KR20140092448A - Metal surface treatment method and steel plate thereof using graphene compound - Google Patents
Metal surface treatment method and steel plate thereof using graphene compound Download PDFInfo
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- KR20140092448A KR20140092448A KR1020120155939A KR20120155939A KR20140092448A KR 20140092448 A KR20140092448 A KR 20140092448A KR 1020120155939 A KR1020120155939 A KR 1020120155939A KR 20120155939 A KR20120155939 A KR 20120155939A KR 20140092448 A KR20140092448 A KR 20140092448A
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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
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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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
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
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Abstract
Description
The present invention relates to a metal surface treatment method and a surface treated steel sheet, and more particularly to a high corrosion resistance metal surface treatment technique using a graphene compound.
Magnesium is an environmentally friendly material with excellent electromagnetic shielding properties, dustproofness, dimensional stability and machinability. In particular, the development of magnesium alloys has attracted attention due to the trend of lightweight automobile, aviation and ship materials. However, the conventional magnesium has a problem of corrosion resistance because of corrosion due to moisture and salt due to its poor corrosion resistance.
Chromate, Conversion Treatment, Anodizing, and Plasma Electrolytic Oxidation (PEO) are the magnesium surface treatment techniques to improve corrosion resistance. However, There is an existing problem. The purpose of this research is to develop surface treatment products with excellent corrosion resistance by combining the properties of Graphene, which has proven outstanding performance in recent years, with the steel industry.
Methods for producing graphene can be broadly classified into physical exfoliation, chemical exfoliation, and direct growth. Physical separation using Scotch tape has the disadvantage that mass production can not be achieved while the graphene having the best physical properties can be produced in the simplest manner. As a direct growth method, a chemical vapor deposition (CVD) method in which a transition metal layer such as nickel or copper is used as a catalyst layer is known. Chemical vapor deposition has the advantage of being able to form graphene with high physical properties, but current technology has difficulties in mass production and has disadvantages that it is produced at a high temperature of 1000 DEG C or more. Further, since the catalyst layer is limited to nickel (Ni) or copper (Cu), it is limited to be utilized for the steel surface treatment at present.
In addition, the chemical exfoliation method exists, and the chemical exfoliation method can be separated by the oxidation reduction method and the non-oxidation method called the Humer's method. Oxidation or redox method is a method of oxidizing graphite and then pulverizing it by using ultrasonic wave or the like to make graphene oxide dispersed in an aqueous solution, and then forming graphene oxide (Reduced Graphene Oxide (RGO) To generate graphene. The graphene using the non-oxidation method is a method of directly dispersing by using a surfactant or the like without passing through the oxidation process.
The present invention provides a technique for forming a highly corrosion-resistant surface by surface-treating graphene on a magnesium alloy and a metal alloy. A high gas barrier property that does not pass through hydrogen is very advantageous in ensuring high corrosion resistance of the surface.
A method of treating a metal surface according to an embodiment of the present invention includes the steps of preparing a composition for metal surface treatment, applying a graphene contained in the composition for metal surface treatment to a steel sheet, And drying.
The metal surface treatment composition may be formed by mixing a Reduced Graphene Oxide (RGO) solution with an organic solvent containing a metal compound.
The metal surface treatment composition may be formed by mixing a graphene powder / platelet with an organic solvent containing a metal compound.
Wherein the step of preparing the metal surface treatment composition comprises: washing the graphene powder / platelet; mixing the graphene powder / platelet with an organic solvent containing a metal compound; And dispersing the mixed graphene powder / platelet.
The organic solvent may include ethanol or isopropyl alcohol.
The step of dispersing the graphene powder / platelet mixed in the organic solvent may be performed using an ultrasonic grinder at 0 to 50 캜 for 30 to 120 minutes.
The steel sheet may be formed of magnesium (Mg) or a magnesium alloy.
The step of applying the composition for metal surface treatment to a steel sheet comprises the steps of applying a voltage having a polarity opposite to the charge of the graphen-metal compound contained in the metal surface treatment composition to the steel sheet, May be applied.
A voltage of 5 V to 100 V, preferably 5 V to 20 V may be applied to the steel sheet.
The step of drying the steel sheet may be performed by hot wind and / or baking.
The surface-treated steel sheet according to the present invention may include a steel sheet and a graphene layer coated on the steel sheet.
The steel sheet may be formed of magnesium (Mg) or a magnesium alloy.
According to the embodiment of the present invention, it is possible to effectively coat a steel sheet by electrophoresis using graphene, which is very excellent in corrosion resistance, and thereby, a surface treated steel sheet having excellent corrosion resistance can be obtained.
1 is a flowchart showing a method of treating a metal surface according to an embodiment of the present invention.
2 is a flowchart showing a method for preparing a composition for metal surface treatment using a graphene powder / platelet according to an embodiment of the present invention.
FIG. 3 is a diagram showing the result of visual observation after coating the surface of a magnesium alloy (AZ31) according to the present invention with a composition for metal surface treatment using graphene oxide (RGO).
FIG. 4 is a graph showing the degree of corrosion after a predetermined time after performing a salt spray (SST) experiment using magnesium hydroxide (AZ31) with sodium hydroxide (NaOH) according to the present invention.
FIG. 5 is a graph showing the results of a salt water spray test using sodium hydroxide (NaOH) after coating with a graphene platelet as a composition for metal surface treatment on the surface of a magnesium alloy (AZ31) according to the present invention, Fig.
6 is a view showing a surface-treated steel sheet produced by a metal surface treatment method according to the present invention.
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.
In addition, in the various embodiments, elements having the same configuration are denoted by the same reference numerals, and only other configurations will be described in the other embodiments.
The drawings are schematic and illustrate that they are not drawn to scale. The relative dimensions and ratios of the parts in the figures are shown exaggerated or reduced in size for clarity and convenience in the figures, and any dimensions are merely illustrative and not restrictive. Also, to the same structure, element, or component appearing in more than one of the figures, the same reference numerals are used to denote similar features. When referring to a portion as being "on" or "on" another portion, it may be directly on the other portion or may be accompanied by another portion therebetween.
The embodiments of the present invention specifically illustrate one embodiment of the present invention. As a result, various variations of the illustration are expected. Thus, the embodiment is not limited to any particular form of the depicted area, but includes modifications of the form, for example, by manufacture.
Hereinafter, a metal surface treatment method according to an embodiment of the present invention will be described with reference to Figs. 1 and 2. Fig.
1 is a flowchart showing a method of treating a metal surface according to an embodiment of the present invention. Referring to FIG. 1, a method of treating a metal surface according to the present invention includes the steps of preparing a composition for metal surface treatment (S101), applying Graphene contained in a composition for metal surface treatment to a steel sheet (S102 , And drying the steel sheet (S103).
The graphene used in the present invention may be a Reduced Graphene Oxide (RGO) solution or a graphene powder / platelet or a mixed solution thereof.
The oxidized graphene (RGO) can be formed by an oxidation-reduction method in which graphite is oxidized and then crushed using ultrasound or the like. After preparing graphene oxide (GO) dispersed in an aqueous solution, a reducing agent And then subjected to thermal expansion and reduction treatment to obtain RGO type graphene again. In addition, the graphene powder / platelet can be formed by a non-oxidation method in which graphite is immediately dispersed by using a surfactant or the like without being subjected to an oxidation process, and when a non-oxidizing method is used, a thinner graphene powder / A platelet can be obtained.
2 is a flowchart showing a method for preparing a composition for metal surface treatment using a graphene powder / platelet according to an embodiment of the present invention. When the graphene powder / platelet is used as the graphene used in the present invention, the graphene powder / platelet production step (S201), the graphene powder / platelet cleaning step (S202) and the graphene powder / Mixing the graphene powder / platelet with an organic solvent containing a metal compound (S203), and dispersing the graphene powder / platel mixed with the organic solvent (S204).
In the graphene powder / platelet cleaning step (S202), the graphene is washed for the purpose of removing impurities of the graphene produced from graphite and increasing the purity. At this time, any method of cleaning the graphene can be applied to the cleaning method, and there is no particular limitation, but a vacuum filter can be preferably used. In washing, acetone, ethanol or methanol may be used as a washing solution. In washing with acetone, graphene of higher purity can be obtained.
Thereafter, the step (S203) of mixing the graphene powder / platelet with the organic solvent containing the metal compound is performed by adding a compound capable of acting as a charger to the organic solvent, Fin surface treating composition. Any solution may be used as a solution for uniformly mixing the metal mixture serving as a charge with the graphene, but an organic solvent, more preferably ethanol or isopropyl alcohol may be used . In the preparation of the graphene compound, a graphene-metal compound can be prepared by mixing the powder with a tool such as a blade for 10 minutes to 30 minutes.
Thereafter, dispersing the graphene powder / platelet mixed in the organic solvent (S204) is a graphene dispersion step in which the graphene clustering from graphite is finely peeled off and uniformly dispersed in the solution. When graphene is not uniformly dispersed in a solution, it is difficult to uniformly deposit the graphene on a steel sheet.
At the time of dispersion, an organic solvent, more preferably ethanol or isopropyl alcohol, may be dispersed by sonication for 30 minutes to 120 minutes. The ultrasonic treatment may be performed by any method capable of dispersing graphene, and preferably an ultrasonic grinder may be used.
The metal surface treatment method according to the present invention comprises the steps of preparing a metal surface treatment composition as shown in FIG. 2 (S101), and applying a graphene contained in the metal surface treatment composition to the steel sheet S102), and drying the steel sheet (S103).
As the steel sheet, any steel sheet with electricity can be used, and a non-steel material containing a non-ferrous metal can also be used. The steel sheet may be formed of magnesium (Mg) or a magnesium alloy (AZ31 or AZ61). In order to ensure excellent corrosion resistance, a uniform coating is an important factor for the steel sheet, and any method that can uniformly coat the entire area can be used, and preferably, it can be coated in a large area using electrophoretic deposition (EPD) .
In the step (S102) of applying the composition for metal surface treatment to the steel sheet, a voltage having a polarity opposite to the charge of the graphene-metal compound contained in the composition for metal surface treatment is applied to the steel sheet, It can be applied. That is, the graphene-metal compound can have a (+) or (-) polarity charge depending on the characteristics of the metal compound. According to the charge of the graphene-metal compound 30, a voltage of polarity opposite to that of the graphene-metal compound is applied to the steel sheet to be coated. By the electric field formed at this time, the graphene-metal compound is accelerated and can be coated on the surface of the steel sheet. A voltage of 5 V to 100 V, preferably a voltage of 50 V or less, more preferably a voltage of about 5 V to about 20 V is applied to the steel sheet, and the graphene is coated with a magnesium alloy and a metal alloy .
The conditions of the graphene coating according to the embodiment of the present invention are shown in Table 1 below.
First, when using graphene powder / platelet, graphene was washed with ethanol using a vacuum filter to obtain a graphene solution having a purity of 90% or more. Each of the chargers shown in Tables 1 and 2 below was mixed with ethanol to prepare a metal compound, and the washed graphene solution was blended with the blade for 30 minutes to prepare a metal compound. Each graphene-metal Lt; / RTI > Then, each of the graphene-metal compounds was ultrasonically treated with an ultrasonic mill for 1 hour to finally prepare a composition for metal surface treatment. Thereafter, the prepared metal surface treatment composition was coated on a steel sheet by electrophoresis, and the steel sheet was dried.
In carrying out the electrophoresis, a magnesium alloy (AZ31, AZ61) was used as a cathode, SUS304 was used as an anode, and 5 mm, 10 mm or 15 mm was used as distance equipment The applied voltage was 5-20 V and the run time was for 1-50 s.
FIG. 3 is a diagram showing the result of visual observation after coating the surface of a magnesium alloy (AZ31) according to the present invention with a composition for metal surface treatment using graphene oxide (RGO). For the results shown in Fig. 3, 0.25 wt% of RGO graphene and 1 wt% of magnesium nitrate (Mg (NO 3 ) 2 ? H 2 O) were applied to the surface of the magnesium alloy (AZ31) Distance of 5 mm, coating time of 10 seconds, and visual observation.
FIG. 4 is a graph showing the degree of corrosion after a predetermined time after performing a salt spray (SST) experiment using magnesium hydroxide (AZ31) with sodium hydroxide (NaOH) according to the present invention. For the results shown in FIG. 4, 3% sodium hydroxide (NaOH) and salt spray (SST) test were conducted at 35 ° C., and the degrees of corrosion after 0Hr, 24Hr and 48Hr elapsed.
FIG. 5 is a graph showing the results of a salt water spray test using sodium hydroxide (NaOH) after coating with a graphene platelet as a composition for metal surface treatment on the surface of a magnesium alloy (AZ31) according to the present invention, Fig. 5, 5 wt% of graphene platelet, 10 wt% of magnesium nitrate (Mg (NO 3 ) 2 .H 2 O) was applied to the surface of the magnesium alloy (AZ61) 5 mm in distance, 5 seconds in coating time, and 5% in sodium hydroxide and salt water spray test at 35 ° C, and the degree of corrosion after 0Hr, 24Hr and 48Hr elapsed.
6 is a view showing a surface-treated steel sheet produced by a metal surface treatment method according to the present invention. 6, the surface treated steel sheet according to the present invention includes a
As in the present invention, a surface treated steel sheet having a graphene layer exhibits excellent corrosion resistance, which can be obtained by a graphene layer deposited on a steel sheet. In other words, the inherent characteristics (gas barrier properties) of graphene which can not pass hydrogen gas can be imparted to the steel sheet, so that the corrosion resistance of the steel sheet can be improved.
As described above, by the method of treating a metal surface and the surface-treated steel sheet according to the present invention, it is possible to effectively coat the steel sheet by electrophoresis using graphene, which is very excellent in corrosion resistance, have.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the following claims. Those who are engaged in the technology field will understand easily.
701: steel plate 702: graphene layer
Claims (12)
Applying a graphene contained in the composition for metal surface treatment to a steel sheet; And
And drying the steel sheet.
The above-mentioned composition for metal surface treatment,
(RGO) solution in an organic solvent containing a metal compound.
The above-mentioned composition for metal surface treatment,
A method of treating a metal surface formed by mixing a graphene powder / platelet with an organic solvent containing a metal compound.
Wherein the step of preparing the composition for metal surface treatment comprises:
Washing the graphene powder / platelet;
Mixing the graphene powder / platelet into an organic solvent containing a metal compound; And
And dispersing the graphene powder / platelet mixed in the organic solvent.
Wherein the organic solvent comprises ethanol or isopropyl alcohol.
The step of dispersing the graphene powder / platelet mixed in the organic solvent includes:
And ultrasonication is performed using an ultrasonic mill at 0 캜 to 50 캜 for 30 minutes to 120 minutes.
Wherein the steel sheet is formed of magnesium (Mg) or a magnesium alloy.
The step of applying the composition for metal surface treatment to a steel sheet comprises:
Wherein the graphene is applied to the surface of the steel sheet by applying a voltage of a polarity opposite to the charge of the graphene-metal compound contained in the metal surface treatment composition to the steel sheet.
Wherein a voltage of 5 to 100 V, preferably 5 to 20 V is applied to the steel sheet.
The step of drying the steel sheet comprises:
Wherein the metal surface is treated with hot air and / or baking.
And a graphene layer coated on the steel sheet.
Wherein the steel sheet is formed of magnesium (Mg) or a magnesium alloy.
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| KR1020120155939A KR20140092448A (en) | 2012-12-28 | 2012-12-28 | Metal surface treatment method and steel plate thereof using graphene compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101691594B1 (en) * | 2016-03-30 | 2016-12-30 | 짱신 | Thermally conductive film having metal-graphene carbon and method of manufacturing the same |
| KR101963447B1 (en) * | 2018-06-20 | 2019-03-28 | 이의열 | Manufacturing and coating methods of reduced graphene oxide |
| CN115477877A (en) * | 2022-10-12 | 2022-12-16 | 雅迪科技集团有限公司 | Composition for electrophoretic pretreatment coating and preparation method and application thereof |
-
2012
- 2012-12-28 KR KR1020120155939A patent/KR20140092448A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101691594B1 (en) * | 2016-03-30 | 2016-12-30 | 짱신 | Thermally conductive film having metal-graphene carbon and method of manufacturing the same |
| KR101963447B1 (en) * | 2018-06-20 | 2019-03-28 | 이의열 | Manufacturing and coating methods of reduced graphene oxide |
| CN115477877A (en) * | 2022-10-12 | 2022-12-16 | 雅迪科技集团有限公司 | Composition for electrophoretic pretreatment coating and preparation method and application thereof |
| CN115477877B (en) * | 2022-10-12 | 2024-01-09 | 雅迪科技集团有限公司 | Composition for electrophoresis pretreatment coating and preparation method and application thereof |
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