EP1458900A1 - Magnesium-werkstück und verfahren zur ausbildung einer korrosionsschützenden deckschicht eines magnesium-werkstücks - Google Patents

Magnesium-werkstück und verfahren zur ausbildung einer korrosionsschützenden deckschicht eines magnesium-werkstücks

Info

Publication number
EP1458900A1
EP1458900A1 EP02805727A EP02805727A EP1458900A1 EP 1458900 A1 EP1458900 A1 EP 1458900A1 EP 02805727 A EP02805727 A EP 02805727A EP 02805727 A EP02805727 A EP 02805727A EP 1458900 A1 EP1458900 A1 EP 1458900A1
Authority
EP
European Patent Office
Prior art keywords
workpiece
magnesium
halogen salt
salt
halogen
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP02805727A
Other languages
German (de)
English (en)
French (fr)
Inventor
Friedrich-Wilhelm Bach
Tai Phan-Tan
Heinrich-Dietrich Haferkamp
Volker Kaese
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leibniz Universitaet Hannover
Original Assignee
Leibniz Universitaet Hannover
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 Leibniz Universitaet Hannover filed Critical Leibniz Universitaet Hannover
Publication of EP1458900A1 publication Critical patent/EP1458900A1/de
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step
    • 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
    • C23C22/70—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 melts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the invention relates to a method for forming a corrosion-protective cover layer of a magnesium workpiece.
  • the invention further relates to a
  • Magnesium workpiece with a corrosion-protective top layer Magnesium workpiece with a corrosion-protective top layer.
  • Magnesium materials will become increasingly important in the near future. This is associated with increased demands on magnesium materials as a construction material.
  • An essential criterion for the use of magnesium materials is the corrosion resistance to corrosive media.
  • oxides e.g. B. chromium oxide and / or metal molybdate, known as a corrosion-protective top layer systems to inhibit the tendency to pitting.
  • the invention is based on the problem of effectively increasing the corrosion resistance of magnesium workpieces in a simple manner and regardless of the geometry of the workpiece.
  • the method of the type mentioned at the outset is characterized in that a halogen salt is introduced into at least one surface layer of the workpiece, which has a lower thermodynamic stability compared to a salt of the same halogen formed with magnesium such that during the introduction of the halogen salt into the workpiece and / or the salt is formed with magnesium under the action of a corrosion medium.
  • a magnesium workpiece according to the invention which can be produced using this method according to the invention is provided with a corrosion-protective cover layer with a thickness> 50 ⁇ m, which contains at least a portion of an oxygen-free halogen salt, a substituted cation of the halogen salt and a salt formed with magnesium with the anion of the halogen salt, wherein the halogen salt has a lower thermodynamic stability than the salt formed with magnesium.
  • the formation of an oxygen-free, corrosion-protecting cover layer is thus achieved by introducing a suitable halogen salt into the workpiece.
  • This introduction can preferably be carried out by alloying (diffusion alloying, gas alloying, molten alloying or mechanical alloying (by centrifugal casting or reaction milling), wherein, for example, by molten alloying, a uniform alloying of the workpiece, by diffusion alloying an alloy of a sufficiently deep Surface layer is done.
  • the alloy fraction of the halogen salt in the surface layer (diffusion alloy) or in the entire workpiece (melt alloy) is at least 1 at%, preferably around 2 at%, but can also be up to 15 at%.
  • Halogen salts are primarily and particularly preferably fluorides.
  • a particularly preferred halogen salt is aluminum fluoride.
  • Successful experiments have also been carried out with potassium borofluoride (KBF 3 ) and sodium aluminum fluoride (Na 3 AIF 6 ).
  • the magnesium material can be pure magnesium, but preferably also a magnesium alloy. It is particularly preferred to use the technical alloys AZ31, ie an alloy with aluminum and zinc, a magnesium alloy with lithium and calcium components or the alloy LAE442 (MgLi4AI4SE2 mas%) containing lithium, aluminum and rare earths. In both cases, alloying takes place, preferably in molten form in the crucible, with 2 at% of a halogen salt, preferably AIF 3 .
  • a pure magnesium semi-finished product is to be treated with aluminum fluoride by diffusion alloying, regardless of the geometry.
  • the semi-finished magnesium product is embedded in concentrated AIF 3 (concentration> 90%) in powder form and diffusion alloyed in the order of magnitude over 24 hours at temperatures of up to 850 ° C, preferably at 420 ° C.
  • the powder packing process is carried out in a laboratory tilting crucible furnace, whereby a weight that is moderate is applied to the powder surface by a CrNi steel stamp Pressure of 3 kPa generated to close process-related caverns in the powder pack.
  • the relatively long holding time of around 24 hours is said to make kinetic inhibitions, which are lower at higher temperatures, negligible.
  • the cover layers obtained in the powder packaging process have a thickness of at least 100 square meters and are up to 200 ⁇ m.
  • the top layer for pure magnesium consists of MgF 2 and AIF 3 . Cover layers with the following components were found for other alloys:
  • the magnesium material has been modified to be molten in a crucible with 2 at% AIF 3 .
  • the fluorine salt can be added to the bottom of the crucible, as a bed or by means of a cartridge, the cartridge consisting, for example, of magnesium or one of its alloys and finally sagging into the melt in order to prevent burn-up or smoking.
  • the magnesium alloys can also contain varying Li fractions and Ca fractions, the Li fraction being between 0 and 30 at% and the Ca fraction between 0 and 5 mas%.
  • the modification with the halogen salt, here the fluoride can be between 1 and 15 at%.
  • the alloy LAE442 (MgLi4AI4SE2 mas%) was alloyed with 2 at% AIF 3 in the crucible. This alloy shows a 10 times better corrosion resistance in aggressive electrolytes (examined with synthetic sea water or with 5% NaCI solution). The alloy already shows satisfactory mechanical properties in the as-cast state, namely

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP02805727A 2001-12-24 2002-11-22 Magnesium-werkstück und verfahren zur ausbildung einer korrosionsschützenden deckschicht eines magnesium-werkstücks Ceased EP1458900A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10163107 2001-12-24
DE10163107A DE10163107C1 (de) 2001-12-24 2001-12-24 Magnesium-Werkstück und Verfahren zur Ausbildung einer korrosionsschützenden Deckschicht eines Magnesium-Werkstücks
PCT/DE2002/004296 WO2003056055A1 (de) 2001-12-24 2002-11-22 Magnesium-werkstück und verfahren zur ausbildung einer korrosionsschützenden deckschicht eines magnesium-werkstücks

Publications (1)

Publication Number Publication Date
EP1458900A1 true EP1458900A1 (de) 2004-09-22

Family

ID=7710264

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02805727A Ceased EP1458900A1 (de) 2001-12-24 2002-11-22 Magnesium-werkstück und verfahren zur ausbildung einer korrosionsschützenden deckschicht eines magnesium-werkstücks

Country Status (7)

Country Link
US (1) US20050042440A1 (ja)
EP (1) EP1458900A1 (ja)
JP (1) JP2005513274A (ja)
AU (1) AU2002357433A1 (ja)
CA (1) CA2473501A1 (ja)
DE (2) DE10163107C1 (ja)
WO (1) WO2003056055A1 (ja)

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US6865810B2 (en) * 2002-06-27 2005-03-15 Scimed Life Systems, Inc. Methods of making medical devices
US8840660B2 (en) 2006-01-05 2014-09-23 Boston Scientific Scimed, Inc. Bioerodible endoprostheses and methods of making the same
US8089029B2 (en) 2006-02-01 2012-01-03 Boston Scientific Scimed, Inc. Bioabsorbable metal medical device and method of manufacture
DE102006011348B4 (de) * 2006-03-11 2015-10-08 Biotronik Vi Patent Ag Verfahren zur Erzeugung einer in physiologischer Umgebung korrosionshemmenden Schicht auf einem Formkörper
US8048150B2 (en) 2006-04-12 2011-11-01 Boston Scientific Scimed, Inc. Endoprosthesis having a fiber meshwork disposed thereon
US8052743B2 (en) 2006-08-02 2011-11-08 Boston Scientific Scimed, Inc. Endoprosthesis with three-dimensional disintegration control
US8808726B2 (en) 2006-09-15 2014-08-19 Boston Scientific Scimed. Inc. Bioerodible endoprostheses and methods of making the same
EP2959925B1 (en) 2006-09-15 2018-08-29 Boston Scientific Limited Medical devices and methods of making the same
DE602007011114D1 (de) 2006-09-15 2011-01-20 Boston Scient Scimed Inc Biologisch erodierbare endoprothese mit biostabilen anorganischen schichten
WO2008034050A2 (en) * 2006-09-15 2008-03-20 Boston Scientific Limited Endoprosthesis containing magnetic induction particles
CA2663303A1 (en) * 2006-09-15 2008-03-20 Boston Scientific Limited Endoprosthesis with adjustable surface features
EP2068782B1 (en) * 2006-09-15 2011-07-27 Boston Scientific Limited Bioerodible endoprostheses
US20080071348A1 (en) * 2006-09-15 2008-03-20 Boston Scientific Scimed, Inc. Medical Devices
CA2663762A1 (en) 2006-09-18 2008-03-27 Boston Scientific Limited Endoprostheses
WO2008036554A2 (en) * 2006-09-18 2008-03-27 Boston Scientific Limited Endoprostheses
US20100145436A1 (en) * 2006-09-18 2010-06-10 Boston Scientific Scimed, Inc. Bio-erodible Stent
US20080097577A1 (en) * 2006-10-20 2008-04-24 Boston Scientific Scimed, Inc. Medical device hydrogen surface treatment by electrochemical reduction
DE102006060501A1 (de) * 2006-12-19 2008-06-26 Biotronik Vi Patent Ag Verfahren zur Herstellung einer korrosionshemmenden Beschichtung auf einem Implantat aus einer biokorrodierbaren Magnesiumlegierung sowie nach dem Verfahren hergestelltes Implantat
WO2008083190A2 (en) 2006-12-28 2008-07-10 Boston Scientific Limited Bioerodible endoprostheses and methods of making same
US8052745B2 (en) 2007-09-13 2011-11-08 Boston Scientific Scimed, Inc. Endoprosthesis
US7998192B2 (en) 2008-05-09 2011-08-16 Boston Scientific Scimed, Inc. Endoprostheses
US8236046B2 (en) * 2008-06-10 2012-08-07 Boston Scientific Scimed, Inc. Bioerodible endoprosthesis
US7985252B2 (en) 2008-07-30 2011-07-26 Boston Scientific Scimed, Inc. Bioerodible endoprosthesis
US8382824B2 (en) 2008-10-03 2013-02-26 Boston Scientific Scimed, Inc. Medical implant having NANO-crystal grains with barrier layers of metal nitrides or fluorides
EP2403546A2 (en) 2009-03-02 2012-01-11 Boston Scientific Scimed, Inc. Self-buffering medical implants
US20110183156A1 (en) * 2010-01-27 2011-07-28 Gm Global Technology Operations, Inc. Sacrificial anodic coatings for magnesium alloys
US8668732B2 (en) 2010-03-23 2014-03-11 Boston Scientific Scimed, Inc. Surface treated bioerodible metal endoprostheses
CN103451595B (zh) * 2013-09-02 2015-09-23 中国科学院金属研究所 镁合金表面熔盐氧碳硫共渗耐腐蚀陶瓷涂层及制备和应用
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

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Also Published As

Publication number Publication date
DE10163107C1 (de) 2003-07-10
AU2002357433A1 (en) 2003-07-15
DE10296141D2 (de) 2004-11-11
JP2005513274A (ja) 2005-05-12
US20050042440A1 (en) 2005-02-24
CA2473501A1 (en) 2003-07-10
WO2003056055A1 (de) 2003-07-10

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