WO2016010541A1 - Revêtement électrocéramique pour alliages de magnésium - Google Patents

Revêtement électrocéramique pour alliages de magnésium Download PDF

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Publication number
WO2016010541A1
WO2016010541A1 PCT/US2014/047026 US2014047026W WO2016010541A1 WO 2016010541 A1 WO2016010541 A1 WO 2016010541A1 US 2014047026 W US2014047026 W US 2014047026W WO 2016010541 A1 WO2016010541 A1 WO 2016010541A1
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WO
WIPO (PCT)
Prior art keywords
inorganic
layer
based coating
magnesium
sub
Prior art date
Application number
PCT/US2014/047026
Other languages
English (en)
Inventor
Shawn E. Dolan
Kirk Kramer
Michael Murphy
Lisa K. Salet
Original Assignee
Dolan Shawn E
Kirk Kramer
Michael Murphy
Salet Lisa K
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dolan Shawn E, Kirk Kramer, Michael Murphy, Salet Lisa K filed Critical Dolan Shawn E
Priority to MX2017000559A priority Critical patent/MX2017000559A/es
Priority to PCT/US2014/047026 priority patent/WO2016010541A1/fr
Priority to KR1020177002941A priority patent/KR20170029545A/ko
Priority to CN201480081973.0A priority patent/CN106715762B/zh
Priority to CA2955317A priority patent/CA2955317A1/fr
Priority to EP14897821.6A priority patent/EP3169831A4/fr
Priority to JP2017502676A priority patent/JP6513180B2/ja
Priority to TW104122814A priority patent/TW201619449A/zh
Publication of WO2016010541A1 publication Critical patent/WO2016010541A1/fr
Priority to US15/405,774 priority patent/US20170121841A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/022—Anodisation on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge

Definitions

  • This invention relates to articles having magnesium-containing metal surfaces with an electroceramic coating chemically bonded to the metal surfaces and to articles having a composite coating comprising first sectors of electroceramic coating and second sectors comprising organic and/or inorganic components different from the electroceramic coating.
  • the invention further relates to processes of making and using the articles.
  • the light weight ( ⁇ 1.74 gm/cm 3 density) and strength of magnesium and magnesium alloys makes products fashioned therefrom highly desirable for use in manufacturing parts, for example, electronic devices, including handheld electronic devices; motor vehicles; aircraft and other products where low density is beneficial.
  • One method used to improve corrosion resistance of metal surfaces is anodization, see for example U.S. Pat. No. 4,978,432, U.S. Pat. No. 4,978,432 and U.S. Pat. No. 5,264,113.
  • a metal (M) surface is electrochemical ly oxidized to form metal oxides (MOx) from the metal surface thereby creating a coating layer.
  • MOx metal oxides
  • anodization of magnesium and magnesium alloys generating MgO affords some protection against corrosion, improvements in corrosion performance are desirable.
  • conventional anodization often fails to form a protective layer on the entire surface of a complex workpiece. Anodized coatings have been found to contain cracks, some down to the metal surface, at sharp corners. Further, adhesion of paint to anodized magnesium surfaces is often insufficient and improvements are needed.
  • PEO Plasma Electrolytic Oxidation
  • MAO Micro Arc Oxidation
  • Spark Anodizing and Microplasma Oxidation referred to herein collectively as "PEO”
  • PEO Plasma Electrolytic Oxidation
  • MAO Micro Arc Oxidation
  • Spark Anodizing and Microplasma Oxidation referred to herein collectively as "PEO”
  • PEO Plasma Electrolytic Oxidation
  • MAO Micro Arc Oxidation
  • Spark Anodizing and Microplasma Oxidation referred to herein collectively as "PEO”
  • PEO Plasma Electrolytic Oxidation
  • MAO Micro Arc Oxidation
  • Spark Anodizing and Microplasma Oxidation referred to herein collectively as "PEO”
  • PEO Plasma Electrolytic Oxidation
  • MAO Micro Arc Oxidation
  • Spark Anodizing and Microplasma Oxidation referred to herein collectively as "PEO”
  • PEO Plasma Electrolytic Oxidation
  • PEO processing of magnesium and its alloys oxidizes the magnesium producing a coating that contains crystalline magnesium oxide (60-80 vol. %) with minor amounts of magnesium silicate and/or magnesium phosphate, depending on the content of the PEO bath.
  • PEO processes have disadvantages including weaker throwing power that can result in thin coatings on inner or less accessible surface areas of the substrate. Due to the voltage and amperage required to generate the "glow” or “sparking" needed for PEO, the process has electricity consumption greater than processes which do not require micro-arc discharges.
  • the resulting oxide layer produced using PEO consists of two sub-layers, the outer layer is a brittle sub-layer with a porosity of more than 15%, which is removed by an additional polishing step. Removal of the outer layer has the disadvantages of additional processing and, often, manual labor, as well as loss of dimensional integrity of the article and challenges in uniformly polishing complex articles or those having non-uniform coating layers due to throw-power limitations of PEO.
  • heterogeneous and alloy rich Mg alloys such as AZ91 , which possess wide microstructural heterogeneity and unequal distribution of Al within different phases.
  • AZ91 ⁇ nominally Mg with 9 wt.% Al— 1 wt.% Zn
  • has three main phases namely primary a ⁇ i.e. matrix), eutectic a (i.e. Al-rich a) and ⁇ phase (Mg17AI12 intermetallic), since the substrate is electrochemically heterogeneous each constituent reacts differently in the an electrolytic coating bath leading to non-uniform coating growth which tends to degrade the corrosion resistance of coatings.
  • the inorganic-based coating may have additional layers deposited thereon, may form a composite coating comprising the inorganic-based coating and a second component distributed throughout at least a portion of the inorganic-based coating and/or the coating on the magnesium containing article may comprise a reaction product the inorganic-based coating and a second component.
  • polymeric composition thereby forming a second layer comprising organic polymer chains and/or inorganic polymer chains;
  • [0013.] !t is an object of the invention to provide a method wherein, prior to generating the first layer, from 0.5 to 50 g/m 2 of metal is removed from the bare metallic magnesium or magnesium alloy surface.
  • It is an object of the invention to provide a method of electrolytically depositing an inorganic- based coating comprising a first sub-layer directly bonded to the bare metallic magnesium or magnesium alloy surface at a first interface, the first sub-layer comprising at least 70 wt.% of a combined mass of fluorine and magnesium, and a positive amount of oxygen present in an amount of less than about 25 wt. %; and a second sub-layer integrally connected to the first sub-layer, the second sub-layer comprising external surfaces at the outer boundary of the inorganic-based coating, and internal surfaces defined by pores in the second sub-layer lying interior to the outer boundary of the inorganic-based coating and in communication therewith, the second sub-layer having a composition wherein:
  • the post-treating step F) is present as a step of contacting a matrix of the first layer of inorganic-based coating with a second component different from the inorganic-based coating; distributing the second component throughout at least a portion of the matrix; and depositing a second layer that is different from the inorganic-based coating and is adhered to at least external surfaces of the inorganic-based coating,
  • step F) i) is present and comprises a step of introducing at least one vanadium containing composition as the second component to the second sub-layer of inorganic-based coating, contacting at least the external surfaces and desirably at least some of the internal surfaces of the second sub-layer, whereby the second component forms a thin film in contact with the external surfaces of the inorganic-based coating and lining at least a portion of the pores in the inorganic-based coating.
  • the infusing step comprises reacting the vanadium containing composition and elements of the inorganic- based coating to thereby form a portion of the second component, which is different from the inorganic-based coating and the vanadium containing composition.
  • step F) ii) is present and comprises contacting the first layer of an inorganic-based coating with a polymeric composition thereby forming a second layer comprising organic polymer chains and/or inorganic polymer chains; and optionally applying a layer of paint after the post- treating step.
  • a magnesium-containing article comprising at least one metallic magnesium or magnesium alloy surface coated according to the methods disclosed herein.
  • a magnesium-containing article comprising at least one metallic magnesium or magnesium alloy surface coated with a first layer of an inorganic-based coating chemically bonded directly to said surface wherein the inorganic-based coating has a bilayer structure.
  • the bilayer structure may comprise: a first sub-layer directly bonded to the bare metallic magnesium or magnesium alloy surface at a first interface, said first sub-layer comprising at least 70 wt.% of a combined mass of fluorine and magnesium, and a positive amount of oxygen present in an average amount of less than about 20 wt.
  • the article may further comprise a second layer that is different from the inorganic-based coating and is adhered to at least external surfaces of the inorganic-based coating.
  • any counterions thus implicitly specified preferably are selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise, such counterions may be freely selected, except for avoiding counterions that act adversely to an object of the invention;
  • molecular weight (MW) is weight average molecular weight;
  • molecular weight (mole) means “gram mole”, and the word itself and all of its grammatical variations may be used for any chemical species defined by all of the types and numbers of atoms present in it, irrespective of whether the species is ionic, neutral, unstable, hypothetical or in fact a stable neutral substance with well-defined molecules; and the terms "solution”, “soluble”, “homogeneous”, and the like are to be understood as including not only true equilibrium solutions or homogeneity but also dis
  • Figure 1 is an electron micrograph of a cross-section of a panel of AZ-31 coated according to Example 1 , prior to post-treating, at 2500x magnification.
  • the line with white arrows indicates a distance of 3.08 micron between the end points.
  • Figure 2 is a graph of elemental composition, in weight percent, of an inorganic-based electrolytically deposited coating according to the invention showing varying chemical composition of a coating of the invention, as a function of distance from the magnesium alloy surface. .
  • Articles according to the invention include magnesium-containing articles having a coating, which may be an electrolytically deposited coating, chemically bonded to one or more metal surfaces of the magnesium-containing article. Such articles are useful as for example, parts for motor vehicles, aircraft, and electronic devices, including handheld electronic devices, and other products where the light weight and strength of magnesium is desired.
  • the articles generally have at least one metal surface, which comprises magnesium metal, and chemically bonded directly to that surface an inorganic-based coating.
  • the inorganic-based coating is post treated to improve corrosion resistance.
  • At least a portion of the article has a metal surface that contains not less than 50% by weight, more preferably not less than 70% by weight, magnesium.
  • magnesium-containing article means an article having at least one surface that may be in whole or in part metallic magnesium or a magnesium alloy.
  • the body of the article may be formed of metallic magnesium or a magnesium alloy or may be formed of other materials, e.g. metals other than magnesium, polymeric materials, refractory materials, such as ceramics, that have a layer of magnesium or magnesium alloy on at least one surface.
  • the other materials may be other metals different from magnesium, non-metallic materials or combinations thereof, such as composites or assemblies.
  • the article may comprise at least one surface of metallic magnesium or a magnesium alloy comprising, in order of increasing preference, at least about 51 , 60, 65, 70, 75, 80, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98 or 99 wt. % magnesium.
  • Chemically bonded to at least one magnesium surface of the magnesium- containing article is a first layer comprising an inorganic-based coating.
  • An inorganic-based coating may include some organic material, but contains a greater mass of inorganic material than of organic molecules.
  • the inorganic material may act as a matrix in which any organic constituent may be distributed.
  • the inorganic-based coating may be applied by an electrolytic deposition process as described herein.
  • the inorganic-based coating contains magnesium, fluorine, oxygen, at least one alloying element from the g substrate and at least one metal from the bath.
  • the inorganic-based coating may comprise carbon. Both the carbon and alloying elements, if present, may be dispersed in an insulating ceramic layer. Even with inclusion of carbon and alloying elements in the inorganic-based coating, a uniform thickness is generated which provides uniform paint and adhesive bonding, as well as corrosion resistance, which is improved as compared to the bare surface of the magnesium containing substrate. This feature of the invention is beneficial in reducing scrap rate where substrates and the inorganic-based coatings deposited thereon achieve good coating quality even in the presence of carbon and alloying elements in the inorganic-based coating.
  • the inorganic-based coating comprises C, O, F, Al, Mg, and alkali metal. Desirably the alkali metal comprises less than 50, 40, 30, 20, 10, 5 or 1% Na.
  • the inorganic-based coating comprises magnesium, which may be present in a total amount ranging from, in order of increasing preference, at least about 10, 12, 14, 16, 18, or 20 atomic % and in order of increasing preference, not more than 45, 40, 35, 33, 30, 28, 26, 24 or 22 atomic %.
  • the inorganic-based coating comprises fluorine, which may be present in a total amount ranging from, in order of increasing preference, at least about 15, 20, 22, 24, 26, 28, 30, 32, 34, 36, or 38 atomic % and in order of increasing preference, not more than 60, 55, 50, 45 or 40 atomic %.
  • the inorganic-based coating comprises oxygen, which may be present in a total amount ranging from, in order of increasing preference, at least about 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, or 20 atomic % and in order of increasing preference, not more than 33, 30, 28, 26, 24 or 22 atomic %.
  • the inorganic-based coating may comprise carbon, which may be present in a total amount ranging from, in order of increasing preference, at least about 3, 4, 5, 6, 7, 8, 9, 10 atomic % and in order of increasing preference, not more than 33, 30, 28, 26, 14 or 12 atomic %.
  • the inorganic-based coating may comprise alloying metals from the magnesium- containing article; alkaline earth metals, different from magnesium; and/or alkali metals, which may be present in a total amount ranging from, in order of increasing preference, at least about 1 , 2, 3, 4, or 5 atomic % and in order of increasing preference, not more than 14, 13, 12, 10, 8 or 6 atomic %.
  • more than 50 wt.% of the total amount of these constituents present in the inorganic-based coating may be localized near the external surface of the inorganic-based coating, meaning the inorganic-based coating surface that is not in direct contact with a metallic surface of the magnesium-containing article.
  • the inorganic-based coating may comprise fluorine and magnesium in atomic ratios of fluorine to magnesium of about 0.25:1 , 0.3:1 , 0.4:1 , 0.5: 1 , 0.75:1 , 1 :1 , 1.25: 1 , 1.5: 1 , 1 .75: 1 , 2:1 , 2.25:1 , 2:5, 2.75:1 , 3:1 , 3.25:1 , 3.5:1 , or 3.75:1 .
  • the ratio of oxygen to fluorine in the inorganic-based coating may exhibit a gradient wherein amount of oxygen relative to amount of fluorine increases as a function of distance from the magnesium-containing article's metal surface. In one embodiment, the ratio may range from about 0.1 :1 up to about 1 :1.
  • the inorganic-based coating may have a bi-layer morphology, as shown in Figure 1 and Figure 2.
  • Figure 1 shows an electron micrograph of a cross-section of a magnesium alloy panel coated according to Example 1 , prior to application of a post- treatment, at 2500x magnification.
  • the inorganic-based coating has a bilayer structure, despite being deposited in a single processing step: a first sub-layer 1 directly bonded to the metal surface 2 and having an interface 5 with the metal surface (first interface); and a second sub-layer 3 in direct contact with the first sub-layer and spaced away from the metal surface by the first sub-layer lying there between.
  • the second sub-layer is directly bonded with the first sub-layer at an interface 6 with the first sub-layer (second interface).
  • the second sub-layer of the inorganic-based coating comprises pores 4, and has internal surfaces 7 and external surfaces 8.
  • the internal surfaces are defined by pores in the second sub-layer and lie interior to the outer boundary 9 of the inorganic-based coating, which comprises the external surfaces of the second sub-layer.
  • the white arrowed line in Figure 1 extending from the metal surface to the outer boundary of the inorganic-based coating, represents a thickness of about 3 microns for the inorganic-based coating.
  • the external surfaces of the second sub-layer lie in a boundary between inorganic-based coating and an external environment or a secondary layer applied to the outer boundary and are not in direct contact with a metallic surface of the magnesium- containing article.
  • the first sub-layer may have few or no pores and has a more dense composition than the second sub-layer. Any pores present in the first sub-layer are desirably not contiguous between the metallic surface of the article and the external surface of the inorganic-based coating layer, and optionally smaller than the pores of the second sub-layer. Some of the pores of the second sub-layer are open pores in communication with the external surface.
  • the second sub-layer may comprise open and closed cell pore structure.
  • Pore size may range from about 0.1 microns to 5 microns and may make up as much as 50 % or more of the volume of the deposited coating.
  • the electrolytically applied inorganic-based coating may have a surface area that is about 75 - 150X that of the uncoated substrate surface.
  • Figure 2 is a graph of an elemental depth profile taken of inorganic-based coatings according to the invention using glow discharge optical emission spectroscopy (GDOES). Amounts of various elements are shown in weight percent at particular distances from the metal surface.
  • Figures 1 and 2 show that the first sub-layer and the second sublayer are different in morphology and elemental content. Composition of the first sub-layer may vary somewhat depending upon the Mg alloy used, and may comprise 50, 60, 70, 80 or 90 wt.% of a combined mass of fluorine and magnesium, and may additionally comprise about 1 to about 20 wt. % oxygen.
  • GDOES glow discharge optical emission spectroscopy
  • the second sub-layer may have a weight percent of fluorine that is less than the weight percent of fluorine found in the first sub-layer; the second sub-layer may have a weight percent of Mg that is less than the weight percent of Mg found in the first sub-layer; and the second sub-layer may have a weight percent of oxygen that is greater than the weight percent of oxygen found in the first sub-layer.
  • the inorganic-based coating has an amorphous structure.
  • Physical morphology of the inorganic-based coating may comprise non-crystalline compounds of magnesium and one or more of elements.
  • the inorganic-based coating shows amorphous structure by X-ray crystallography (XRD).
  • the inorganic-based coating may be a hard (Vickers 400-900 by nanoindentation), amorphous coating comprising non-stoichiometric magnesium compounds.
  • Nonstoichiometric glasses of Mg and F, with or without oxygen may be present.
  • the inorganic- based coating is an inorganic composition comprising Mg, O & F, including stoichiometric and non-stoichiometric compounds of said elements with each other.
  • the inorganic composition comprises crystalline and non-crystalline compounds comprising magnesium, with more than 50 atomic percent of the composition comprising non-crystalline compounds.
  • Coating thickness of the inorganic-based electrolytically deposited coating may range from 0.1 microns to about 50 microns, desirably 1-20 microns depending upon the desired use of the coated article. Coating thickness of the inorganic-based
  • electrolytically deposited coating desirably is at least, in increasing order of preference 0,5, 1 , 3, 5, 7, 9, 10 or 11 microns thick, and no more than, if only for economic reasons, in increasing order of preference, 50, 30, 25, 20, 15, 14, 13, or 12 microns thick.
  • the coating may range from 2- 5 microns. In one embodiment, the coating thickness ranges from 3 to 8.5 microns.
  • electrolytically applied inorganic-based coatings according to the invention perform better than commercially available conversion coatings for magnesium in unpainted and painted corrosion testing, as well as providing improved corrosion resistance when compared to PEO coatings on magnesium alloys typically used in the automotive industry, e.g. magnesium casting alloys and forged alloys.
  • the electrolytically applied inorganic-based coatings perform better than commercially available conversion coatings for magnesium in unpainted and painted corrosion testing, as well as providing improved corrosion resistance when compared to PEO coatings on magnesium alloys typically used in the automotive industry, e.g. magnesium casting alloys and forged alloys.
  • magnesium-containing article may have a composite coating wherein the inorganic-based coating may act as a matrix.
  • This embodiment may include a coating comprising:
  • the coating on the magnesium containing article may comprise:
  • a second component e.g. a vanadium post-treatment, that is different from the
  • inorganic-based coating and distributed throughout at least a portion of the inorganic- based coating and
  • the second component may have the same composition as the second layer. In another embodiment of the invention, the second component may be different from both A) and C), In one embodiment, the second component and/or the second layer may form reaction products with elements in the inorganic-based coating. In one embodiment, the inorganic-based coating has a layer of paint deposited thereon, which may comprise the second layer or may be in addition to the second layer,
  • inorganic-based coatings according to the invention and aqueous compositions for depositing the inorganic-based coatings, as defined above, may be substantially free from many ingredients used in compositions for similar purposes in the prior art.
  • aqueous compositions according to the invention when directly contacted with metal in a process according to this invention, contain no more than 1.0, 0.5, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01 , 0.001 , or 0.0002 percent, more preferably said numerical values in grams per liter, of each of the following constituents: chromium, cyanide, nitrite ions; organic materials, e.g. organic surfactants; amines, e.g. hydroxylamines; ammonia and ammonium cations; silicon, e.g.
  • sulfur e.g. sulfate; permanganate; perchlorate; borate and/or free chloride.
  • as-deposited inorganic-based coatings and inorganic secondary layers according to the invention contain no more than 1.0, 0.5, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01 , 0.001 , or 0.0002 percent, more preferably said numerical values in parts per thousand (ppt), of each of the following constituents: chromium, cyanide, nitrite ions; organic materials, e.g.
  • organic surfactants amines, e.g. hydroxylamines; ammonia and ammonium cations; silicon, e.g. siloxanes, organosiloxanes, silanes, silicate; phosphorus; rare earth metals; sodium; sulfur, e.g. sulfate; permanganate; perchlorate; borate and/or free chloride.
  • Inorganic-based coatings can be produced by a variety of processes capable of generating hard, amorphous coatings chemically bonded to magnesium-containing metals.
  • the inorganic-based coating may be formed using electrolytic deposition according to the inventive process described herein.
  • Processes according to the invention are directed to methods of improving corrosion resistance on magnesium containing substrates comprising:
  • an alkaline electrolyte comprised of water, a source of hydroxide ion, and one or more additional components selected from the group consisting of: water-soluble inorganic fluorides, water-soluble organic fluorides, water-dispersible inorganic fluorides, and water-dispersible organic fluorides and mixtures thereof; • providing a cathode electrically connected to, desirably in physical contact with the electrolyte;
  • the process may comprise optional steps of: cleaning, etching, deoxidizing and desmutting with or without intervening steps of rinsing with water.
  • a rinse water may be counterflowed into a preceding bath.
  • a step 5) of masking or closing off portions of the article to limit or prevent contact with the electrolyte may be performed prior to contacting the magnesium containing article with the electrolyte.
  • masking may be applied to magnesium containing portions of the article where no coating is desired or may be applied to protect article components or surfaces that might be damaged by the electrolyte, likewise hollow portions of an article, e.g. the lumen of a pipe, may be closed off or plugged to prevent electrolyte contact of interior surfaces.
  • the inorganic-based coating is not physically or chemically removed or etched. Specifically, no more than 1000, 500, 100, 50, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0.5 mg/m2 of the inorganic-based coating may be removed from the article. Preferably none of the deposited inorganic-based coating is removed.
  • the surface to be electrolytically coated has sufficient magnesium metal or other light metal in combination with magnesium, desirably in the zero oxidation state, to permit coating generation and the non-magnesiferous surfaces are not negatively affected by the treatments.
  • Masking of selected surfaces to prevent contact with electrolyte can be accomplished by methods known in the art.
  • the electrolytic treatment is advantageously applicable to magnesium-base alloys containing one or more other elements such as Al, Zn, Mn, Zr, Si and rare earth metals.
  • the magnesium containing surfaces to be coated are contacted with an electrolyte, desirably an aqueous electrolyte comprising dissolved fluoride ions and free of phosphorus.
  • the electrolyte may have a pH of 10 or more, desirably greater than 10, 11 , 12 or 13.
  • an electrolyte is employed which may be maintained at a temperature between about 5° C. and about 90° C, desirably from about 20° to about 45°C.
  • a magnesium or magnesium alloy surface is contacted with, desirably immersed in, an aqueous electrolyte and electrolyzed as the anode in the circuit.
  • One such process comprises immersing at least a portion of the article in the electrolyte, which is preferably contained within a bath, tank or other such container.
  • a second article that is cathodic relative to the anode is also placed in the electrolyte.
  • the electrolyte is placed in a container which is itself cathodic relative to the article (anode).
  • Voltage is applied across the anode and cathode for a time sufficient to form an inorganic-based electrolytic coating.
  • the time required to produce a coating in an electrolytic process according to the invention may range, in increasing order of preference, from about 30, 60, 90, 120 seconds, up to about 150, 180, 210, 240, 300 seconds. Longer deposition times may be utilized but are considered commercially undesirable.
  • Electrolytic processing time can be varied to maximize efficiency by reducing time to Vmax and to control coating weight.
  • Alternating current, direct current or a combination may be used to apply the desired voltage, e.g. straight DC, pulsed DC, AC waveforms or combinations thereof.
  • pulsed DC current is used.
  • a period of at least 0.1 , 0.5, 1.0, 3.0, 5.0, 7.0, 9.0, or 10 millisecond and not more than 50, 45, 40, 35, 30, 25, 20, or 15 millisecond may be used, which period may be held constant or may be varied during the immersion period.
  • Waveforms may be rectangular, including square; sinusoidal; triangular, sawtooth; and combinations thereof, such as by way of non-limiting example a modified rectangle having at least one vertical leg that is not perpendicular to the horizontal portion of the rectangular wave.
  • Peak voltage potential desirably may be, in increasing order of preference, up to about 800, 700, 600, 500, 400 volts, and may desirably is at least in increasing order of preference 140, 150, 160, 170, 180, 200, 300 volts. In one embodiment peak voltage can range from 120-200 volts.
  • Average voltage may be in increasing order of preference at least 50, 70, 90, 100, 120, 130, 140, or 150 volts and independently preferably may be less than 600, 550, 500, 450, 400, 350, 300, 250, 200 or 180 volts. In one embodiment, average voltage can range from about 120-300 volts. In another embodiment, average voltage may be selected to be in a higher range of 310- 500 volts.
  • Voltage is applied across the electrodes until a coating of the desired thickness is formed on the surface of the article. Generally, higher voltages result in increased overall coating thickness and sparking may ensue. Higher voltages may be used within the scope of the invention provided that the substrate is not damaged and coating formation is not negatively affected.
  • the electrolyte for the process may be an aqueous alkaline composition comprising a source of fluorine and a source of hydroxide ions.
  • the source of hydroxide may be inorganic or organic, provided that it can be dissolved or dispersed in the aqueous electrolyte and does not interfere with the deposition of the inorganic-based coating.
  • Suitable examples include NaOH and KOH, with KOH being preferred.
  • the source of fluoride may be inorganic or organic, provided that it can be dissolved or dispersed in the aqueous electrolyte and does not interfere with the deposition of the inorganic-based coating.
  • Suitable examples include at least one of alkali metal fluorides, certain alkaline earth metal fluorides and ammonium bifluoride.
  • the electrolyte may comprise KF and KOH. Desirably, free alkalinity is measured and maintained at
  • alkalinity titration Pipet 50 mis (volumetric pipet) of bath into a beaker and titrate with phenolphthalein indicator until a clear endpoint is reached using 0.10 M HCI titrant.
  • the process alkalinity is controlled to be at least in order of increasing preference 7, 8, 9,10, 1 1 , 12, 13, or 14 ml and is not more than 24, 23, 22, 21 , 20, 19, 18, 17, 16 or 15 ml.
  • the above-described coating process provides improved energy efficiency by lower electrical consumption compared to PEO/MAO processes.
  • the inventive process generally requires less than 20%, 15% or 10% of the electricity consumption (in kWh) to apply an electroceramic coating equal in thickness to a PEO coating per unit surface area.
  • the inventive process utilizes in increasing order of preference, no more than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1 kWh /m 2 and energy consumption may be as low as in increasing order of preference 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 kWh /m 2 .
  • electroceramic coating process also has lower cooling requirements for the electrolyte compared to PEO/MAO, generally less than 20%, 15% or 10% cooling of the electrolyte needed, which is in part due to the lack of spark generation.
  • magnesium-containing surfaces Prior to electrolytic coating, magnesium-containing surfaces may be subjected to one or more of cleaning, etching, deoxidizing and desmutting steps, with or without rinsing steps. Cleaning may be alkaline cleaning and a cleaner may be used to etch the surfaces. A suitable cleaner for this purpose is Parco Cleaner 305, an alkaline cleaner commercially available from Henkel Corporation. Desirably, the magnesium-containing surfaces may be etched by at least in increasing order of preference , 3, 5, 7, 10, or 15 g/m2 and independently preferably, at least for economy, not more than 20, 25, 30, 35, 40, 45 or 50 g/m2. Etching can be accomplished using commercially available etchants and/or deoxidizers for magnesium.
  • a desmutting step may also be included in processing.
  • Suitable desmutters include acids such as carboxylic acids, e.g. hydroxyacetic acid, alone or in combination with chelators and nitrates. If any of the above-described steps is utilized, the magnesium- containing surfaces are typically rinsed as a final step to reduce introduction of the prior steps' chemistries into the electrolyte.
  • Additional processing steps may be used after deposition of the inorganic- based coating, such as rinsing with water, alkaline solutions, acid solutions and
  • the process may include steps of applying at least one post-treatment, which may be dispersed in the inorganic-based coating, may form reaction products therewith, and/ or may form an additional layer and combinations thereof.
  • the additional layer may be an inorganic layer, an organic layer or a layer that comprises inorganic and organic components.
  • any post- treatments including for example additional layers described herein, are durably bound to the inorganic-based coating; while other removable layers for masking during manufacture or for shipping after coating may be applied.
  • porous structure of the electrolytically deposited inorganic-based coatings on the magnesium containing article was a particular challenge for post-treatments that are not pore closing due to the significant surface area present on the internal surfaces of inorganic-based coatings.
  • Surface area of inorganic-based coatings according to the invention is generally 75 to 100 times that of the original metal surface, by BET
  • a vanadium-containing post- treatment step was surprisingly found to be a suitable method for introducing a second component for additional corrosion protection, in processes according to the invention, despite other post-treatments useful for anodized layers having little or no positive effect on corrosion resistance.
  • conventional post-treatments for anodized magnesium, including nickel based salts and lithium salts were found to provide insufficient unpainted corrosion resistance.
  • post-treatment of the in organic- based coating with a vanadium-containing composition provided improvements in corrosion resistance.
  • the vanadium containing post-treatment step may be used immediately after deposition of the inorganic-based coating, which may be dried. Articles having the inorganic-based coating deposited thereon via electrolytic deposition may be rinsed for 1-30 seconds and then contacted with the vanadium containing composition.
  • Vanadium can be present in the post-treatment in various oxidation states such as III, IV, and V.
  • Sources of vanadium ions in the post-treatment can include metallic V, organic and inorganic V-containing materials, for example V-containing minerals and compounds.
  • Suitable compounds of V include by way of non-limiting example oxides, acids and their salts, and V- containing organic materials, e.g.
  • decavanadate salts have been characterized: NH 4+ , Ca 2 ⁇ Ba 2+ , Sr 2+ , and group I decavanadate salts may be prepared by the acid-base reaction between V2O5 and the oxide, hydroxide, carbonate, or hydrogen carbonate of the desired positive ion.
  • Suitable decavanadate post-treatments include: Vanadium acetyl acetonate, (NH ) 6 [V IO 0 2B ] , 6H 2 0, K6[Vi 0 O28]-9H 2 O, Ke
  • Suitable vanadium containing compositions according to this invention comprise, consist essentially of, or preferably consist of, water and vanadate ions, particularly decavanadate ions.
  • the concentration of vanadium atoms present in vanadate ions in the composition according to this invention preferably is, with increasing preference in the order given, at least 0.0005, 0.001 , 0.002, 0.004, 0.007, 0.012, 0.020, 0.030, 0.040, 0.050, 0.055, 0.060, 0.065, 0.068, 0.070, or 0.071 M and independently preferably is, with increasing preference in the order given, primarily for reasons of economy, not more than 1.0, 0.5, 0.30, 0.20, 0.15, 0.12, 0.10, 0.090, 0.080, 0.077, 0.074, or 0.072M.
  • the temperature of such a post-treating composition, during contact with the inorganic- based coating on the magnesium containing article as described above preferably is, with increasing preference in the order given, at least 30° C, 35° C, 40° C, 45° C, 48° C, 51 ° C, 53° C, 55° C, 56° C, 57° C, 58° C or 59° C and independently preferably is, with increasing preference in the order given, not more than 90° C, 80° C, 75° C, 72° C, 69° C, 67° C, 65° C, 63° C, 62" C or 61 ° C.
  • the time of contact between the vanadium containing composition and the inorganic-based coating on the magnesium containing article as described above preferably is, with increasing preference in the order given, not less than 0.5, 1.0, 2.0, 2.5, 3.0, 3.5, 4.0, 4.3, 4.6, or 4.9 min and independently preferably is, with increasing preference in the order given, primarily for reasons of economy, not greater than 60, 30, 15, 12, 10, 8, 7.0, 6.5, 6.0, 5.7, 5.4, or 5.1 min.
  • At least one vanadium containing composition is desirably introduced to the second sub-layer of inorganic-based coating, contacting at least the external surfaces and desirably at least some of the internal surfaces thereof.
  • the second component may comprise the vanadium containing composition and/or may comprise reaction products of the vanadium containing composition and elements of the inorganic-based coating.
  • the vanadium containing composition reacts with elements of the inorganic- based coating to thereby form a second component, which is different from the inorganic- based coating at least in that the second component comprises vanadium.
  • the second component may form a thin film in contact with the externa! surfaces of the inorganic-based coating and lining at least a portion of the pores in the inorganic-based coating.
  • the vanadium containing compositions may also contact internal surfaces of the inorganic-based coating and/or react with elements of the internal surfaces rendering the inorganic-based coating more resistant to corrosion producing agents reaching the magnesium containing surface. Vanadium may further infiltrate the inorganic-based coating such that vanadium is distributed throughout at least a portion of the inorganic-based coating. Analysis of inorganic-based coatings according to the invention that have been contacted with a vanadium containing composition showed the presence of vanadium in the inorganic-based coating matrix.
  • Depth of penetration of vanadium second components into the inorganic-based coating matrix may include up to 100, 90, 80, 70, 65, 60, 55 or 50% of total thickness of the porous second sub-layer of the inorganic-based coating, said total thickness being measured from the second interface to the external surface of the inorganic-based coating.
  • the vanadium containing composition may be reactive with elements in the inorganic-based coating. Contacting the inorganic-based coating with a vanadium-containing composition provides improved corrosion resistance and does not cover up the pores in external surfaces of the inorganic-based coating. This is beneficial if a subsequent paint step is to be used because the pores provide anchoring sites for adhering paint to the surface.
  • Another post-treatment step which may be employed is depositing an additional layer comprising a polymer, preferably this may be done using a thermosetting resin which may or may not react with the inorganic-based coating.
  • Average thickness of the polymeric second layer as measured from an external surface of the inorganic-based coating to an outer surface of the second layer, may range from, in order of increasing preference, at least about 0.1 , 0.25, 0.5, 0.75, 1 , 2, 3, 4, or 5 microns and in order of increasing preference, not more than about 14, 12, 10, 8 or 6 microns.
  • typical paint thicknesses are at least 25 microns thick.
  • Use of either a thin polymeric layer, as described above, or a paint generally covers the pores in the external surfaces of the inorganic-based coating, the pores providing improved adhesion of the polymer or paint and surprisingly resulting in a uniform surface.
  • polymers forming the second layer may comprise organic polymer chains or inorganic polymer chains.
  • polymers suitable for an additional layer include by way of non-limiting example, silicone, epoxy, phenolic, acrylic, polyurethane, polyester, and polyimide.
  • organic polymers selected from epoxy, phenolic and polyimide are utilized.
  • Preferred polymers forming additional layers include phenol-formaldehyde-based polymers and copolymers generated from, for example novolac resins, which have a formaldehyde to phenol molar ratio of less than one, and resole resins having a formaldehyde to phenol molar ratio of greater than one.
  • Such polyphenol polymers can be made as is known in the art for example according to US Patent No. 5,891 ,952.
  • Novolac resins are desirably used in combination with a crosslinking agent to facilitate curing.
  • a resole resin having a formaldehyde to phenol molar ratio of about 1.5 is utilized to form a polymer additional layer on the inorganic-based coating.
  • Phenolic resins useful in forming polymeric layers desirably have molecular weights of about 1000 to about 5000 g/mole, preferably 2000 to 4000 g/mole.
  • At least one of the above-described resins is desirably introduced to the first layer of inorganic-based coating, contacting at least the external surfaces thereof, and crosslinking to thereby form a polymeric layer on external surfaces of the inorganic-based coating.
  • This polymeric second layer is different from the inorganic-based coating and is adhered to the inorganic-based coating.
  • the resin may also contact internal surfaces of the inorganic-based coating and upon curing form a polymeric second component that is different from the inorganic-based coating and distributed throughout at least a portion of the inorganic-based coating.
  • Analysis of inorganic-based coatings according to the invention that have been contacted with a resole resin having a formaldehyde to phenol molar ratio of 1.5 showed the polymeric components present in the inorganic-based coating matrix thereby forming a composite coating.
  • Depth of penetration of polymeric second components into the inorganic-based coating matrix may range in increasing order of preference from 1 , 2, 5, 10, 15, 20 or 25% and in increasing order of preference may be not more than 70, 65, 60, 55 or 50, 45, 40 or 35% of total thickness of the inorganic-based coating, said total thickness being measured from the first interface to the external surface of the inorganic-based coating.
  • the resin may comprise functional groups reactive with elements in the inorganic-based coating, which may form bonds between the resin and the inorganic-based coating.
  • uncured novolac and resole resins comprise OH functional groups which may react with metals in the inorganic-based coating thereby linking the polymer to the inorganic-based coating.
  • Coated substrates according to the invention are useful in motor vehicles; aircraft and electronics where the combination of the inorganic-based coating and post- treatment layers can provide more corrosion protection than paint or anodizing alone, while ceramic-type hardness of the combination imparts additional toughness to external layers because sharp objects have greater difficulty in deforming a harder substrate prime layer than magnesium, which is relatively soft as compared to ceramic. Coatings according to the invention also can be beneficial in keeping the topcoat gloss and color readings relatively consistent by providing a relatively uniform paint base.
  • the process and coated articles of the invention provide a more uniform surface layer on magnesium alloys, by way of non-limiting example AZ91 B, AZ91 D and AZ31 B, and magnesium containing surfaces having contamination, which provides improved corrosion resistance.
  • the AZ-31 Mg alloy panels were about 93-97 wt.% Mg, the remainder being made up of Al, Zn, Mn, and less than 0,5 wt.% of other metal and metalloid impurities.
  • the AZ-91 Mg alloy panels had less magnesium, about 87-91 wt.% Mg, with the remainder being made up of Al, Zn, Mn, and less than 1.2 wt.% of other metal and metalloid impurities.
  • All AZ-31 panels were cleaned in 5% BONDERITE ® C-AK 305, an alkaline cleaner commercially available from Henkel Corp., at 60 °C for 3 minutes; rinsed with Dl water; deoxidized in 3% BONDERITE ® C-IC HX-357 at 20-22 °C for 90 seconds, which was about a 30 g/m 2 etch rate.
  • BONDERITE ® C-AK 305 an alkaline cleaner commercially available from Henkel Corp.
  • Example 1 Inorganic-based coating with post-treatment and no paint
  • AZ-31 Mg alloy panels were immersed in an electrolyte bath containing 40 grams/liter KF and 5 grams/liter of KOH. The panels were electrolyzed as the anode using a 25 msec, on and 9 msec off square waveform for about 180 seconds generating an edge- covering, inorganic-based coating. The coated panels were removed from the electrolyte bath and rinsed with Dl water for 300 sec. The coating was observed to have a uniform surface appearance and a thickness of 4 microns. The electro lytically deposited inorganic- based coating was not dried. Thereafter, each coated panel was immersed in an aqueous post-treatment containing one of the compositions recited in Table 1. The coated panels were subjected to 3 minutes of immersion time in the post-treatment tank.
  • Post-treatment containing SAVAN sodium ammonium decavanadate
  • Post-treatment 1 was a commercially available calcium containing post-treatment
  • Post-treatment 2 was a benchmarking solution of 6.1 g/l calcium nitrate
  • Post-treatment 3 was a benchmarking solution of 0.60 g/l phosphoric acid.
  • Example 2 Inorganic-based coating with post-treatment and no paint
  • Example 1 A new set of samples treated according to the procedure of Example 1 were prepared using test panels of a different Mg alloy (AZ-91 ) having higher levels of impurities. Some samples were post-treated with a second commercially available post-treatment instead of the SAVAN. All panels were tested according to the procedure of Example 1 and the test results are shown in Table 2. Table 2. Post-treatment study for AZ-91 alloy unpainted salt fog testing
  • AZ-31 Mg alloy panels were treated as described in the below Table. All panels had a bare 6061 aluminum skin bonded to the test panel with Terocal 5089 adhesive, commercially available from Henkel Corp. The dissimilar metals were used to set up galvanic reactions in the samples. The panels were scribed through the paint and underlying coatings down to the metal surface and then subjected to 504 hours of salt fog testing according to ASTM B- 17. The results are shown in Table 3.
  • Conversion Coating 1 was a commercially available chromium free conversion coating formulated for treating non-ferrous alloys applied at coating weights customary for these type products.
  • Electroceramic coating was an electrolytically applied inorganic-based coating according to the invention having amorphous two layered structure. Paints were
  • PEO Coating was a crystalline MgO-based coating applied using a commercially available plasma electrolytic oxidation process.
  • Conversion Coating 2 was a commercially available chromium free conversion coating formulated for treating Mg having a typical layer thickness of less than 1 ⁇ .
  • Electroceramic coating was an inorganic-based coating electrolytically applied according to the invention having amorphous regions and a two layered structure.
  • Urethane paint utilized was PCU 73101 silver powder paint (PPG) cured at 375 °F for 25 min.
  • Example 5 Inorganic-based coating process variations in painted corrosion performance
  • AZ-91 Mg alloy panels were used for this example and were cleaned as described above. Each of the panels was immersed in one of the electrolyte baths shown in the below table. Fluoride concentration measurement was made with a 101 D meter which measures the fluoride attack on a silicon wafer according to the manufacturer's instructions. The panels were electrolyzed as the anode using a 25 msec, on and 9 msec off square waveform for about 180 seconds. An edge-covering, inorganic-based coating having a uniform surface containing pores, resulted on each of the panels. The coated panels were removed from the electrolyte baths, rinsed with Dl water for 240 sec. and allowed to dry.
  • the panels were painted with a liquid paint cured according to manufacturer's specification.
  • the Mg alloy panels coated with the inorganic-based coating and cured layer of paint were tested for corrosion resistance according to ASTM B-117 for 504 hours and were tested for cross-hatch adhesion according to ASTM 3359 method B and the results are shown in the Table 5 below. Table 5
  • N means no corrosion visible at the scribe.
  • ASTM 3359 scale is 0 to 5, 5: no removal or peeling, edges of the cuts are smooth and none of the squares of the lattice is detached.
  • Sample Groups 5.1 to 5.12 having an inorganic-based coating and a layer of paint showed excellent corrosion resistance and paint adhesion across a range of process parameters and coating thicknesses.
  • the above table shows that by controlling the alkalinity, fluoride concentration and temperature of the electrolyte, the ramp time to Vmax can be and coating thickness can be controlled for a given contact time, current and waveform. Using these non-linear relationships Vmax can be reduced thereby increasing throughput of the process without adversely affecting corrosion resistance or paint adhesion
  • Example 6 Inorganic-based coating with an organic second layer
  • This experiment tested a new set of samples according to the procedure of Example 1 except that the panels were electrolyzed for a time sufficient to generate a uniform, edge-covering, inorganic-based coating, and an organic-based post-treatment was used instead of a post-treatment.
  • the post-treatment used was a resole resin comprising phenol formaldehyde condensate with a degree of polymerization greater than 1.5.
  • the panel was allowed to dry. Thereafter the organic-based post-treatment was applied and dried for 20 minutes at 160 C C (320 °F).
  • a first set of panels were provided with a post-treatment having a dried thickness of 6 microns, resulting in a total inorganic/organic coating thickness of 12 microns.
  • a second set of panels were provided with a post-treatment having a dried thickness of 10 microns, resulting in a total inorganic/organic coating thickness of 16 microns. All panels were tested for corrosion resistance according to ASTM B-117. After 1000 hours of testing the panels showed no corrosion at the scribe and did not show any field or edge corrosion.
  • Example 8 Bare inorganic-based coating performance
  • Thermal Shock Testing comprises baking panels at 550 °C for 60 minutes, removing panels from the oven, immersing the panels in ice water (0°C) without a cooling step and testing for adhesion using ASTM 3359 method B (Crosshatch).
  • Adhesive Bonding was tested by creating specimens from uncoated Mg alloy panels and from panels coated according to Example 8. Each specimen had a lap joint with 1" overlapping epoxy structural adhesive and 1" wide shear specimens. Force was applied at a controlled rate to each specimen until the bond at the lap joint failed and the maximum force was recorded. Reverse Impact Resistance was tested according to ASTM D2794. Vickers hardness measurement was by nanoindentation and appears to be affected by the underlying alloy.

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Abstract

La présente invention concerne des articles à surfaces métalliques contenant du magnésium avec un revêtement électrocéramique chimiquement lié aux surfaces métalliques et des articles ayant un revêtement composite comprenant des premiers secteurs de revêtement électrocéramique et des second secteurs comprenant des composants organiques et/ou inorganiques différents du revêtement électrocéramique. En outre, l'invention concerne des procédés de production et d'utilisation des articles.
PCT/US2014/047026 2014-07-17 2014-07-17 Revêtement électrocéramique pour alliages de magnésium WO2016010541A1 (fr)

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MX2017000559A MX2017000559A (es) 2014-07-17 2014-07-17 Revestimiento electroceramico para aleaciones de magnesio.
PCT/US2014/047026 WO2016010541A1 (fr) 2014-07-17 2014-07-17 Revêtement électrocéramique pour alliages de magnésium
KR1020177002941A KR20170029545A (ko) 2014-07-17 2014-07-17 마그네슘 합금을 위한 전자세라믹 코팅
CN201480081973.0A CN106715762B (zh) 2014-07-17 2014-07-17 用于镁合金的电瓷涂料
CA2955317A CA2955317A1 (fr) 2014-07-17 2014-07-17 Revetement electroceramique pour alliages de magnesium
EP14897821.6A EP3169831A4 (fr) 2014-07-17 2014-07-17 Revêtement électrocéramique pour alliages de magnésium
JP2017502676A JP6513180B2 (ja) 2014-07-17 2014-07-17 マグネシウム合金のための電気セラミックコーティング
TW104122814A TW201619449A (zh) 2014-07-17 2015-07-14 用於鎂合金之電陶瓷塗層
US15/405,774 US20170121841A1 (en) 2014-07-17 2017-01-13 Electroceramic Coating for Magnesium Alloys

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11180832B2 (en) 2018-12-17 2021-11-23 Canon Kabushiki Kaisha Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object
US11613624B2 (en) 2019-11-07 2023-03-28 The Boeing Company Ceramic coated iron particles and methods for making ceramic coated particles

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201700055002A1 (it) * 2017-05-22 2018-11-22 Campagnolo Srl Ingranaggio per bicicletta e metodo per la fabbricazione di tale ingranaggio
CN110505766A (zh) * 2018-05-17 2019-11-26 安克创新科技股份有限公司 保护涂层的制备方法、电路板组件以及电子设备
JP7418117B2 (ja) * 2018-12-17 2024-01-19 キヤノン株式会社 マグネシウム－リチウム系合金部材及びその製造方法
CN112247097B (zh) * 2020-10-22 2022-03-18 重庆建谊祥科技有限公司 一种镁合金建筑模板半固态压铸及双氟化联合制造方法
EP4053309A1 (fr) * 2021-03-01 2022-09-07 Canon Kabushiki Kaisha Élément d'alliage, élément de glissement, appareil, et procédé de fabrication d'un élément d'alliage
CN113514390B (zh) * 2021-03-10 2023-06-13 首钢集团有限公司 一种汽车板电泳漆膜附着力测试方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4184926A (en) * 1979-01-17 1980-01-22 Otto Kozak Anti-corrosive coating on magnesium and its alloys
WO1992014868A1 (fr) * 1991-02-26 1992-09-03 Technology Applications Group, Inc. Procede chimique/electrochimique a deux etapes d'application d'un revetement sur du magnesium
US5226976A (en) * 1991-04-15 1993-07-13 Henkel Corporation Metal treatment
US5266412A (en) * 1991-07-15 1993-11-30 Technology Applications Group, Inc. Coated magnesium alloys
US20070256591A1 (en) * 2005-12-30 2007-11-08 Simmons Walter J Corrosion inhibiting inorganic coatings for magnesium alloys
CN101721753B (zh) * 2009-12-23 2014-04-09 天津大学 无机有机防腐生物相容性复合涂层的可吸收镁合金支架及其制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4744872A (en) * 1986-05-30 1988-05-17 Ube Industries, Ltd. Anodizing solution for anodic oxidation of magnesium or its alloys
JPS63100195A (ja) * 1986-05-30 1988-05-02 Ube Ind Ltd マグネシウムまたはその合金の陽極酸化処理液
DE3808610A1 (de) * 1988-03-15 1989-09-28 Electro Chem Eng Gmbh Verfahren zur oberflaechenveredelung von magnesium und magnesiumlegierungen
DE3808609A1 (de) * 1988-03-15 1989-09-28 Electro Chem Eng Gmbh Verfahren zur erzeugung von korrosions- und verschleissbestaendigen schutzschichten auf magnesium und magnesiumlegierungen
US5470664A (en) * 1991-02-26 1995-11-28 Technology Applications Group Hard anodic coating for magnesium alloys
JPH11323571A (ja) * 1998-03-17 1999-11-26 Matsushita Electric Ind Co Ltd 表面処理したマグネシウム又はマグネシウム合金製品並びに塗装下地処理方法及び塗装方法
JP2000345370A (ja) * 1999-06-07 2000-12-12 Ueda Alumite Kogyo Kk マグネシウム又はマグネシウム合金の表面処理方法
US6495267B1 (en) * 2001-10-04 2002-12-17 Briggs & Stratton Corporation Anodized magnesium or magnesium alloy piston and method for manufacturing the same
JP2005272853A (ja) * 2004-03-22 2005-10-06 Nsk Ltd 酸化物被膜を有する機械部品及び該機械部品を備える転動装置、並びに該機械部品の表面処理方法
JP2006183065A (ja) * 2004-12-24 2006-07-13 Aisin Keikinzoku Co Ltd 軽金属等の表面処理方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4184926A (en) * 1979-01-17 1980-01-22 Otto Kozak Anti-corrosive coating on magnesium and its alloys
WO1992014868A1 (fr) * 1991-02-26 1992-09-03 Technology Applications Group, Inc. Procede chimique/electrochimique a deux etapes d'application d'un revetement sur du magnesium
US5226976A (en) * 1991-04-15 1993-07-13 Henkel Corporation Metal treatment
US5266412A (en) * 1991-07-15 1993-11-30 Technology Applications Group, Inc. Coated magnesium alloys
US20070256591A1 (en) * 2005-12-30 2007-11-08 Simmons Walter J Corrosion inhibiting inorganic coatings for magnesium alloys
CN101721753B (zh) * 2009-12-23 2014-04-09 天津大学 无机有机防腐生物相容性复合涂层的可吸收镁合金支架及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3169831A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11180832B2 (en) 2018-12-17 2021-11-23 Canon Kabushiki Kaisha Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object
US11613624B2 (en) 2019-11-07 2023-03-28 The Boeing Company Ceramic coated iron particles and methods for making ceramic coated particles

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TW201619449A (zh) 2016-06-01

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