EP0438971B1 - Substrat métallique revêtu - Google Patents

Substrat métallique revêtu Download PDF

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Publication number
EP0438971B1
EP0438971B1 EP90810867A EP90810867A EP0438971B1 EP 0438971 B1 EP0438971 B1 EP 0438971B1 EP 90810867 A EP90810867 A EP 90810867A EP 90810867 A EP90810867 A EP 90810867A EP 0438971 B1 EP0438971 B1 EP 0438971B1
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EP
European Patent Office
Prior art keywords
substrate
layer
melting
protective layer
sigma phase
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.)
Expired - Lifetime
Application number
EP90810867A
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German (de)
English (en)
Other versions
EP0438971A1 (fr
Inventor
James Dr. Simpson
Roger Dr. Dekumbis
Michel Dr. Les Hauts De Garenne Pierantoni
Roberto Busin
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.)
Sulzer Markets and Technology AG
Original Assignee
Sulzer Innotec AG
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Publication date
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Priority to AT9090810867T priority Critical patent/ATE105594T1/de
Publication of EP0438971A1 publication Critical patent/EP0438971A1/fr
Application granted granted Critical
Publication of EP0438971B1 publication Critical patent/EP0438971B1/fr
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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • 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
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment

Definitions

  • the invention relates to a coated metallic substrate according to the preamble of claim 1 and - according to claim 6 - a method for producing such a coated substrate.
  • JP-A-61-253 357 a method is known in which a substrate made of steel is thermally coated with metals such as Cu, Ni, Co, Cr, Ti or Mo or their alloys.
  • the adhesion of the coating is improved with laser treatment, although this results in reduced hardness.
  • a thermal aftertreatment is carried out by heating the coated substrate to a temperature in the range from 200 to 700 ° C. and then cooling it again with air.
  • the object of the invention is to create and produce a protective layer for a metallic substrate, which has a high hardness of at least 800 HV0.1. This object is solved by the characterizing features of claims 1 and 6, respectively.
  • the protective effect is achieved by the formation of a sigma phase, the proportion of which is at least 5% by volume in order to achieve the required minimum hardness, and by its high chromium (or chromium and molybdenum) content.
  • the sigma phase contains approximately 55% iron and 45% chromium; it is characterized by high hardness and very low plastic deformability.
  • too other phases such as Chi, Alpha-prime and Gamma-prime, and excretions, such as carbides and nitrides, contribute to the increased hardness.
  • the proportion of the sigma phase in the structure is increased; this can advantageously be, for example, at least 50% by volume.
  • the layer material is blown into the melt bath as a powder through a nozzle, the layer material being remelted at the same time and metallurgically bonded to the substrate;
  • the layer material can also be supplied as a rod or wire.
  • precoat the substrate with the layer material and then to connect the two materials to one another metallurgically by remelting.
  • the precoating is advantageously carried out galvanically or by a thermal spraying process, such as, for example, vacuum plasma spraying CVD or PVD.
  • a thermal spraying process such as, for example, vacuum plasma spraying CVD or PVD.
  • the melting and remelting can be carried out, for example, with a laser beam or an arc.
  • a laser beam or an arc With pre-coated substrates it is also possible to use an electron beam as the energy source for the melting.
  • the substrate can optionally be preheated before the precoating and / or before the melting process.
  • the heat treatment to form the sigma phase is carried out at about 700 ° C. for at least six hours.
  • the surface of the substrate to be coated is first degreased and galvanically coated with an approximately 80 ⁇ m thick coating of pure chrome.
  • the galvanically chromed substrate is then subjected to a heat treatment in air at about 200 ° C. for 4 to 6 hours.
  • the protective layer is produced by remelting the chrome-plated surface using a laser beam.
  • a laser beam with a power of 1500 W and a beam diameter on the surface to be remelted of 1.23 mm - which results in a power density of 1260 W / mm2 - is row by row under a helium protective gas atmosphere with a lateral offset of 0.2 mm per line performed in three passes over the surface of the chromium-plated substrate to be remelted, the feed speeds being 1900, 1500 and 1000 mm / min; from this, exposure times of 31, 39 and 58 ms can be calculated, which, in this case, results in a cooling rate of at least 2000 K / sec given the total mass of the substrate used and its thermal conductivity.
  • the multiple melting serves the purpose of the protective layer metallurgically connected to the substrate by the melting, which after the melting has the required composition of about 45% chromium and 55% iron in addition has low proportions of carbon, silicon, manganese and other trace elements from the steel St37.
  • the layer After the laser treatment, the layer has an intermediate hardness of HV0.1 240-260 and its structure does not contain a sigma phase.
  • a partial transformation of the structure into a sigma phase is achieved by a subsequent heat treatment, which is carried out at about 700 ° C. in an oven in air for about 12 hours, with neither the heating rate nor the cooling rate being critical parameters; it is only necessary to ensure that the necessary holding time at the treatment temperature is observed.
  • the protective layer has proven to be particularly resistant to corrosion, which is confirmed by corrosion tests in 5% NaCl, whereby the resistance to local forms of corrosion (pitting or crevice corrosion) after heat treatment is better than that of austenitic stainless steel DIN 1.4435 (X2 CrNiMo 18 12. AISI 316L); the critical pitting temperatures determined were for a Fe-44% Cr heat-treated, laser-remelted protective layer on St 37 or for a 1.4435 stainless steel 16 or 11.5 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Heat Treatment Of Articles (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Chemically Coating (AREA)

Claims (12)

  1. Substrat métallique revêtu d'une couche de protection, notamment contre la corrosion, l'érosion et/ou l'usure, caractérisé en ce que la couche protectrice présente, du fait de la formation de phases de grande dureté, principalement une phase sigma, une dureté minimale de 800 HVO.1 et en ce qu'elle est composée des éléments suivants (en % en masse) :
       35-50 % de chrome (Cr) + molybdène (Mo), avec une proportion de Mo de 0 à 10 %, au moins 25 % de fer (Fe), le reste étant constitué de fer et/ou d'au moins l'un des éléments suivants :
    Figure imgb0003
  2. Substrat revêtu suivant la revendication 1, caractérisé en ce que l'épaisseur de la couche protectrice s'élève à 0,1-3 mm.
  3. Substrat revêtu suivant la revendication 1 ou 2, caractérisé en ce qu'une proportion d'au moins 5 % en volume de la couche protectrice est présente à l'état de phase sigma.
  4. Substrat revêtu suivant l'une des revendications 1 à 3, caractérisé en ce que la proportion de phase sigma est d'au moins 50 % en volume.
  5. Substrat revêtu suivant l'une des revendications 1 à 4, caractérisé en ce que la couche et le substrat sont liés ensemble par un processus métallurgique.
  6. Procédé de production d'un substrat revêtu suivant l'une des revendications 1 à 5, procédé dans lequel la matière de revêtement est fondue conjointement avec la surface du substrat à revêtir, à l'aide d'un processus de fusion thermique puis elle est traitée à la chaleur après un refroidissement à au moins 500°C, caractérisé en ce que, après la fusion, on effectue le refroidissement à au moins 500°C à une vitesse minimale de refroidissement de 100 K/s, en produisant ainsi une couche protectrice en liaison métallurgique ayant une dureté inférieure à 500 HVO.1, et en ce que la couche protectrice est ensuite traitée à la chaleur à une température au maximum égale à 950°C jusqu'à ce que la dureté s'élève à au moins 800 HVO.1.
  7. Procédé suivant la revendication 6, caractérisé en ce que la matière constituant la couche est insufflée sous forme de poudre par une buse dans le bain de fusion, la matière formant la couche étant en même temps refondue et liée par un processus métallurgique avec le substrat.
  8. Procédé suivant la revendication 6, caractérisé en ce que le substrat est préalablement revêtu d'une couche de matière puis les deux matières sont reliées ensemble par un processus métallurgique par refonte.
  9. Procédé suivant l'une des revendications 6 à 8, caractérisé en ce que la fusion ou la refonte est effectuée avec un rayon laser, un faisceau d'électrons ou un arc électrique.
  10. Procédé suivant la revendication 8 ou 9, caractérisé en ce que le substrat est préchauffé avant le revêtement préalable.
  11. Procédé suivant l'une des revendications 8 à 10, caractérisé en ce que le substrat est préalablement revêtu par voie galvanique ou par un procédé de pulvérisation thermique.
  12. Procédé suivant l'une des revendications 6 à 11, caractérisé en ce que le traitement thermique est conduit à une température de 700 ± 25°C, que l'on maintient pendant au moins 6 heures.
EP90810867A 1990-01-22 1990-11-12 Substrat métallique revêtu Expired - Lifetime EP0438971B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT9090810867T ATE105594T1 (de) 1990-01-22 1990-11-12 Beschichtetes metallisches substrat.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH18190 1990-01-22
CH181/90 1990-01-22

Publications (2)

Publication Number Publication Date
EP0438971A1 EP0438971A1 (fr) 1991-07-31
EP0438971B1 true EP0438971B1 (fr) 1994-05-11

Family

ID=4181121

Family Applications (1)

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EP90810867A Expired - Lifetime EP0438971B1 (fr) 1990-01-22 1990-11-12 Substrat métallique revêtu

Country Status (6)

Country Link
US (1) US5230755A (fr)
EP (1) EP0438971B1 (fr)
JP (1) JP3065674B2 (fr)
AT (1) ATE105594T1 (fr)
DE (1) DE59005683D1 (fr)
ES (1) ES2053163T3 (fr)

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US5198268A (en) * 1991-11-14 1993-03-30 Xaloy, Incorporated Method for preparing a feed screw for processing plastics
WO1995029274A1 (fr) * 1994-04-26 1995-11-02 Igenwert Gmbh Procede permettant d'incorporer une matiere dans la region superficielle d'un corps solide et de la modifier, en particulier la region superficielle d'un materiau
US6350326B1 (en) 1996-01-15 2002-02-26 The University Of Tennessee Research Corporation Method for practicing a feedback controlled laser induced surface modification
DE19740696A1 (de) * 1997-09-16 1999-03-18 Bayerische Motoren Werke Ag Verfahren zur Herstellung und Bearbeitung metallischer Schichten
DK1045175T3 (da) * 1999-04-12 2007-02-19 Waertsilae Nsd Schweiz Ag Pakring
US6294225B1 (en) 1999-05-10 2001-09-25 The University Of Tennessee Research Corporation Method for improving the wear and corrosion resistance of material transport trailer surfaces
US6173886B1 (en) 1999-05-24 2001-01-16 The University Of Tennessee Research Corportion Method for joining dissimilar metals or alloys
US6299707B1 (en) 1999-05-24 2001-10-09 The University Of Tennessee Research Corporation Method for increasing the wear resistance in an aluminum cylinder bore
US6497985B2 (en) 1999-06-09 2002-12-24 University Of Tennessee Research Corporation Method for marking steel and aluminum alloys
US6284067B1 (en) 1999-07-02 2001-09-04 The University Of Tennessee Research Corporation Method for producing alloyed bands or strips on pistons for internal combustion engines
US6423162B1 (en) 1999-07-02 2002-07-23 The University Of Tennesse Research Corporation Method for producing decorative appearing bumper surfaces
US6229111B1 (en) 1999-10-13 2001-05-08 The University Of Tennessee Research Corporation Method for laser/plasma surface alloying
US6328026B1 (en) 1999-10-13 2001-12-11 The University Of Tennessee Research Corporation Method for increasing wear resistance in an engine cylinder bore and improved automotive engine
JP2004342845A (ja) * 2003-05-15 2004-12-02 Kobe Steel Ltd 微細構造体の洗浄装置
US7141110B2 (en) * 2003-11-21 2006-11-28 General Electric Company Erosion resistant coatings and methods thereof
US20050112399A1 (en) * 2003-11-21 2005-05-26 Gray Dennis M. Erosion resistant coatings and methods thereof
US7458358B2 (en) * 2006-05-10 2008-12-02 Federal Mogul World Wide, Inc. Thermal oxidation protective surface for steel pistons
JP2013241635A (ja) * 2012-05-18 2013-12-05 National Institute Of Advanced Industrial Science & Technology 鉄クロム合金
BR102014016213A2 (pt) * 2014-06-30 2016-02-10 Mahle Int Gmbh válvula para motores de combustão interna e processo para obtenção de uma válvula
CN104894560A (zh) * 2015-04-27 2015-09-09 苏州统明机械有限公司 一种用于金属表面抗氧化性能强的涂层及其制备方法
CN113549915B (zh) * 2021-06-16 2023-01-24 太原理工大学 一种矿用刮板机齿轨抗磨复合涂层及制备方法

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EP0266149A2 (fr) * 1986-10-27 1988-05-04 Hitachi, Ltd. Membre résistant à l'usure, son procédé de fabrication et valve l'utilisant dans une machine à combustion interne

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EP0266149A2 (fr) * 1986-10-27 1988-05-04 Hitachi, Ltd. Membre résistant à l'usure, son procédé de fabrication et valve l'utilisant dans une machine à combustion interne

Also Published As

Publication number Publication date
EP0438971A1 (fr) 1991-07-31
JPH04214879A (ja) 1992-08-05
US5230755A (en) 1993-07-27
ATE105594T1 (de) 1994-05-15
JP3065674B2 (ja) 2000-07-17
ES2053163T3 (es) 1994-07-16
DE59005683D1 (de) 1994-06-16

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