EP2668308B1 - Matériau de pulvérisation en forme de fil pour le dépôt par pulverisation themique d'une couche ayant des phases perlitiques, bainitiques et martensitiques - Google Patents

Matériau de pulvérisation en forme de fil pour le dépôt par pulverisation themique d'une couche ayant des phases perlitiques, bainitiques et martensitiques Download PDF

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Publication number
EP2668308B1
EP2668308B1 EP11791465.5A EP11791465A EP2668308B1 EP 2668308 B1 EP2668308 B1 EP 2668308B1 EP 11791465 A EP11791465 A EP 11791465A EP 2668308 B1 EP2668308 B1 EP 2668308B1
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EP
European Patent Office
Prior art keywords
wire
spraying
layer
weight
spray material
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Application number
EP11791465.5A
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German (de)
English (en)
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EP2668308A1 (fr
Inventor
Patrick Izquierdo
Eyuep Akin ÖZDENIZ
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.)
Mercedes Benz Group AG
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Daimler AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]

Definitions

  • the invention relates to a wire-shaped spray material, in particular for arc wire spraying, comprising essentially iron and a thermally sprayed layer which is deposited on a substrate.
  • engine components such as cylinder bores or their walls are provided with a tread layer or it liners are inserted into the cylinder bores, which are provided with a tread layer.
  • the application of such tread layers mostly takes place by means of thermal spraying, for example electric arc wire spraying.
  • arc wire spraying an electric arc is generated by applying a voltage between two wire-shaped spray materials.
  • the wire tips melt and are conveyed, for example, by means of a nebulizer gas to the surface to be coated, for example, the cylinder wall, where they accumulate.
  • a cylinder liner for internal combustion engines comprising a base body with a wear protection coating on the tread, based on a hard iron alloy with carbon and oxygen, wherein the wear protection layer martensitic Has phases and oxides and the wear protection layer in the arc-wire spraying method is applicable and the alloy of the coating has a carbon content of 0.05 to 3 wt .-%.
  • wire-formed spray material for a thermally sprayed iron-based layer having a bainitic martinsitic structure which has a carbon content of 0.23 wt.% to 0.4 wt.% and a chromium content of 0.75 wt.% to 0.95 wt .% and other alloying constituents.
  • wire-formed spray material for a thermally sprayed iron-based layer having a bainitic martinsitic structure which has a carbon content of 0.35 wt.% to 0.55 wt.% and a copper content of 0.25 wt.% to 0.35 wt .% and other alloying constituents.
  • a wire-shaped spray material for a thermally sprayed iron-based layer having a pearlitic, bainitic, martinsitic structure which has a carbon content of from 0.1% by weight to 0.28% by weight and a silicon content of from 0.05% by weight to zero , 3 wt.% And other alloying constituents.
  • wire-shaped spray material for a thermally sprayed iron-based layer known which has a carbon content of 0.04% by weight to 0.2% by weight, a silicon content of 0.025% by weight to 0.04% by weight, a manganese content of 0.04% by weight to 2% by weight, a Chromium content of 0.02% by weight to 2% by weight, a molybdenum content of 0.02% by weight to 2% by weight, a nickel content of 0.02% by weight to 4 and a copper content of 0.02% by weight. to 0.5 wt.% And other alloying ingredients.
  • the spray properties of the wire-shaped spray material and the machinability of the spray layer are selectively influenced in addition to the layer properties.
  • An inventive wire-shaped spray material in particular for arc wire spraying, essentially comprises iron.
  • the spray material is formed at least with carbon as a micro-alloy in such a way that at least pearlite and bainite are formed upon solidification of the spray material, micro-alloying elements being additionally provided for forming wear-resistant phases and for improving the tribological properties.
  • Microalloys are those alloys which are predominantly formed from a constituent to which only minor amounts of further constituents are added relative to a total mass.
  • Fine-grained pearlite consisting of hard Fe3C and ferrite, is a tribologically positive effective phase.
  • Bainite is a conversion phase of medium hardness and wear resistance.
  • Martensite is a hard, wear-resistant structure. The formation of martensite can be selectively influenced by the type of cooling of the spray material and by the choice of alloying components of the microalloy.
  • the ratio of bainite to perlite can be influenced in a targeted manner by the type of cooling of the spray material and by the choice of the alloy constituents of the microalloy.
  • a layer on a substrate, for example a cylinder running surface, produced by means of an arc wire spraying using the spray material according to the invention comprises perlite and bainite and wear-resistant martensite islands.
  • Tribologically active phases serve to improve the running behavior in critical system states, so that z. B. when tearing off lubricating films excessive wear of the friction partners or their damage can be avoided by adhesive reactions. These states occur especially in mixed friction regions, e.g. OT and UT areas in tribological systems Cylinder surfaces / piston rings.
  • FIG. 1 For example, a substrate 1 with a sheet 2 deposited by arc wire spraying (LDS) is shown.
  • LDS arc wire spraying
  • two wire-shaped spray materials 4 are supplied. Between the wire-shaped spray materials 4, an arc 5 is ignited.
  • the wire-shaped spray material 4 melts and is selectively applied by means of a carrier gas to the substrate 1 to be coated, where it cools, solidifies and forms the layer 2.
  • the wire-shaped spray material 4 essentially comprises iron.
  • the spray material is formed at least with carbon as a micro-alloy in such a way that pearlite and bainite are already formed upon solidification of the spray material.
  • alloy constituents are provided in the microplating for the formation of wear-resistant phases of martensite and for reducing the coefficient of friction.
  • the quantities are in percent by weight in each case based on a total weight, unless otherwise specified.
  • the elements vanadium, molybdenum, phosphorus, sulfur and aluminum and nickel are preferably contained at least in traces, i. in proportions of at least 0.001% by weight. Preference is given to maximum contents of 0.15% by weight. for vanadium, 0.1% by weight. for nickel, 0.03 wt.%. for molybdenum and 0.01 wt.%. for the other elements mentioned.
  • the main component of the microalloy is iron.
  • Arc wire spraying with a wire-shaped spray material 4 formed from these micro alloys results in a particularly homogeneous layer 2 with low porosity and low roughness.
  • the low carbon content and the increased manganese content and the increased silicon content of the microalloy result in an improved spray behavior, which is characterized in that small regular, viscous droplets are formed in the arc wire spraying. Due to their viscosity, they decay only slightly in flight and on impact to finer particles and thus tend less to oxidation. Lower surface oxidation promotes adhesion of the particles to the substrate - layer adhesion - and adhesion of the particles to each other - layered cohesion.
  • the increased manganese content leads to a predominantly pearlitic / bainitic microstructure during the solidification of the sprayed layer 2.
  • Bainite is a tough intermediate structure of carbonaceous steels.
  • Perlite is a mixed structure of soft ferritic and hard carbide phases. The formation of bainite and perlite can be influenced by spray parameters, the type of cooling of the spray material and the choice of the alloy components of the microalloy.
  • the layer 2 is formed in the form of a soft, ductile matrix of pearlite and bainite with hard, wear-resistant islands of martensite.
  • the wire-shaped spray material 4 is preferably hot rolled and / or hot drawn and then cooled slowly and controlled in an oven and / or annealed to obtain a ductile structure, so that the wire-shaped spray material 4 remains flexible.
  • the alloy components of the wire are dimensioned so that the burn-up of certain elements, eg carbon, is taken into account.
  • the alloy composition of layer 2 is changed according to the burnup.
  • the wire composition is tuned to the target properties of the sprayed layer
  • a surface of the wire-shaped spray material 4 is copper plated in order to avoid corrosion.
  • the wire is low alloy, with the choice being geared specifically to low cost alloying elements.
  • the resulting sprayed coating exhibits good machinability and improved tribological properties as well as good wear resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating By Spraying Or Casting (AREA)

Claims (5)

  1. Substance de pulvérisation (4) sous forme de fil, en particulier destinée à la projection à l'arc électrique, caractérisée en ce que la substance de pulvérisation (4) comprend au moins du carbone en tant que micro-alliage de sorte que lors de la solidification de la substance de pulvérisation, se forment de la perlite, de la bainite et de la martensite, caractérisée en ce que les composants d'alliage étant les suivants :
    • le carbone compris entre 0,28 % en poids et 0,6 % en poids,
    • le silicium compris entre 0,6 % en poids et 0,8 % en poids,
    • le manganèse compris entre 1,0 % en poids et 1,4 % en poids,
    • le chrome compris entre 0,05 % en poids et 0,35 % en poids,
    • le cuivre compris entre 0,04 % en poids et 0,15 % en poids,
    • l'azote compris entre 0,005 % en poids et 0,03 % en poids,
    et des composants sélectionnés en option tels que la vanadinite, le nickel, le molybdène, le phosphore, le soufre et l'aluminium, le reste étant constitué de fer et des impuretés inévitables respectivement par rapport au poids total.
  2. Substance de pulvérisation (4) sous la forme de fil selon la revendication 1, caractérisé en que sont compris par rapport au poids total :
    une teneur de vanadinite inférieure ou égale à 0,15 % en poids,
    une teneur de nickel inférieure ou égale à 0,1 % en poids,
    une teneur de molybdène inférieure ou égale à 0,03 % en poids,
    une teneur en phosphore, en soufre et en aluminium inférieure ou égale à 0,01 % en poids.
  3. Substance de pulvérisation (4) sous forme de fil selon l'une quelconque des revendications précédentes, caractérisée en ce qu'il est prévu un cuivrage d'une face de la substance de pulvérisation (4).
  4. Couche pulvérisée thermiquement à base de fer, caractérisée en ce qu'elle comprend les composants d'alliage suivants :
    • du carbone compris entre 0,28 % en poids et 0,6 % en poids,
    • du silicium compris entre 0,6 % en poids et 0,8 % en poids,
    • du manganèse compris entre 1,0 % en poids et 1,4 % en poids,
    • du chrome compris entre 0,05 % en poids et 0,35 % en poids,
    • du cuivre compris entre 0,04 % en poids et 0,15 % en poids,
    • de l'azote compris entre 0,005 % en poids et 0,03 % en poids,
    et des composants sélectionnés en option tels que la vanadinite, le nickel, le molybdène, le phosphore, le soufre et l'aluminium, le reste étant constitué de fer et des impuretés inévitables respectivement par rapport au poids total.
  5. Couche pulvérisée thermiquement selon la revendication 4, caractérisée en ce qu'elle est disposée en tant que couche de bande de roulement à l'intérieur d'un carter de vilebrequin.
EP11791465.5A 2011-01-26 2011-12-07 Matériau de pulvérisation en forme de fil pour le dépôt par pulverisation themique d'une couche ayant des phases perlitiques, bainitiques et martensitiques Active EP2668308B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011009443A DE102011009443B3 (de) 2011-01-26 2011-01-26 Drahtförmiger Spritzwerkstoff
PCT/EP2011/006130 WO2012100798A1 (fr) 2011-01-26 2011-12-07 Matériau à projeter filiforme permettant l'obtention d'une couche à structure perlitique, bainitique, martensitique par projection thermique

Publications (2)

Publication Number Publication Date
EP2668308A1 EP2668308A1 (fr) 2013-12-04
EP2668308B1 true EP2668308B1 (fr) 2016-06-08

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US (1) US9546414B2 (fr)
EP (1) EP2668308B1 (fr)
JP (1) JP5710025B2 (fr)
CN (1) CN103328678B (fr)
DE (1) DE102011009443B3 (fr)
WO (1) WO2012100798A1 (fr)

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DE102012009496B4 (de) 2012-05-14 2017-05-11 Stahlwerk Ergste Westig Gmbh Chromstahl
DE102015207833A1 (de) 2015-04-28 2016-11-03 Volkswagen Aktiengesellschaft Zylinderkurbelgehäuse für einen Verbrennungsmotor
KR101719201B1 (ko) * 2015-07-10 2017-04-10 한성피앤에스(주) 스테인리스 클래드 강판과 그 제조방법
KR101912415B1 (ko) * 2016-11-17 2018-10-26 한성피앤에스(주) 스테인리스 클래드 강판과 그 제조방법
US10982310B2 (en) 2018-04-09 2021-04-20 ResOps, LLC Corrosion resistant thermal spray alloy
US11742605B2 (en) * 2019-11-20 2023-08-29 Lawrence Livermore National Security, Llc Apparatus and method for high density detachable electrical interface
CN112502845A (zh) * 2020-11-30 2021-03-16 安庆帝伯格茨缸套有限公司 一种内圆三段式高耐磨气密性气缸套

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DE102010021300B4 (de) * 2010-05-22 2012-03-22 Daimler Ag Drahtförmiger Spritzwerkstoff, damit erzeugbare Funktionsschicht und Verfahren zum Beschichten eines Substrats mit einem Spritzwerkstoff

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Publication number Publication date
CN103328678A (zh) 2013-09-25
JP2014509260A (ja) 2014-04-17
DE102011009443B3 (de) 2012-03-29
EP2668308A1 (fr) 2013-12-04
WO2012100798A1 (fr) 2012-08-02
US20130295412A1 (en) 2013-11-07
CN103328678B (zh) 2015-12-02
JP5710025B2 (ja) 2015-04-30
US9546414B2 (en) 2017-01-17

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