better anticorrosion capability for steel alloy workpieces.

Example 3

A kind of graphene oxide zinc composite plating solution, calculated by every liter of graphene oxide zinc composite plating solution, its composition and content are as follows:

The compound additive is composed of saccharin, benzacetone and pecaid, and the mass ratio of the said saccharin, benzacetone and pepina is 1:2:15.

Above-mentioned a kind of graphene oxide zinc composite plating solution is prepared by the method of following steps:

Zinc chloride, ammonium chloride, hexamethylenetetramine, trisodium citrate, and composite additives were sequentially added to distilled water to dissolve, and then graphene oxide was added under stirring conditions, and then 10% hydrochloric acid solution was used to The pH value was adjusted to 4.5-5.0, and finally the plating solution was ultrasonicated for 2 hours at an ultrasonic power of 100W to obtain a graphene oxide-zinc composite plating solution with good dispersion.

Application Example 3

The graphene oxide composite electroplating solution of embodiment 3 gained is applied to the surface of iron and steel alloy to form the method for graphene oxide zinc composite coating coating, specifically comprises the steps:

(1) Surface pretreatment of steel and alloy workpieces

The surface of the steel alloy workpiece is polished with 280#, 800# and 1500# sandpaper in sequence, and then rinsed with deionized water to remove the residual matrix wear stripping and sandpaper abrasive grains on the steel surface, then polished with 0.5# diamond abrasive paste, and then used The sodium hydroxide aqueous solution with a mass percentage concentration of 20% is soaked at a temperature of 70-80° C. for 10-15 minutes to degrease and degrease, and then washed with tap water and distilled water in order to obtain a smooth and pollution-free surface;

Then, pickle with 10% hydrochloric acid aqueous solution for surface activation for 30-60s, then rinse the surface acid solution with tap water and distilled water successively, and finally soak the steel workpiece treated above in distilled water for later use.

(2), preparation of graphene oxide zinc composite coating on the surface of iron and steel alloy workpiece

Put the iron and steel alloy workpiece and pure zinc material processed in step (1) into the graphene oxide zinc composite electroplating solution, and connect them to the negative pole and positive pole of the DC stabilized current power supply respectively, at a current density of 5A/dm ² , The temperature of the electroplating solution is 30°C and the condition of continuous mechanical stirring is deposited for 10 minutes, taken out, rinsed with tap water and distilled water in turn, and dried with a hair dryer or dried in the shade in a dry environment, and the steel coated with graphene oxide zinc composite coating on the surface is obtained alloy workpiece.

Above-mentioned gained surface is coated with the coating surface of the iron and steel alloy plated part of graphene oxide zinc composite coating, scans the figure that gains with scanning electron microscope as shown in 2, as can be seen from Figure 2, is different from comparative example 1 The morphology characteristics of the pure zinc coating formed on the surface of the obtained iron and steel alloy workpiece, and the surface morphology of the graphene oxide zinc composite coating formed on the surface of the iron and steel alloy workpiece present a rice grain cluster structure.

Carry out linear polarization curve measurement to the iron and steel alloy plated piece that the above-mentioned obtained surface is plated with graphene oxide zinc coating. Measuring method: the electrolyte is a mass concentration of 3.5wt% NaCl solution, using a three-electrode method, wherein the reference electrode is a calomel electrode, the counter electrode is a platinum electrode, and the working electrode is the graphene oxide zinc coating on the surface obtained in Example 3 Steel alloy plated parts, the scan rate is 50mV/s. Gained polarization curve test results are as shown in Figure 6, as can be seen from Figure 6 compared with the iron and steel workpiece of the zinc coating formed on the surface of Comparative Example 1 gained, the surface gained through Example 3 is coated with graphene oxide zinc The corrosion current of steel alloy plated parts with composite coating decreased by three orders of magnitude, about 6.188×10 ^-7 A.cm ^-2 ; the corrosion potential increased by 110mv, reaching -1.180V. The reduction of corrosion current and the increase of corrosion potential fully demonstrate that the graphene oxide zinc composite coating obtained in Example 3 can provide better anticorrosion capability for steel alloy workpieces.

Example 4

A kind of graphene oxide zinc composite plating solution, calculated by every liter of graphene oxide zinc composite plating solution, its composition and content are as follows:

The compound additive is composed of saccharin, benzacetone and pecaid, and the mass ratio of the said saccharin, benzacetone and pepina is 1:2:15.

Above-mentioned a kind of graphene oxide zinc composite plating solution is prepared by the method of following steps:

Zinc chloride, ammonium chloride, hexamethylenetetramine, trisodium citrate, and composite additives were sequentially added to distilled water to dissolve, and then graphene oxide was added under stirring conditions, and then 10% hydrochloric acid solution was used to The pH value was adjusted to 4.5-5.0, and finally the plating solution was ultrasonicated for 2 hours at an ultrasonic power of 100W to obtain a graphene oxide-zinc composite plating solution with good dispersion.

Application Example 4

The graphene oxide composite electroplating solution of embodiment 4 gained is applied to the surface of iron and steel alloy to form the method for graphene oxide zinc composite coating coating, specifically comprises the steps:

(1) Surface pretreatment of steel and alloy workpieces

The surface of the steel alloy workpiece is polished with 280#, 800# and 1500# sandpaper in sequence, and then rinsed with deionized water to remove the residual matrix wear stripping and sandpaper abrasive grains on the steel surface, then polished with 0.5# diamond abrasive paste, and then used The sodium hydroxide aqueous solution with a mass percentage concentration of 20% is soaked at a temperature of 70-80° C. for 10-15 minutes to degrease and degrease, and then washed with tap water and distilled water in order to obtain a smooth and pollution-free surface;

Then, pickle with 10% hydrochloric acid aqueous solution for surface activation for 30-60s, then rinse the surface acid solution with tap water and distilled water successively, and finally soak the steel workpiece treated above in distilled water for later use.

(2), preparation of graphene oxide zinc composite coating on the surface of iron and steel alloy workpiece

Put the iron and steel alloy workpiece and pure zinc material processed in step (1) into the graphene oxide zinc composite electroplating solution, and connect them to the negative pole and positive pole of the DC stabilized current power supply respectively, at a current density of 5A/dm ² , The temperature of the electroplating solution is 30°C and the condition of continuous mechanical stirring is deposited for 10 minutes, taken out, rinsed with tap water and distilled water in turn, and dried with a hair dryer or dried in the shade in a dry environment, and the steel coated with graphene oxide zinc composite coating on the surface is obtained alloy workpiece.

Above-mentioned gained surface is coated with the coating surface of the iron and steel alloy plated part of graphene oxide zinc composite coating, scans the figure that gains with scanning electron microscope as shown in 2, as can be seen from Figure 2, is different from comparative example 1 The morphology characteristics of the pure zinc coating formed on the surface of the obtained iron and steel alloy workpiece, and the surface morphology of the graphene oxide zinc composite coating formed on the surface of the iron and steel alloy workpiece present a rice grain cluster structure.

Carry out linear polarization curve measurement to the iron and steel alloy plated piece that the above-mentioned obtained surface is plated with graphene oxide zinc coating. Measuring method: the electrolyte is a mass concentration of 3.5wt% NaCl solution, using a three-electrode method, wherein the reference electrode is a calomel electrode, the counter electrode is a platinum electrode, and the working electrode is coated with a graphene oxide zinc coating on the surface obtained in Example 4 Steel alloy plated parts, the scan rate is 50mV/s. Gained polarization curve test result is as shown in Figure 6, as can be seen from Figure 6 compared with the iron and steel workpiece of the zinc coating formed on the surface of Comparative Example 1 gained, the surface gained through Example 4 is coated with graphene oxide zinc The corrosion current of steel alloy plated parts with composite coating decreased by nearly two orders of magnitude, about 5.984×10 ^-6 A.cm ^-2 ; the corrosion potential increased by 160mV, reaching -1.129V. The reduction of corrosion current and the increase of corrosion potential fully demonstrate that the graphene oxide zinc composite coating obtained in Example 4 can provide better anticorrosion capability for steel alloy workpieces.

In summary, applying a graphene oxide-zinc composite electroplating solution of the present invention to the surface of steel alloys to form a graphene oxide-zinc composite coating with a rice-like cluster structure can provide more excellent corrosion resistance for steel alloy coatings .

The embodiments described above describe the technical solution of the present invention in detail. It should be understood that the above is only a specific embodiment of the present invention, and is not intended to limit the present invention. Any modification made according to the technical solution of the present invention , Supplement or equivalent replacement and other transformations shall all belong to the protection scope of the present invention.

Claims (4)

1. a kind of graphene oxide zinc composite plating solution, it is characterised in that：Calculated by every liter of graphene oxide zinc composite plating solution, Its composition and content are as follows：

Graphene oxide 0.05-0.3g；

Zinc chloride 35-40 g；

Ammonium chloride 160-165g；

Hexamethylenetetramine 10-16g；

Trisodium citrate 10-15g；

Compound additive 0.8g；

Balance of distilled water；

The compound additive is made up of saccharin, Bian fork acetone and peregal, the matter of described saccharin, Bian fork acetone and peregal Amount is than being 1：2：15.

2. the preparation method of a kind of graphene oxide zinc composite plating solution described in claim 1, it is characterised in that：According to every liter The quality of contained material weighs graphene oxide, zinc chloride, ammonium chloride, six respectively in graphene oxide zinc composite plating solution Methine tetramine, trisodium citrate, compound additive and distilled water, by zinc chloride, ammonium chloride, hexamethylenetetramine, citric acid Trisodium and compound additive dissolve in sequentially adding distilled water, and add graphene oxide under agitation, then use hydrochloric acid Solution adjusts pH value to 4.5-5.0, and finally by plating solution ultrasound 1 ~ 3 hour, that is, the graphene oxide zinc for obtaining favorable dispersibility is answered Close electroplate liquid.

3. a kind of graphene oxide zinc electroplate liquid described in claim 1 is used for surface of steel workpiece and forms zinc-Graphene oxidation stone Black alkene zinc composite coating.

4. the graphene oxide electroplate liquid described in claim 3 forms graphene oxide zinc composite coating in surface of steel workpiece Method, it is characterised in that comprise the following steps：

1）The step of one surface to steel and alloy workpiece pre-processes；

By the surface of steel and alloy workpiece successively use 280#, 800# and 1500# sand papering, afterwards with deionized water rinsing with Removal steel surface residual matrix adhesion in wear thing and sand paper abrasive particle, are polished using 0.5# diamond pastes afterwards, then 10-15min is soaked under the conditions of being 70-80 DEG C in temperature with the sodium hydroxide solution that mass percent concentration is 20%, degreasing is removed Oil, then flushing is cleaned with running water successively and distilled water is cleaned to the free of contamination surface of surfacing；

Surface active is finally carried out with the aqueous hydrochloric acid solution pickling 30-60s that mass percent concentration is 10%, then successively with originally Water and distilled water rinse surface acid solution well, then by by standby in the iron and steel parts of above-mentioned treatment immersion distilled water；

2）One on the surface of steel and alloy workpiece the step of prepare graphene oxide zinc composite coating；

Will be by step 1）Steel and alloy workpiece and pure zinc material after treatment are put into graphene oxide zinc composite plating solution, and point It is not connected with the negative pole and positive pole of DC current regulator power supply, is 5A/dm in current density², temperature of electroplating solution be 30 DEG C and even Deposited under continuous mechanical agitation, be rinsed with running water and distilled water successively after taking-up, and dried up with hair-dryer or Dried in the shade under dry environment, that is, obtaining plated surface has the steel and alloy workpiece of the compound coated coating of graphene oxide zinc.