EP2392693B1 - Auf mg basierendes strukturiertes element - Google Patents

Auf mg basierendes strukturiertes element Download PDF

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Publication number
EP2392693B1
EP2392693B1 EP10735918.4A EP10735918A EP2392693B1 EP 2392693 B1 EP2392693 B1 EP 2392693B1 EP 10735918 A EP10735918 A EP 10735918A EP 2392693 B1 EP2392693 B1 EP 2392693B1
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Prior art keywords
base
coating film
magnesium
apatite
samples
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English (en)
French (fr)
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EP2392693A4 (de
EP2392693A1 (de
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Sachiko Hiromoto
Akiko Yamamoto
Norio Maruyama
Toshiji Mukai
Hidetoshi Somekawa
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National Institute for Materials Science
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National Institute for Materials Science
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • 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
    • C23C22/05—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
    • C23C22/68—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 solutions with pH between 6 and 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • the present invention relates to an Mg-based structural material comprising magnesium or a magnesium alloy, which is formed in a desired structured shape of parts of transportation equipment such as automobiles, IT instruments such as mobile telephones, housings of home electric appliances such as televisions, etc. More precisely, the invention relates to improvement in corrosion resistance of an Mg-based structural material.
  • a magnesium alloy has relatively high specific strength and its abundant resources are available, and therefore its application to lightweight parts for improving the fuel efficiency of automobiles and aircrafts is now under investigation.
  • the strength and the electromagnetic wave-shielding effect thereof are higher than those of plastics, it is utilized as housings for IT instruments such as typically mobile telephones and personal computers and as those for home electric appliances such as televisions. These parts are required to have high corrosion resistance in various environments.
  • magnesium is a chemically active substance and is therefore disadvantageous in that its corrosion resistance is low especially in acidic/neutral environments containing chloride ions.
  • Transportation equipment and home electric appliances are exposed to rain and seawater droplets and human sweat containing chloride ions. Therefore, it is said necessary to form a highly corrosion-resistant coating film to cover them, and for some parts, to make painting in addition to the highly corrosion-resistant coating film.
  • the mainstream of conventional coating films for improving the corrosion resistance of magnesium materials is one that contains an element having a high environmental load such as chromium, manganese, fluorine or the like. Accordingly, a corrosion-resistant film is desired that is composed of elements of which the environmental load in the production process is low and of which the safety to the environment during use is high.
  • a chemical treatment solution and an electrolytic solution for anodic oxidation containing phosphoric acid, manganic acid and/or calcium oxide have been developed (Patent References 1 to 5), and the formed films have high corrosion resistance and good adhesiveness to paints.
  • manganic acid is a substance that requires waste treatment, and therefore a corrosion-resistant film of which the environmental load is further low and its production method are desired.
  • CN-A-101249280 describes a method for preparing an apatite coating on a pure magnesium surface.
  • an object of the present invention is to provide an Mg-based structural material having a corrosion-resistant film composed of environment-safe elements. Another object is to provide its production method in which the environmental load for its production is low.
  • the coating film that serves as the corrosion-resistant film comprises, as the main component thereof, apatite having high thermodynamic stability among calcium phosphate of which the environmental load is low.
  • the invention is as follows:
  • the invention provides a production method for an Mg-based structural material comprising a magnesium or magnesium alloy base and formed in a desired structural shape, wherein the surface of the base is coated with a film comprising apatite crystals as the main component thereof, and wherein the coating film and said base are integrated via a magnesium hydroxide layer, wherein the base formed in a desired shape is dipped in an aqueous solution containing a phosphate ion and a non-chloride calcium ion derived from Ca-EDTA dissolved in a supersaturation state, thereby precipitating a coating film comprising apatite crystals as the main component thereof, on the surface of the base.
  • the surface of the coating film is painted with a resin paint.
  • the thickness of the coating film is from 1 to 5 ⁇ m.
  • Calcium phosphate such as typically apatite has a low solubility in neutral environments and is not corroded by a chloride ion.
  • apatite is in the form of a crystal structure having high thermodynamic stability, and therefore its solubility in an aqueous solution is lower than that of other calcium phosphate.
  • Calcium phosphate is a main component of the bone of a living body, and is therefore a highly environment-safe material composed of elements of which the environmental load is low.
  • magnesium is an element that inhibits crystallization of apatite, and the related technical knowledge is that direct precipitation of apatite from an aqueous solution on the surface of a magnesium material would be impossible.
  • the present invention has broken down the technical knowledge.
  • the Mg-based structural material of the invention has a coating film comprising apatite as the main component thereof, and is therefore effective for preventing the corrosion of the magnesium or magnesium alloy base thereof.
  • the Mg-based structural material is composed of environment-safe elements alone, and is therefore effective for reducing the environmental load in recycling the magnesium material.
  • the solution for coating film formation is an aqueous solution containing environment-safe elements alone, and is therefore effective for securing the environmental protection around factories and for reducing the waste treatment cost.
  • a phosphate-containing coating film has high adhesiveness to paint and is therefore expected to have excellent paint adhesiveness to the coating film comprising an apatite crystal as the main component thereof; and in addition, since the apatite crystal is a transparent or white crystal, another advantage is expected that the coating film does not detract from coloration of the overcoating paint.
  • the coating film that comprises an apatite crystal as the main component thereof and covers the surface of the base is a film formed through precipitation of the phosphate ion and the calcium ion contained in the treatment solution on the surface of the base as an apatite crystal thereon, and therefore can be formed irrespective of the composition of the base.
  • the composition of the base is not specifically defined, and may be pure magnesium or a magnesium alloy.
  • the coating film is formed through dipping treatment in an aqueous solution, and even though the surface configuration of the base is a complicated one, it does not have any influence on the coating film.
  • the coating film comprises, as described in the above, an apatite crystal as the main component thereof and has, depending on the dipping treatment condition, a layer comprising crystalline Mg(OH) 2 as the main component thereof, in the boundary to the base.
  • the solubility in a salt solution of the apatite crystal having a thermodynamically stable crystal structure is extremely low.
  • the solubility of the crystalline Mg(OH) 2 is extremely lower than that of the amorphous Mg(OH) 2 formed on the surface of a magnesium material in air. Accordingly, the Mg-based structural material of the invention can exhibit high corrosion resistance as compared with a magnesium material having a coating film formed through oxidation in air.
  • the surface treatment solution for producing the Mg-based structural material of the invention is an aqueous solution containing a calcium chelate compound (Ca-EDTA) and a phosphate ion and having pH of from 5 to 13.
  • Ca-EDTA calcium chelate compound
  • phosphate ion a phosphate ion
  • the calcium compound capable of dissolving a high-concentration calcium ion in a broad pH range is a calcium compound of the chelate EDTA. So far as it is a neutral to acidic treatment solution, also usable is an inorganic salt such as calcium hydroxide, calcium nitrate, calcium carbonate, calcium acetate, calcium dihydrogenphosphate, calcium thiosulfate, etc. Adding a chelating agent along with an inorganic salt increases the calcium ion concentration. In such a manner, when a chelate compound is employed as the calcium source, a relatively high-concentration calcium ion can be dissolved not only in an acidic aqueous solution but also in an alkaline aqueous solution.
  • An alkaline aqueous solution containing a chelating agent such as EDTA is used for smut removal from the surface of an acid-washed magnesium material. Therefore, when the concentration of the chelating agent is too high, then the surface of the base, magnesium may tend to be roughened. For example, when the EDTA concentration is higher than 2.5 ⁇ 10 -1 M for pure magnesium, then the surface of the magnesium base may be greatly roughened and a coating film comprising calcium phosphate as the main component thereof could not homogeneously cover the surface.
  • the presence of the chelating agent promotes degreasing of the base surface and removal of the release agent, oxide film and smut from the surface along with film formation, and is therefore expected to reduce the impurities in the coating film to be formed.
  • the inorganic phosphate salt constituting the treatment solution includes various alkali salts, ammonium salts, alkaline earth orthodihydrogen salts and the like, such as potassium dihydrogenphosphate, disodium hydrogenphosphate, ammonium dihydrogenphosphate, diammonium hydrogenphosphate, calcium monohydrogenphosphate, etc.
  • the apatite crystal precipitation speed may tend to be extremely low. In this case, the dipping time will have to be prolonged.
  • an alkaline solution of sodium hydroxide, potassium hydroxide, ammonia or the like is used for the purpose of controlling the pH of the treatment solution prepared from a calcium compound and an inorganic phosphate salt.
  • the pH range to be controlled is preferably within a range of pH 5 to pH 13.
  • the magnesium base dipped in the treatment solution may start to dissolve, and owing to the pH increase through the dissolution reaction, the pH around the surface of the magnesium base could be pH 7 or more at which the apatite crystal phase could be stable. Even in the pH range of pH 11 or more in which magnesium hydroxide is insoluble, the apatite crystal phase is still stable, and therefore apatite can be precipitated on the surface of the magnesium base.
  • the thickness of the coating film that comprises an apatite crystal as the main component thereof is preferably from 1 ⁇ 10 -2 ⁇ m to 5 ⁇ 10 1 ⁇ m. More preferably, the lowermost limit is at least 1 ⁇ 10 -1 ⁇ m, even more preferably at least 5 ⁇ 10 -1 ⁇ m, still more preferably at least 1 ⁇ m. The uppermost limit is more preferably at most 2.5 ⁇ 10 1 ⁇ m, even more preferably at most 1 ⁇ 10 1 ⁇ m, still more preferably at most 5 ⁇ m. When the coating film is too thin, then it could not uniformly coat the surface of the base and the corrosion resistance may be poor; but when too thick, the film may readily peel off from the base surface.
  • the Mg-based structural material obtained by the invention is used in various applications. It may be used for parts of automobiles and two-wheeled vehicles, and housings of mobile telephones, personal computers, video cameras, etc.
  • the Mg-based structural material obtained by the invention exhibits excellent corrosion resistance as it is just treated, but for further improving the corrosion resistance thereof, or for improving the aesthetic appearance of the magnesium material, the Mg-based structural material may be painted, if desired.
  • the paint may be either a water-bases paint or a solvent-bases paint.
  • the painting method may be any known method of dip painting, spray painting, electrodeposition painting, etc.
  • a base of pure magnesium of which the surface had been finished with a 0.1- ⁇ m alumina lapping film was dipped in a solution prepared by adding 1 N NaOH solution to an aqueous solution of 50 mM Ca-EDTA/50 mM KH 2 PO 4 in a ratio of 0, 1/40, 1/20 or 3/40 by volume to the latter so as to have a controlled pH value, and statically kept therein at 95°C for 8 hours to thereby prepare samples A to D.
  • Fig. 1 shows the XRD patterns of the treated samples A to D. All the samples gave peaks of hydroxyapatite (HAp) and Mg(OH) 2 (Brucite form). With the increase in the pH of the treatment solution, the HAp peak intensity increased and the Mg(OH) 2 (Brucite) peak intensity decreased.
  • HAp hydroxyapatite
  • Mg(OH) 2 Brucite
  • Figs. 2 to 5 each show the electron microscopic picture of the surface and the cross section of Samples B and C. It is confirmed that in every sample, the surface is uniformly covered with an apatite crystal.
  • the apatite is a tabular or needle-like crystal having a size of from 1 ⁇ m to 10 ⁇ m or so.
  • the coating film is composed of a layer comprising, as the main component thereof, apatite crystals having a high concentration of Ca, P and O, and a boundary layer comprising, as the main component thereof, Mg(OH) 2 having a high concentration of O and Mg.
  • the Mg(OH) 2 boundary layer is extremely thin so that it could not be definitely observed through SEM, or is absent.
  • the thickness of the formed film is shown in Table 1. With the increase in the pH of the treatment solution, the thickness tended to increase.
  • Example 2 As shown in Table 2, a pure magnesium base that had been surface-finished in the same manner as in Example 1 was dipped in an aqueous solution of 50 mM Ca-EDTA/50 mM KH 2 PO 4 prepared by adding 1 N NaOH thereto in a ratio of 1/40 by volume to the former so as to have a controlled pH value, and statically kept therein at 95°C for 24, 96 or 168 hours to thereby prepare samples E to G.
  • a pure magnesium base that had been surface-finished in the same manner as in Example 1 was dipped in an aqueous solution of 50 mM Ca-EDTA/50 mM KH 2 PO 4 prepared by adding 1 N NaOH thereto in a ratio of 1/20 by volume to the former so as to have a controlled pH value, and statically kept therein at 95°C for 2, 4, 16, 24, 96 or 168 hours to thereby prepare samples H to M.
  • Fig. 6 shows the XRD patterns of the samples H and I treated with a solution having a pH of from 7.1 to 7.4; and
  • Fig. 7 shows the XRD patterns of the surfaces of the samples K to M treated with a solution having a pH of from 7.1 to 7.4.
  • the thickness of the coating film is shown in Table 2.
  • the thickness of the coating film thinner than 1 ⁇ m is a value presumed from the relationship between the treatment time and the film thickness. Even when the treatment time is 2 hours and is short, the apatite crystal uniformly covers the surface of the base, as shown in Fig. 8 , and with the increase in the treatment time, the thickness of the apatite crystal layer tended to increase. When the treatment time is 96 hours or more and is long, the apatite crystal precipitation amount increased, but in many cases, a part or all of the coating film peeled from the surface of the base.
  • the apatite crystal layer can be formed even when the treatment time is short, and that the apatite crystal precipitation amount can be varied by changing the treatment time and the film thickness can be thereby controlled.
  • the coating film is often peeled.
  • Example 3 a pure magnesium base that had been surface-finished in the same manner as in Example 1 was dipped in an aqueous solution of 250 mM Ca-EDTA/250 mM KH 2 PO 4 prepared by adding 1 N NaOH thereto in a ratio of 1/40, 1/20 or 3/40 by volume to the former so as to have a controlled pH value, and statically kept therein at 95°C for 8 hours to thereby prepare samples N to P.
  • the phosphate ion and the calcium ion concentration was 5 times that of the solution used in Example 1 and Example 2.
  • Fig. 9 shows the XRD patterns of the treated samples N to P. All the samples gave HAp peaks of hydroxyapatite. With the increase in the pH of the treatment solution, the HAp peak intensity increased. Samples O and P gave Mg(OH) 2 (Brucite) peaks; however, sample N for which the pH of the treatment solution was relatively low did not give a definite peak. The Mg(OH) 2 peaks of samples O and P were extremely small as compared with those of samples A to D. These indicate that the magnesium hydroxide layer is difficult to be formed in the solution having a high calcium ion and phosphate ion concentration. The thickness of the formed film is shown in Table 3.
  • the HAp peak intensity of the surface treated with the 250 mM solution was higher.
  • the Mg(OH) 2 peak intensity of the surface treated with the 250 mM solution was lower.
  • the treatment of the invention forms a coating film comprising an apatite crystal as the main component thereof on the surface of the base, irrespective of the composition of the base, magnesium alloy.
  • Table 4 Sample Code Q R S T Base Alloy AZ31 AZ61 AZ91 Mg-1.0 Al Ca-EDTA Concentration mM 50 50 KH 2 PO 4 Concentration mM 50 50 Addition Ratio of 1N NaOH (*1) - 1/40 pH of Treatment Solution (*2) pH 5.3-5.5 7.7-7.9 Treatment Time h 8 8 Apatite Formation (*3) ⁇ ⁇ ⁇ ⁇ Film Thickness ⁇ m 15 26 24 4 *1 Added amount in terms of volume relative to the volume of the Ca-EDTA/KH 2 PO 4 solution taken as the denominator.
  • a pure magnesium base of which the surface had been finished with a 0.1- ⁇ m alumina lapping film was dipped in an aqueous solution of which the Ca-EDTA and KH 2 PO 4 concentration had been so designed that the ratio of Ca/P could be the same as that, 1.67 of HAp, and statically kept therein at 95°C for 8 hours to thereby prepare samples U to W.
  • Fig. 11 shows the XRD patterns of samples U to W.
  • the calcium ion concentration was 1 mM
  • the samples gave only trace-level HAp peaks except a HAp(002) plane-derived peak, but with the increase in the calcium ion concentration, the HAp peaks increased.
  • the calcium ion and phosphate ion concentration in the treatment solution is preferably higher.
  • the samples U and V for which the calcium ion and phosphate ion concentration in the treatment solution was low did not give definite Mg(OH) 2 peaks. This indicates that the presence of the magnesium hydroxide layer depends on the calcium ion and phosphate ion concentration in the treatment solution.
  • NaCl in an amount of 1 g/m 2 was deposited to the surface of the samples C, J and K shown in Table 1 and Table 2 and to a just-polished sample, and at room temperature, subjected to a dry-wet cycle test for a total of 96 hours in which the relative humidity was controlled to be from 55% to 95% and again 55% at intervals of 8 hours.
  • the comparative sample, just-polished sample is a 0.1- ⁇ m alumina lapping-finished sample.
  • the NaCl deposition amount of 1 g/m 2 is close to the NaCl deposition amount in a seaside region, and means an extremely severe corrosion environment. Even though corroded in this test, the samples are not always corroded in actual environments.
  • Fig. 12 to Fig. 15 are pictures each showing the surface of the samples C, J and K and the just-polished sample after the 96-hour dry-wet cycle test, from which the surface-treated layer and the corrosion product had been removed.
  • the samples C and K had small filiform corrosion at the edge thereof; however, the sample J did not have any remarkable corrosion.
  • the just-polished sample was covered with filiform corrosion almost on the entire surface thereof. This clarifies that the surface treatment in the invention provides sufficient corrosion resistance against atmospheric corrosion. It addition, it is known that even a thin coating film having a thickness of less than 5 ⁇ m secures sufficient corrosion resistance.
  • Fig. 16 shows the polarization curves of the samples C, J and K and the just-polished sample.
  • SCE anode current density at a potential of - 1.45 V
  • the current density of the just-polished sample rapidly increased, which showed an anode current density of larger than 10 mA/cm 2 ; however, the magnesium material having the coating film of the invention had a pseudo-passive region in a potential width of several tens mV around the corrosion potential, therefore still showing a low current density of lower than 1 mA/cm 2 even after rapid increase in the current density owing to film breakdown.
  • a water-based epoxy paint was applied to the surface of the samples H, I and C shown in Table 1 and Table 2 and to the surface of the just-polished sample, and tested in a cross-cut test (JIS K 5600-5-6). According to the JIS classification, the paint peeling ratio was evaluated. The test results are shown in Table 7.
  • the just-polished sample was graded in GT 3, but the sample I was in GT 2. This clarifies that the coating film in the invention improves the adhesiveness to the paint. It is known that the adhesiveness to the water-based epoxy paint depends on the thickness of the coating film, and the thickness is preferably from 1 to 2 ⁇ m.
  • the Mg-based structural material obtained by the invention is used in various applications. It may be used for parts of transportation equipment such as automobiles and two-wheeled vehicles, and housings of mobile telephones, personal computers, video cameras, etc.
  • the production method for the Mg-based structural material of the invention reduces the environmental load of the production process and is effective for environmental protection.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
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  • Chemical Treatment Of Metals (AREA)

Claims (3)

  1. Herstellungsverfahren für einen Mg-basierten Strukturwerkstoff, der eine Basis aus Magnesium oder einer Magnesiumlegierung umfasst und in einer gewünschten strukturellen Form ausgebildet ist, wobei die Oberfläche der Basis mit einem Film beschichtet ist, der Apatitkristalle als Hauptkomponente davon umfasst, und wobei der Beschichtungsfilm und die Basis über eine Magnesiumhydroxid-Schicht integriert sind, wobei die in einer gewünschten Form ausgebildete Basis in eine wässrige Lösung getaucht wird, die ein Phosphation und ein von Ca-EDTA abgeleitetes Nicht-Chlorid-Calciumion gelöst in einem Übersättigungszustand enthält, wodurch ein Beschichtungsfilm, der Apatitkristalle als Hauptkomponente davon umfasst, auf die Oberfläche der Basis abgeschieden wird.
  2. Herstellungsverfahren nach Anspruch 1, wobei die Oberfläche des Beschichtungsfilms mit einer Harzlackfarbe lackiert ist.
  3. Herstellungsverfahren nach einem der Ansprüche 1 und 2, wobei die Dicke des Beschichtungsfilms 1 bis 5 µm beträgt.
EP10735918.4A 2009-02-02 2010-01-29 Auf mg basierendes strukturiertes element Not-in-force EP2392693B1 (de)

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PCT/JP2010/051284 WO2010087456A1 (ja) 2009-02-02 2010-01-29 Ｍｇ基構造部材

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DE102016002852A1 (de) * 2016-03-10 2017-09-14 Audi Ag Verfahren zur Passivierung einer Oberfläche eines Metallbauteils
JP6783465B2 (ja) * 2017-01-19 2020-11-11 国立研究開発法人物質・材料研究機構 医療用生体吸収性部材とその製造方法
JP6872987B2 (ja) * 2017-06-22 2021-05-19 日本パーカライジング株式会社 皮膜付きマグネシウム含有金属材
DE102017011379A1 (de) * 2017-12-11 2019-06-13 Audi Ag Anti-Korrosionsbeschichtung für metallische Substrate
CN108273133B (zh) * 2018-03-05 2020-05-19 北京科技大学 一种凝胶注模制备生物医用合金ha涂层的方法
CN113463156B (zh) * 2021-07-23 2022-09-20 中国科学院青海盐湖研究所 一种氢氧化镁膜层及其制备方法与系统
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CN102301034B (zh) 2013-09-18
WO2010087456A1 (ja) 2010-08-05
EP2392693A1 (de) 2011-12-07

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