WO2017118751A1 - Method for producing a corrosion resistant metal substrate and corrosion resistant metal substrate provided thereby - Google Patents

Method for producing a corrosion resistant metal substrate and corrosion resistant metal substrate provided thereby Download PDF

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Publication number
WO2017118751A1
WO2017118751A1 PCT/EP2017/050291 EP2017050291W WO2017118751A1 WO 2017118751 A1 WO2017118751 A1 WO 2017118751A1 EP 2017050291 W EP2017050291 W EP 2017050291W WO 2017118751 A1 WO2017118751 A1 WO 2017118751A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
substrate
layer
molybdenum
molybdenum oxide
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
PCT/EP2017/050291
Other languages
English (en)
French (fr)
Inventor
Annette Borisch
Philip SCHMITZ
Ken-Dominic FLECHTNER
Martin SCHWAGEREIT
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.)
Hille and Muller GmbH
Original Assignee
Hille and Muller GmbH
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 Hille and Muller GmbH filed Critical Hille and Muller GmbH
Priority to CN201780011655.0A priority Critical patent/CN108699719B/zh
Priority to JP2018535393A priority patent/JP6880038B2/ja
Priority to EP17700205.2A priority patent/EP3400324B1/en
Priority to CA3010553A priority patent/CA3010553C/en
Publication of WO2017118751A1 publication Critical patent/WO2017118751A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/04—Pretreatment of the material to be coated
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
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    • C23C18/1646—Characteristics of the product obtained
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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    • 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
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    • 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
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    • 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]
    • Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • 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
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • 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
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • 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
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • This invention relates to a method for producing a corrosion resistant metal substrate and corrosion resistant metal substrate provided thereby.
  • One particularly important ferrous alloy alloying element is chromium.
  • stainless steel By adding sufficient chromium, stainless steel is formed. When stainless steel is heated, chromium forms a protective chromium oxide coating that delays further oxidation. A minimum of about 10.5% chromium is usually required to passivate the surface and to classify a material as stainless steel. So long as this oxide layer is stable and continuous, the metal substrate is well protected from corrosion. Since about the mid-1990s, plain carbon and low alloy steels have been replaced by stainless steel as the primary material for exhaust systems. This transition has taken place because of market demands for extended warranties, and because of demands mandated by emission standards. Technologies to meet increasingly stringent emission standards can raise exhaust temperatures which makes the task of meeting strength and durability requirements especially challenging. Emission standards also require that exhaust systems are designed in a manner that facilitates leak- free assembly, installation and operation for the full useful life of the vehicle.
  • a nickel or nickel-based layer on a steel or aluminium substrate or ii. a nickel or nickel-based layer on a steel or aluminium substrate followed by providing a cobalt layer on the nickel or nickel-based layer, to form a plated substrate followed by electrodepositing a molybdenum oxide layer from an aqueous solution onto the plated substrate, wherein the plated substrate acts as a cathode, wherein the aqueous solution comprises a molybdenum salt and an alkali metal phosphate and wherein the pH of the aqueous solution is adjusted to between 4.0 and 6.5, wherein the plated substrate provided with the molybdenum oxide layer is subjected to an annealing step in a reducing atmosphere to, at least partly, reduce the molybdenum oxide in the molybdenum oxide layer to molybdenum metal in a reduction annealing step and to form, simultaneously or subsequently, in the annealing step a diffusion layer which contains nickel and molyb
  • the diffusion layer contains nickel, molybdenum and optionally cobalt. There may be other components in the diffusion layer such as phosphate.
  • the metal substrate which may be provided in the form of a coiled strip of steel such as (low) carbon steel or stainless steel, or in the form a coiled strip of aluminium or aluminium alloy with a suitable chemical composition for the application of the final product, is provided with a nickel layer, or a nickel- based layer, and optionally with a cobalt layer on top of the nickel or nickel- based layer to form a plated substrate.
  • Nickel layers can for instance be deposited onto the substrate in a Watts nickel plating bath.
  • a nickel-based layer is a layer predominantly consisting of nickel but not solely of nickel.
  • a nickel alloy layer is therefore considered a nickel based layer.
  • nickel layer hereinafter intends to include “nickel-based layer”.
  • the corrosion protection offered by the nickel layer may be insufficient for certain applications as a result of the presence of pores in the nickel layer.
  • the cobalt layer is used to improve the corrosion resistance of the nickel plated substrate.
  • the plated substrate is then led through the said aqueous solution in an electroplating device in which the plated substrate acts as the cathode, and provided with the molybdenum oxide layer.
  • the molybdenum oxide in the molybdenum oxide layer is then reduced to molybdenum metal in a reduction annealing step and, as a consequence of the high temperature during the reduction annealing step, the molybdenum diffuses into the nickel and/or cobalt layer, thereby forming a diffusion layer comprising nickel, molybdenum and optionally cobalt.
  • the reduction annealing step is also the diffusion annealing step. This is the preferable case.
  • the annealing step can be prolonged to further promote the diffusion after the reduction of the molybdenum oxide has been completed.
  • the reducing atmosphere is a hydrogen containing atmosphere, such as substantially pure hydrogen or HNX.
  • the diffusion layer comprising nickel and molybdenum, and optionally cobalt, is pore free, and provides an excellent protection of the substrate.
  • the molybdenum salt is ammonium molybdate
  • the phosphate is sodium dihydrogen phosphate
  • KH 2 P0 4 Potassium dihydrogen phosphate
  • the nickel layer (or nickel- based layer) provided on the substrate is between 0.5 and 5 ⁇ in thickness.
  • This thickness range provides sufficient thickness for the diffusion layer after the reduction annealing to be effective.
  • the diffusion layer comprising of nickel, originating from the nickel or nickel-based layer, and optionally cobalt, originating from the optional cobalt layer, and molybdenum, originating from the reduced molybdenum oxide layer, has a thickness of between 10 and 200 nm.
  • a preferable minimum thickness is 20 nm, and a preferable maximum thickness is 150 nm.
  • the thickness of the diffusion layer is between 50 and 100 nm.
  • the temperature of the aqueous solution for the electrodeposition of the molybdenum oxide layer onto the nickel plated substrate is between 40 °C and 75 °C, and/or
  • the plating time for the electrodeposition of the molybdenum oxide layer onto the nickel plated substrate is between 5 and 30 seconds, and/or the current density for the electrodeposition of the molybdenum oxide layer onto the nickel plated substrate is between 2 and 25 A/dm 2 , and/or the maximum annealing temperature during the annealing step is between 500 and 1050 °C, and/or
  • the annealing time is between 6 and 10 hours for a batch annealing process or between 10 and 120 seconds for a continuous annealing process.
  • the temperature of the aqueous solution is at least 51 °C and/or at most 69 °C.
  • the plating time is preferably at most 20 seconds, whereas it is preferable that the current density for the electrodeposition of the molybdenum oxide layer is at least 6 and/or at most 22 A/dm 2 . More preferably the temperature of the aqueous solution is at least 55 °C and/or at most 65 °C.
  • the plating time for the electrodeposition of the cobalt layer onto the nickel plated substrate is between 5 and 40 seconds, and/or the current density for the electrodeposition of the cobalt layer onto the nickel plated substrate is between 2 and 25 A/dm 2 , and/or
  • the plating bath for the cobalt layer is a chloride based cobalt plating bath, see e.g. Table 10, page 354 of "Nickel, Cobalt, and their Alloys", ASM Specialty Handbook, ed. J.R. Davis., ASM International, 2000 (See Figure 4).
  • the maximum annealing temperature is 700 °C, preferably 650 °C and more preferably 600 °C to prevent too large an impact on the properties of the steel substrate.
  • the maximum annealing temperature is 900 °C, preferably 850 °C and more preferably 800 °C to prevent too large an impact on the properties of the steel substrate.
  • the lower limit of the annealing temperature is controlled largely by the lay-out of the annealing facilities and of the economy of the process. The lower the temperature, the longer it takes for a Ni-Mo-diffusion layer of a desired thickness to form.
  • the allowable temperatures are lower.
  • the maximum annealing temperature depends on the alloy is at most 500 and preferably at most 450 °C to prevent too large an impact on the properties of the substrate.
  • a suitable temperature can be determined easily by simple trial and error. As the temperature is lower, the required diffusion time increases.
  • the annealing time in the batch annealing process is between 6 and 10 hours, preferably at most 8.5 hours and more preferably at most 7.5 hours.
  • the annealing time is at most 120 seconds, preferably at most 95 s, more preferably at most 75 s and even more preferably at most 40 s.
  • a suitable minimum continuous annealing temperature is 5 s, preferably at least 10 s. There is a degree of interchangeability between the annealing time and the annealing temperature.
  • the aqueous solution for the electrodeposition of the molybdenum oxide layer onto the plated substrate comprises:
  • This composition allows to effectively and reproducibly deposit the molybdenum oxide layer. It is noted that 30 g/l of ( ⁇ 4 ) 6 ⁇ 7 ⁇ 2 4 corresponds to 0.024 mol/l and 50 g/l of NaH 2 P0 4 to 0.42 mol/l.
  • the thickness of the deposited molybdenum oxide layer is at most 100 nm, preferably at most 75, more preferably 50 nm, and even more preferably 40 nm.
  • the minimum thickness is at least 10 nm.
  • the pH of the aqueous solution is at least 4.5 and/or at most 6.
  • the pH is at least 5.25 and/or at most 5.75.
  • the cathodic current density for depositing the molybdenum oxide layer is at least 12.5 A/dm 2 and preferably at least 15 A/dm 2 .
  • the steel substrate is a carbon steel, preferably a low carbon steel, extra-low carbon steel or a HSLA-steel.
  • These unalloyed (LC and ELC) or micro-alloyed (HSLA) steels are relatively cheap substrates and provide good strength and formability.
  • the steels are produced by means of commonly known processes such as casting, hot-rolling and cold-rolling.
  • Low carbon steels typically comprise 0.05 to 0.15 wt.% C and extra low carbon steels typically comprise 0.02 to 0.05 wt.% C.
  • Other elements may be present in addition to carbon in accordance with EN 10020-2000 which prescribes how much of a certain element may be present to still be considered an unalloyed steel.
  • High-strength low-alloy (HSLA) steels are designed to provide better mechanical properties and/or greater resistance to atmospheric corrosion than carbon steels.
  • the HSLA steels have low carbon contents (0.05-0.15% C) in order to produce adequate formability and weldability, and they have manganese contents up to 2.0%.
  • Small quantities of chromium, nickel, molybdenum, copper, nitrogen, vanadium, niobium, titanium and zirconium are used in various combinations to achieve the desired properties.
  • the steel substrate has been cold- rolled to its final thickness, usually between 0.15 and 1.5 mm, and the cold- rolled steel substrate may or may not have been recrystallisation or recovery annealed prior to depositing the nickel and optional cobalt layer according to the invention.
  • the steel substrate is preferably supplied in the form of a coiled strip.
  • the steel substrate is a ferritic stainless steel, such as an SAE 400-series, which generally are considered to have better engineering properties than austenitic stainless steel grades, but have reduced corrosion resistance, because of the lower chromium and nickel content. They are also usually less expensive.
  • Ferritic stainless steels have a body-centered cubic crystal structure and contain between 10.5% and 27% chromium with very little nickel, if any.
  • the steel SAE 430 (1.4016) proved to be a useful substrate for the method according to the invention.
  • the stainless steel substrate has been cold-rolled to its final thickness, usually between 0.15 and 1.5 mm, and the cold-rolled steel substrate may or may not have been recrystallisation or recovery annealed prior to depositing the nickel and optional cobalt layer according to the invention.
  • the stainless steel substrate is preferably supplied in the form of a coiled strip.
  • the substrate for the method according to the invention may also be an aluminium or an aluminium alloy substrate.
  • the diffusion layer comprising of nickel originating from the nickel or nickel-based layer and molybdenum originating from the molybdenum oxide layer also comprises phosphor, preferably 5 to 15 wt.% of phosphor, more preferably 6 to 13 wt.%. A suitable maximum amount is 10 wt.%. A suitable minimum amount is 7 wt.%.
  • phosphor preferably 5 to 15 wt.% of phosphor, more preferably 6 to 13 wt.%.
  • a suitable maximum amount is 10 wt.%.
  • a suitable minimum amount is 7 wt.%.
  • the invention is also embodied in a corrosion resistant metal substrate provided with a diffusion layer comprising nickel, molybdenum and optionally cobalt, produced according to the invention wherein the diffusion layer (i.e. the Ni-Mo- or Ni-Mo-Co-diffusion layer) has a thickness of between 10 and 200 nm.
  • the diffusion layer i.e. the Ni-Mo- or Ni-Mo-Co-diffusion layer
  • the thickness of the Ni-Mo-diffusion layer is between 50 and 100 nm. This thickness can be determined e.g. by means of GDOES.
  • the thickness of the layer is determined by locating the halfvalue (ignoring the surface effects) of the Mo-curve.
  • the invention is embodied in an exhaust system or parts for an exhaust system produced from the metal substrate according to the invention.
  • the metal substrate according to the invention is used in fuel lines for instance for internal combustion engines.
  • Ni-Mo-diffusion layer has a thickness of about 150 nm at the surface of the coated substrate.
  • igure 1 shows a non-limitative example of the implementation of the process according to the invention.
  • the hot-rolled starting product is pickled to remove the oxides from the strip and clean the surface.
  • the strip is cold-rolled.
  • the various layers are electrodeposited.
  • the diffusion annealing takes place.
  • the cold-rolling can obviously also take place elsewhere when the cold-rolled coil is bought from a supplier of cold rolled coil.
  • Figure 2 shows a GDOES-measurement of the surface after depositing the molybdenum oxide on the nickel layer.
  • the X-axis gives the thickness in nm and the Y-axis gives the concentration in wt%. Note that the values for carbon and sulphur are in fact 10 times as low as presented.
  • the nickel layer is 2 ⁇ (i.e. 2000 nm), whereas the molybdenum oxide layer is about 60 nm.
  • Figure 3 shows a GDOES-measurement of the surface after annealing the layers of Figure 2. Note that the values for carbon and sulphur are in fact 10 times as low as presented. The clearly discernable layer of molybdenum oxide on top of the nickel layer has vanished, and a diffusion layer comprising nickel and molybdenum is shown. There is still a degree of oxygen present in the surface layers, but this is believed to be associated with re-oxidation if the surface, and with the presence of the phosphates, and not with the molybdenum oxide which has reduced to metallic molybdenum.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Exhaust Silencers (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Chemically Coating (AREA)
  • Laminated Bodies (AREA)
PCT/EP2017/050291 2016-01-07 2017-01-08 Method for producing a corrosion resistant metal substrate and corrosion resistant metal substrate provided thereby Ceased WO2017118751A1 (en)

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CN201780011655.0A CN108699719B (zh) 2016-01-07 2017-01-08 用于制造耐腐蚀金属基材的方法和由此提供的耐腐蚀金属基材
JP2018535393A JP6880038B2 (ja) 2016-01-07 2017-01-08 耐食性金属基板の製造方法およびそれにより提供される耐食性金属基板
EP17700205.2A EP3400324B1 (en) 2016-01-07 2017-01-08 Method for producing a corrosion resistant metal substrate and corrosion resistant metal substrate provided thereby
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WO2019011932A1 (en) * 2017-07-12 2019-01-17 Hille & Müller GMBH LOW INTERFACIAL CONTACT RESISTANCE MATERIAL, USE THEREOF, AND PROCESS FOR PRODUCING SAID MATERIAL

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JP7251527B2 (ja) * 2020-07-14 2023-04-04 株式会社デンソー ガスセンサ
CN114559046B (zh) * 2022-01-26 2023-07-25 中北大学 一种增材制造用稀土改性17-4ph高强钢粉末的制备方法

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US20100167087A1 (en) * 2007-07-13 2010-07-01 Hille & Muller Gmbh Method of providing a metallic coating layer and substrate provided with said coating layer
JP2010209405A (ja) * 2009-03-10 2010-09-24 Nisshin Steel Co Ltd 表面電気伝導性に優れたステンレス鋼材およびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019011932A1 (en) * 2017-07-12 2019-01-17 Hille & Müller GMBH LOW INTERFACIAL CONTACT RESISTANCE MATERIAL, USE THEREOF, AND PROCESS FOR PRODUCING SAID MATERIAL
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JP6880038B2 (ja) 2021-06-02
US20170198624A1 (en) 2017-07-13
CA3010553C (en) 2020-12-29
US9951674B2 (en) 2018-04-24
JP2019508580A (ja) 2019-03-28
CN108699719A (zh) 2018-10-23
US10337388B2 (en) 2019-07-02
CA3010553A1 (en) 2017-07-13
US20180171858A1 (en) 2018-06-21

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