EP3415659B1 - Composition alcaline de traitement de conversion pour du magnésium et de l'alliage de magnésium et procédé pour la mise en uvre d'un traitement de surface sur du magnésium et du matériau en alliage de magnésium à l'aide de cette dernière - Google Patents

Composition alcaline de traitement de conversion pour du magnésium et de l'alliage de magnésium et procédé pour la mise en uvre d'un traitement de surface sur du magnésium et du matériau en alliage de magnésium à l'aide de cette dernière Download PDF

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EP3415659B1
EP3415659B1 EP17750406.5A EP17750406A EP3415659B1 EP 3415659 B1 EP3415659 B1 EP 3415659B1 EP 17750406 A EP17750406 A EP 17750406A EP 3415659 B1 EP3415659 B1 EP 3415659B1
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Prior art keywords
magnesium
magnesium alloy
vanadium
alloy material
weight
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German (de)
English (en)
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EP3415659A4 (fr
EP3415659A1 (fr
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Eun-Kyeong Kim
Chang-Hyun Park
Young-Sam Park
Dong-Yun Kim
Myung-hee CHOI
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Noroo Coil Coatings Co Ltd
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Noroo Coil Coatings Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/22—Acidic compositions for etching magnesium or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals

Definitions

  • Example embodiments relate to an alkali conversion treatment composition for magnesium and magnesium alloy and a surface treating method using the same. More particularly, example embodiments relate to an alkali conversion treatment composition for magnesium and magnesium alloy, which is applied to provide high corrosion resistance to surfaces of magnesium or magnesium alloy, and a surface treating method using the same.
  • Magnesium is the eighth most abundant metal in the world and lightest metal among practically usable metals. Magnesium has excellent non-strength, machinability and dimensional stability. Magnesium alloy has an advantage of being applicable to electronic devices and transportation equipment aiming at lightweight because of excellent electromagnetic wave shielding property, heat radiation property and vibration absorption property. In recent years, magnesium and magnesium alloy are being applied to automobile structural materials such as handles, cylinder heads, ventilation fans and seat frames, or electronic devices such as computers, cameras, MP3s and mobile phones, and other application fields are expected to increase rapidly.
  • metal material members aluminum alloy, steel, magnesium alloy, etc.
  • the purpose of the surface treatment is to remove contaminants such as cutting oil and processing oil remaining on the surface of the workpiece to form a dense chemical film to provide corrosion resistance and coating adhesion.
  • the magnesium alloy is painted after surface treatment like steel or aluminum alloy.
  • the magnesium alloy is the most active metal among the practically usable metal and is easily corroded. Furthermore, since the surface of the magnesium alloy is chemically irregular, the magnesium alloy is an extremely difficult material to form a dense and uniform chemical film.
  • a chemical conversion treatment liquid containing hexavalent chromium having excellent corrosion resistance has been used to secure corrosion resistance and coating adhesion ( Japanese Patent Registration No. 10-0869402 ).
  • use of hexavalent chromium is currently regulated because it is fatal to humans and causes environmental pollution problems. Accordingly, in recent years, a method of forming a dense chemical conversion coating by using a non-chromium conversion treatment composition containing no chromium to provide corrosion resistance and coating adhesion is being applied.
  • Known non-chromium conversion treatment may include "Surface treatment method of a metal ( Japanese Patent Laid-open Publication No. 9-228062 )" using film-forming composition including at least one organometallic compound selected from the group consisting of metal alkoxide, metal acetylacetonate and metal carboxylate, and at least one organic compound selected from the group consisting of an acid, an alkali and a salt thereof, or at least one organic compound containing a hydroxyl group, a carboxyl group or an amino group, and "Phosphate treatment ( Japanese Patent Publication No. 7-126858 )" based on a magnesium phosphate treatment with a metal other than chromium, such as zirconium, titanium, zinc, etc.
  • the chemical conversion treatment composition is impractical due to a long treatment time, and is difficult to provide sufficient corrosion resistance, rust inhibition property and film adhesion property.
  • these chemical conversion treatment compositions tend to be affected by the non-uniformity of the material, so that the performance may not be stable.
  • the present applicant has obtained a patent registration ( 10-1559285 ) for a chemical conversion treatment composition for magnesium or magnesium alloy.
  • the present patent has an advantage of forming a high performance chemical conversion coating, however, since the chemical conversion treatment composition has an acidic characteristic, magnesium is rapidly eluted from the chemical conversion treatment composition when the process of forming a chemical conversion coating is repeated. An eluting of magnesium may cause the deterioration of the chemical conversion treatment composition, which may make it difficult to continuously form a chemical conversion coating having excellent corrosion resistance and water resistance.
  • KR 2014 0106938 A describes a chrome-free conversion treatment composition forms a conversion film on the surfaces of a magnesium material and a magnesium alloy material and may comprises: 2-10 wt% of a phosphate compound; 0.5-3 wt% of a manganese ion compound; 0.1-1 wt% of a zirconium-based compound; 1-4 wt% of inorganic metal sol; 0.05-1 wt% of a vanadium-based compound; and the remainder aqueous solvent.
  • JP 5 647326 B1 describes a treatment method for treating a surface of a zinc-aluminum-magnesium alloy plated steel sheet excellent in corrosion resistance is provided in which the surface is treated using a metal surface treatment agent that contains a zirconyl group-containing zirconium compound (A), a vanadium compound (B), a titanium-containing fluoro complex compound (C), a phosphate group and/or phosphonic acid group-containing organic phosphorus compound (Da), an inorganic phosphorus compound (Db), a specific aqueous acrylic resin (E), and a predetermined amount of an oxazoline group-containing polymer (F) as a hardener, the metal surface treatment agent having a pH of 3 - 6.
  • WO0175190 discloses a conversion coating composition having a corrosion resistance on a surface magnesium or magnesium alloy with a pH between 1 and 10.
  • Example embodiments provide an alkali conversion treatment composition for forming a uniform and dense chemical conversion coating on a surface of a magnesium or magnesium alloy material, and having remarkably low aging characteristics compared to conventional acidic chemical conversion solutions.
  • Example embodiments provide a surface treating method using an alkali conversion treatment composition to form a uniform and dense chemical conversion coating after removing contaminants and an oxide layer existing on a surface of a magnesium or magnesium alloy.
  • an alkali conversion composition for forming a chemical conversion coating having a corrosion resistance on a surface magnesium and magnesium alloy, as defined in claim 1.
  • composition described above may form a uniform and dense chemical conversion coating on a surface of magnesium or magnesium alloy material, and may provide corrosion resistance, topcoat painting adhesion and water resistance, and may not cause defects on a surface of the topcoat painting.
  • a conventional chemical conversion treatment composition has an acidic property.
  • magnesium ions are continuously eluted from the magnesium material to accelerate aging of the chemical conversion treatment composition.
  • magnesium ions may not be eluted from a magnesium material during chemical conversion treatment, and reactivity with the magnesium material may be well-controlled.
  • the alkali conversion treatment composition may be capable of forming a chemically treated coating film having excellent characteristics on a surface of the magnesium material even at a room temperature.
  • An alkali conversion treatment composition of the present invention having characteristics described above may include a phosphoric acid compound, an inorganic metal sol, a vanadium compound, a basic compound, an acrylic resin and a water-soluble solvent.
  • the alkali conversion treatment composition for magnesium and magnesium alloy includes 2 to 10% by weight of the phosphoric acid compound, 1 to 5% by weight of the inorganic metal sol, 0.03 to 0.3% by weight of the vanadium compound, 0.5 to 5% by weight of the basic compound, 0.01 to 0.1% by weight of the acrylic resin and a remainder of water-soluble solvent.
  • the phosphoric acid compound included in the alkali conversion treatment composition may be applied to provide corrosion resistance to a chemical conversion coating and to improve film adhesion.
  • the phosphoric acid compound may include, e.g., ammonium monophosphate, sodium diphosphate, potassium diphosphate and orthophosphoric acid, etc. These may be used each alone or in combination thereof.
  • the chemical conversion coating may not be sufficiently formed to secure corrosion resistance and coating adhesion.
  • the content thereof exceeds 10% by weight, the chemical conversion coating may be excessively formed to improve the corrosion resistance, but it may be difficult to secure the coating adhesion.
  • the phosphoric acid compound is used in 2 to 10% by weight, more preferably in 3 to 9% by weight.
  • the inorganic metal sol included in the alkali conversion treatment composition may be applied to secure corrosion resistance and to form a uniform chemical conversion coating.
  • the inorganic metal sol may include, e.g., silica sol, alumina sol, titania sol, and zirconia sol, etc. These may be used each alone or in combination thereof.
  • the silica sol of the inorganic metal sol may include, e.g., Ludox HS-30, Ludox HS-40, Ludox TM, Ludox SM, Ludox AM, Ludox AS, Ludox LS, Ludox CL-X, Ludox SK, Ludox TMA, Ludox PG, Ludox CL, Ludox CL-P, Ludox DF, Ludox FM, Ludox HAS marketed by GRACE & Co, SNOWTEX ST-20L, SNOWTEX ST-40, SNOWTEX ST-50, SNOWTEX ST-C, SNOWTEX ST-N, SNOWTEX ST-O, SNOWTEX ST-OL, SNOWTEX ST-ZL, SNOWTEX ST-PS-M, SNOWTEX ST-PS-S, SNOWTEX ST-PS-SO, SNOWTEX ST-OUP, SNOWTEX ST-UP marketed by NISSAN CHEMICAL & Co, and SS-SOL 30SG, SS-SOL 30E, SS
  • the alumina sol of the inorganic metal sol may include, e.g., ALUMINASOL TM AS-100, ALUMINASOL TM AS-200 marketed by NISSAN CHEMICAL & Co, Ultra-Sol 200A, Ultra-Sol 201A/60, Ultra-Sol 201A/280 marketed by GerardKluyskens Co., Inc., Wesol A, Wesol C12, Wesol D30 marketed by WESBOND & Co., etc. These may be used each alone or in combination thereof.
  • the inorganic metal sol included in the alkali conversion treatment composition When the content of the inorganic metal sol included in the alkali conversion treatment composition is less than 1% by weight, the chemical conversion coating may not be uniformly formed, and the corrosion resistance may be reduced. On the other hand, when the content thereof exceeds 5% by weight, water resistance and stability of the chemical conversion treatment composition may be lowered, respectively.
  • the inorganic metal sol is used in 1 to 5% by weight, more preferably in 1.5 to 4% by weight.
  • the vanadium compound included in the alkali conversion treatment composition may be applied to further improve the corrosion resistance and to provide a self-healing effect to the magnesium alloy material.
  • the vanadium compound may have a vanadium oxidation number of five, four or three.
  • the vanadium compound having a vanadium oxidation number of five may include, e.g., vanadium pentoxide (V 2 O 5 ), metavanadic acid (HVO 3 ), ammonium metavanadate, sodium metavanadate, vanadium trichloride (VOCl 3 ), etc.
  • the inorganic metal sol may be preferably used in 0.03 to 0.3% by weight, more preferably in 0.05 to 0.2% by weight.
  • the basic compound included in the alkali conversion treatment composition may serve to raise pH of the chemical conversion treatment composition to produce more stable alkali conversion treatment composition.
  • the basic compound may include, e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide and lithium hydroxide, etc. These may be used each alone or in combination thereof.
  • the inorganic metal sol may be preferably used in 0.5 to 5% by weight.
  • the acrylic resin included in the alkali conversion treatment composition may improve durability of the chemical conversion coating to be formed, thereby forming a more dense chemical conversion coating and enhancing the water resistance.
  • the acrylic resin may include, e.g., acrylic polyol, acrylic acid copolymer, modified acrylic acid copolymer, polyacrylate, etc. These may be used each alone or in combination thereof.
  • the inorganic metal sol may be preferably used in 0.01 to 0.1% by weight.
  • the alkali conversion treatment composition in accordance with the example embodiments has pH of 8.5 to 10.5.
  • the pH of the alkali conversion treatment composition is less than 8.5, the reactivity of the magnesium alloy material may be increased, and the chemical conversion coating may be actively formed, however, the magnesium ions may be eluted quickly on the surface of the material to accelerate aging of the solution.
  • the pH thereof exceeds 10.5, the reactivity of the magnesium alloy material may be remarkably reduced, and the chemical conversion coating may be hardly formed on the surface of the magnesium material.
  • the alkali conversion treatment composition for magnesium and magnesium alloy may have a low elution property of magnesium ions.
  • the alkali conversion treatment composition may be prevented from being contaminated by the chemical conversion treating process.
  • a dense chemical conversion coating may be formed even if the chemical conversion coating is reused by tens of times or more.
  • the magnesium material may have high corrosion resistance, excellent coating adhesion and water resistance, without causing surface defects of a topcoat painting layer formed thereafter.
  • the surface treating method for magnesium and magnesium alloy may be performed through a surface cleaning process and a chemical conversion treatment process.
  • the surface cleaning process may remove contaminants (processing oil, oil, etc.) and an oxide layer existing on a surface of magnesium alloy before a chemical conversion treatment to promote forming a uniform and dense chemical film.
  • the surface cleaning process may include a degreasing (alkali degreasing) process, a first washing process, an etching process, a second washing process, a desmutting process, and a third washing process.
  • the degreasing process may be a step of primarily removing oil and processing oil components on the surface of the magnesium alloy prior to the etching process.
  • a degreasing solution of the degreasing process may not be particularly limited as long as it can remove organic contaminants, but it is preferable to use an alkaline aqueous solution containing a surfactant.
  • An alkali builder of the degreasing solution may include a hydrate of an alkali metal, a phosphate, a silicate, a carbonate, etc.
  • the surfactant may include any of nonionic, cationic and anionic surfactants.
  • a chelating agent may be added to improve the degreasing efficiency.
  • the temperature and time for bringing the degreasing solution into contact with the magnesium alloy may not be particularly limited, but it is preferably within a range of 30 to 70°C for 2 to 10 minutes depending on degree of contamination of the magnesium surface.
  • a concentration of the degreasing solution may also be appropriately adjusted according to the degree of contamination on the surface of the magnesium alloy, the degreasing solution component, etc.
  • the first washing process may be a washing step using water to remove the cleaning fluid applied in the degreasing process.
  • the first washing process may be performed by a method, e.g., dipping, spraying, submerging, etc., and may be performed using all kinds of water including, e.g., deionized water, distilled water, pure water, etc.
  • a temperature There is no particular limitation on a temperature, however, the first washing process may be performed preferably at a temperature range of 25 to 80°C.
  • hot water water cleaning may be more efficient, and dehydration drying may be improved.
  • an ultrasonic vibration may be applied to enhance the cleaning effect during the washing process.
  • the etching process may be performed to remove the processing oil on the surface of the magnesium alloy or to remove the oxide layer.
  • An etching treatment in the etching process may be performed by bringing an acidic aqueous solution into contact with the magnesium alloy material to be treated.
  • the acidic aqueous solution may not be particularly limited so long as the contaminants on the surface of the magnesium alloy can be dissolved and removed, and may be preferable to use one or more of sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and carbonic acid in combination.
  • An organic acid may be mixed to improve an etching efficiency.
  • concentration of the acidic aqueous solution, temperature, and contact time with the surface of the magnesium alloy may not be specifically limited, and may appropriately adjusted according to degree of contamination of the magnesium alloy, components of the acidic aqueous solution used, etc.
  • the second washing process may be a cleaning step using water to remove the acidic aqueous solution to be applied in the etching process.
  • the second washing process may be performed by a method such as dipping, spraying, submerging, etc., and may be performed using all kinds of water including deionized water, distilled water, pure water, etc. There is no particular limitation on temperature range.
  • the desmutting process may be performed to remove a smut remaining on the surface of the magnesium alloy after the etching process.
  • the desmutting in the desmutting process may be performed by contacting a desmutting solution with the magnesium alloy to be treated.
  • the desmutting solution may not be particularly limited as long as it can remove the smut remaining on the magnesium surface after the etching process, and may be preferable to use a strong alkaline aqueous solution (pH 12 or higher) mixed with one or two kinds of tartaric acid, ascorbic acid, gluconic acid, citric acid and oxalic acid.
  • the conditions such as concentration of the desmutting solution, temperature, and contact time with the surface of the magnesium alloy may not be specifically limited, and may be appropriately adjusted according to amount of smut generated after the etching process, component of the desmutting solution, etc.
  • the third washing process may be a cleaning step using water to remove the remaining desmutting solution to be applied in the desmutting process.
  • a third washing may be performed by a method such as dipping, spraying, submerging, etc., and may be performed using all kinds of water including deionized water, distilled water, pure water, etc. There is no particular limitation on temperature range.
  • the etching process and the desmutting process may not be performed in the surface cleaning process.
  • the chemical conversion treatment process according to the present invention is the process for forming the chemical conversion coating on the surface of the magnesium and the magnesium alloy material having a cleaned surface using the chemical conversion treatment composition.
  • the alkali conversion treatment composition of magnesium and magnesium alloy may include 2 to 10% by weight of the phosphoric acid compound, 1 to 5% by weight of the inorganic metal sol, 0.03 to 0.3% by weight of the vanadium compound, 0.5 to 5% by weight of the basic compound, 0.01 to 0.1% by weight of the acrylic resin and a remainder of water-soluble solvent.
  • a detailed description of the alkali conversion treatment composition is disclosed in the detailed description of the present invention and is omitted in order to avoid redundancy.
  • the chemical conversion coating may be preferably formed to have a thickness of 0.1 to 2.5 ⁇ m.
  • the chemical conversion coating having a thickness of 0.1 ⁇ m or less may have a good coating adhesion, however, a corrosion resistance and a water resistance may be significantly deteriorated.
  • the chemical conversion coating having a thickness of 2.5 ⁇ m or more may have a good corrosion resistance, however, the coating adhesion and the water resistance may be deteriorated.
  • the thickness of the chemical conversion coating may be adjusted by adjusting temperature of the chemical conversion solution and time of chemical conversion treatment.
  • the magnesium and magnesium alloy materials formed by performing the surface cleaning process described above may be used for replacing automobile parts or other steel after topcoat painting.
  • the topcoat film formed by an electro-deposition coating may be deteriorated.
  • a drying process may be preferably performed before the topcoat painting.
  • the drying process may not be particularly limited, and it is preferable to perform oven drying with a hot air heater or an infrared heater, and a drying temperature is preferably within a range of 80 to 160 ° C for 20 to 60 minutes.
  • drying conditions after the electro-deposition coating may be changed depending on types and characteristics of the electro-deposition paint.
  • type of paint used in coating may not be specifically limited, and any of water-based or solvent-based coatings may be used.
  • a method of coating the paint may not be specifically limited, and any conventionally known coating method, e.g., spraying, dipping, powder coating, etc., may be applied.
  • Each of the magnesium alloy materials (AZ31B plate; ASTM standard product, pneumatic plate, 70mm X 140mm X 0.8mm AZ31B (hot press)) was prepared.
  • a surface of the prepared alloy material was subjected to the surface cleaning process under the conditions shown in Table 3 below.
  • Test specimens were prepared by the processes of forming chemical conversion coatings, washing and electro-deposition coating using the respective chemical conversion treatment compositions prepared in each of Examples and Comparative Examples, respectively.
  • Conditions of electro-deposition coating are as follows [Table 3] Surface cleaning process a degreasing process Gardoclean 4292 A solution, B solution [Samyang Chemical Industry Co., Ltd], A solution 30g/L, B solution 3g/L, 5O°C, 3 minutes ultrasonic treatment a first washing process Using room temperature deionized water an etching process Using mixture of 85% phosphoric acid and 1.96g/L hydrochloric acid, pH 1 to 2, 50°C, immersion treatment a second washing process Using deionized water of a room temperature a desmutting process Using mixture of 50g/L sodium hydroxide and 4.5g/L oxalic acid, 50°C, 3 minutes immersion treatment a third washing process Using room temperature deionized water
  • the coating adhesion test (ASTM D3359, 1 mm X 1 mm, 100 pieces) was performed by the Cross Cut Test (CCT) method after the water resistance test (40°C, 240 hours immersion treatment).
  • CCT Cross Cut Test
  • An evaluation standard is shown in Table 3 below.
  • Example 11 Coating adhesion Corrosion resistance Water resistance Comparative Example 11 5B ⁇ 5B Example 1 5B ⁇ 5B Comparative Example 1 3B X 3B Comparative Example 2 1B ⁇ 1B Comparative Example 3 3B ⁇ 3B Comparative Examole 4 3B ⁇ 2B Comparative Example 5 4B ⁇ 3B Comparative Example 6 4B ⁇ 3B Comparative Example 7 2B ⁇ 2B Comparative Example 8 0B ⁇ 0B Comparative Example 9 3B ⁇ 2B Comparative Example 10 3B ⁇ 2B
  • Example 6 As shown in Table 6 above, when the inorganic metal sol was added (Example 1) as suggested in the present invention, all of the physical properties showed excellent results. On the other hand, when the inorganic metal sol was added too little (Comparative Example 3), all of the physical properties showed deteriorated results. When the inorganic metal sol was added too much (Comparative Example 4), some of the physical properties showed deteriorated results. From the above results, it may be noted that in order to obtain a uniform film, the inorganic metal sol should be used within the scope of the present invention since the inorganic metal sol may affect the denseness and uniformity of the coating when forming the chemical conversion coating.
  • Magnesium alloy material (AZ31B) was treated with the chemical conversion treatment compositions of Example 1 and Comparative Example 11 to measure the pH variance of the solution. The measurement results are shown in FIG. 1 .
  • a graph of FIG. 1 shows the pH change when the magnesium alloy material was continuously treated using each of the chemical conversion treatment compositions (Example 1 and Comparative Example 11).
  • An X-axis of the graph of FIG. 1 is expressed by converting the amount of the solution (m2/L) per treatment area by continuously treating the magnesium alloy.
  • Comparative Example 11 shows that the pH increases sharply as the treatment capacity of the magnesium alloy increases, however, Example 1 shows that the pH gradually decreases.
  • Comparative Example 11 shows that the pH increases sharply as the treatment capacity of the magnesium alloy increases, however, Example 1 shows that the pH gradually decreases.
  • Comparative Example 11 shows that the pH increases sharply as the treatment capacity of the magnesium alloy increases, however, Example 1 shows that the pH gradually decreases.
  • Comparative Example 11 shows that the pH gradually decreases.
  • Comparative Example 11 as described in the existing patent, when the pH may exceed 5 or more, the physical properties may be deteriorated and the composition may not be used as a chemical conversion treatment composition.
  • Example 1 A material of AZ31B (25cm x 9cm) was evaluated for a degree of contamination before and after the chemical conversion treatment of the two chemical conversion treatment compositions (Example 1 and Comparative Example 11).
  • Each of the magnesium alloy materials were treated in the chemical conversion treatment composition having the compositions of Example 1 and Comparative Example 11, and then the degree of contamination of the solution was measured by inductively coupled plasma mass spectrometry (ICP) analysis.
  • ICP inductively coupled plasma mass spectrometry
  • each of the initial physical properties of the chemical conversion treatment composition of Comparative Example 11 and Example 1 were all excellent.
  • the physical properties were equivalent to those of initial properties up to the treatment capacity of 0.15m 2 /L, and after that, the physical properties were lowered.
  • the physical properties were equivalent to those of initial properties up to the treatment capacity of 2.0m 2 /L.
  • the magnesium ions continuously dissolve during the continuous chemical conversion treatment, the pH of the solution was increased, and the solution was rapidly aged.
  • the magnesium ions did not dissolve during the conversion treatment, and the aging of the solution were hardly progressed.
  • FIG. 2 is an enlarged photograph of a microstructure of a chemical conversion coating formed using the chemical conversion treatment composition of Example 1.
  • the microstructure of the chemical conversion coating on the surface of the magnesium alloy material (AZ31B) in accordance with Example 1 of the present invention may have a unique structure and a structure similar to that of the Dendrite structure.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (10)

  1. Composition de conversion alcaline permettant de former un revêtement de conversion chimique présentant une résistance à la corrosion sur une surface de magnésium et d'alliage de magnésium, la composition de conversion alcaline de magnésium et d'alliage de magnésium comprenant de 2 à 10 % en poids d'un composé d'acide phosphorique, de 1 à 5 % en poids d'un sol métallique inorganique, de 0,03 à 0,3 % en poids d'un composé de vanadium, et caractérisée en ce que la composition de conversion alcaline comprend en outre de 0,5 à 5 % en poids d'un composé de base, de 0,01 à 0,1 % en poids d'une résine acrylique et d'un reste de solvant soluble dans l'eau, dans laquelle le pH a une valeur comprise entre 8,5 et 10,5.
  2. Composition de conversion alcaline selon la revendication 1, dans laquelle le composé d'acide phosphorique est un composé qui génère des ions d'acide phosphorique, et comprend au moins un composé choisi dans le groupe constitué par le monophosphate d'ammonium, le diphosphate de sodium, le diphosphate de potassium et l'acide orthophosphorique.
  3. Composition de conversion alcaline selon la revendication 1, dans laquelle le composé de base comprend au moins un composé choisi dans le groupe constitué par l'hydroxyde de sodium, l'hydroxyde de potassium, l'hydroxyde de calcium, l'hydroxyde de baryum, l'hydroxyde d'ammonium et l'hydroxyde de lithium.
  4. Composition de conversion alcaline selon la revendication 1, dans laquelle le sol métallique inorganique comprend au moins un sol choisi dans le groupe constitué par le sol de silice, le sol d'alumine, le sol de dioxyde de titane et le sol de zircone.
  5. Composition de conversion alcaline selon la revendication 1, dans laquelle le composé de vanadium comprend au moins un composé choisi dans le groupe constitué par le pentoxyde de vanadium (V2O5), l'acide métavanadique (HVO3), le métavanadate d'ammonium, le métavanadate de sodium, le trichlorure de vanadium (VOCI3), le trioxyde de vanadium (V2O3), le dioxyde de vanadium (VO2), l'oxysulfate de vanadium (VOSO4), l'oxyacétylacétate de vanadium VO(OC(=CH2)CH2COCH3))2, l'acétylacétate de vanadium V(OC(=CH2)CH2COCH3))3, le trichlorure de vanadium (VCI3) et le phospho-vanado-molybdate.
  6. Composition de conversion alcaline selon la revendication 1, dans laquelle la résine acrylique comprend au moins un élément choisi dans le groupe constitué par un polyol acrylique, un copolymère d'acide acrylique, un copolymère d'acide acrylique modifié et un polyacrylate.
  7. Procédé de traitement d'une surface de matériau de magnésium et d'alliage de magnésium, le procédé comprenant :
    la réalisation d'un processus de nettoyage de surface sur le matériau de magnésium et d'alliage de magnésium ; et
    la formation d'un revêtement de conversion chimique sur une surface du matériau de magnésium et d'alliage de magnésium à l'aide d'une composition de conversion alcaline ; et
    dans lequel le revêtement de conversion chimique est formé à l'aide d'une composition de conversion alcaline pour le magnésium et l'alliage de magnésium, qui comprend de 2 à 10 % en poids d'un composé d'acide phosphorique, de 1 à 5 % en poids d'un sol métallique inorganique, de 0,03 à 0,3 % en poids d'un composé de vanadium, et caractérisé en ce que la composition de conversion alcaline comprend en outre de 0,5 à 5 % en poids d'un composé de base, de 0,01 à 0,1 % en poids d'une résine acrylique et d'un reste de solvant soluble dans l'eau, dans lequel le pH a une valeur comprise entre 8,5 et 10,5.
  8. Procédé selon la revendication 7, le processus de nettoyage de surface comprenant :
    la réalisation d'un processus de dégraissage sur le matériau de magnésium et d'alliage de magnésium ;
    la réalisation d'un premier processus de lavage sur le matériau de magnésium et d'alliage de magnésium dégraissé ;
    la réalisation d'un processus d'attaque chimique utilisant une solution aqueuse acide sur la surface du matériau de magnésium et d'alliage de magnésium ;
    la réalisation d'un deuxième processus de lavage sur le matériau de magnésium et d'alliage de magnésium attaqué chimiquement ;
    la réalisation d'un processus de décapage pour éliminer un dépôt sur le matériau de magnésium et d'alliage de magnésium ; et
    la réalisation d'un troisième processus de lavage sur le matériau de magnésium et d'alliage de magnésium décapé.
  9. Procédé selon la revendication 7, le processus de nettoyage de surface comprenant :
    la réalisation d'un processus de dégraissage sur le matériau de magnésium et d'alliage de magnésium ; et
    la réalisation d'un premier processus de lavage sur le matériau de magnésium et d'alliage de magnésium dégraissé.
  10. Procédé selon la revendication 7, dans lequel le revêtement de conversion chimique est formé pour avoir une épaisseur comprise entre 0,1 et 2,5 µm.
EP17750406.5A 2016-02-11 2017-02-02 Composition alcaline de traitement de conversion pour du magnésium et de l'alliage de magnésium et procédé pour la mise en uvre d'un traitement de surface sur du magnésium et du matériau en alliage de magnésium à l'aide de cette dernière Active EP3415659B1 (fr)

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KR1020160015698A KR101751453B1 (ko) 2016-02-11 2016-02-11 마그네슘 및 마그네슘 합금용 알칼리 화성처리 조성물 및 이를 이용한 마그네슘 및 마그네슘 합금 소재의 표면 처리방법
PCT/KR2017/001129 WO2017138714A1 (fr) 2016-02-11 2017-02-02 Composition alcaline de traitement de conversion pour du magnésium et de l'alliage de magnésium et procédé pour la mise en œuvre d'un traitement de surface sur du magnésium et du matériau en alliage de magnésium à l'aide de cette dernière

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JP3325366B2 (ja) 1993-10-29 2002-09-17 日本パーカライジング株式会社 マグネシウム含有金属用化成処理液組成物、化成処理方法、および化成処理された材料
JP3598163B2 (ja) 1996-02-20 2004-12-08 ソニー株式会社 金属の表面処理方法
DE19754108A1 (de) * 1997-12-05 1999-06-10 Henkel Kgaa Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren
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TW567242B (en) 2002-03-05 2003-12-21 Nihon Parkerizing Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment
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AU2009249174B2 (en) * 2008-05-19 2015-05-28 Henkel Ag & Co. Kgaa Midly alkaline thin inorganic corrosion protective coating for metal substrates
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KR101559285B1 (ko) * 2014-02-28 2015-10-08 주식회사 노루코일코팅 마그네슘 및 마그네슘 합금용 화성처리 조성물 및 이를 이용한 마그네슘 및 마그네슘 합금 소재의 표면처리방법
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EP3415659A1 (fr) 2018-12-19
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WO2017138714A1 (fr) 2017-08-17

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