EP0139784A1 - Alliages nickel-fer et leurs emplois et applications - Google Patents

Alliages nickel-fer et leurs emplois et applications Download PDF

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Publication number
EP0139784A1
EP0139784A1 EP83110885A EP83110885A EP0139784A1 EP 0139784 A1 EP0139784 A1 EP 0139784A1 EP 83110885 A EP83110885 A EP 83110885A EP 83110885 A EP83110885 A EP 83110885A EP 0139784 A1 EP0139784 A1 EP 0139784A1
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EP
European Patent Office
Prior art keywords
nickel
iron
atomic
awaruite
product according
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EP83110885A
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German (de)
English (en)
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John Malcolm Bird
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Individual
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • 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

Definitions

  • Industrial metals especially the industrial ferrous metals, are used in a great variety of applications in natural environments, such as pipes, bridges, ships, towers, oil and gas drilling rigs, marine piping and valves, rock mining equipment, electrical facilities, and pipe lines for the transport of fluids and slurries.
  • Corrosion protection for ferrous metals used in various natural and artificial environments is provided by coatings such as paints, wrappings and galvanizings, and metal laminations.
  • coatings such as paints, wrappings and galvanizings, and metal laminations.
  • ferrous alloy formulations known as stainless steels that are corrosion resistant.
  • ferrous metal and alloys thereof will become corroded and decomposed by rusting within several to tens of years when exposed to the weather, or used in marine and underground applications, or used in corrosive environments such as boilers and heat exchangers. Many various coatings used to retard corrosion of ferrous metals are themselves unstable in natural environments.
  • Awaruite is the mineral name for naturally occurring iron-nickel alloys having the y' (gamma-prime) structure.
  • the most common composition of awaruite corresponds to the formula FeNi 3 which is that of an ordered, stoichiometric phase.
  • Awaruite may contain small amounts of copper and cobalt metal, e.g., less than about 5 atomic percent each. It is formed in nature during the hydrothermal alteration of ultramafic rock (serpentinization) at temperatures around 300-400° centigrade.
  • Awaruite is known both as a mineral component of altered ultramafic rocks and as detrital grains in sediments produced by the erosion of altered ultramafic rocks.
  • Awaruite has survived for thousands to millions of years.
  • Awaruite is stable over wide ranges of Eh, pH, temperature, pressure and varying compositions of groundwater.
  • Awaruite is stable in groundwater containing substantial amounts of chloride ions, oxygen and other solutes in natural geochemical environments.
  • the ranges of compositions and temperatures within which alloys of iron and nickel have the ordered face-centered cubic structure ( ⁇ or gamma-prime) have been studied by Josso (1) (1950), Geisler( 2 ) (1953), V iting( 3 ) (1957) and Heumann and Karsten( 4 ) (1963).
  • the single-phase stability field for y' is centered about the composition FeNi3; see Figure 1.
  • the stability field first appears at approximately 500°C and broadens to compositions with greater and less nickel with decreasing temperature.
  • the single-phase stability field of y' is separated from the single phase field of disordered face-centered cubic iron-nickel alloys (y' or gamma) by a two-phase region of co-existing y and y' .
  • relatively nickel-poor y' alloy transforms to a two-phase assemblage of a (alpha) iron and ⁇ alloy. This transformation may be inhibited or prevented at low temperatures by slow kinetics.
  • compositions of terrestial iron-nickel alloys range from 64 to 96 atomic percent nickel, but occurrences of natural, single-phase alloys known to have the y' structure exhibit a more limited range of compositions, supporting the interpretation of Viting of a narrow ⁇ ' field; see Figure 3.
  • the invention is directed to novel industrial metals, especially industrial ferrous metals, the surface of which is characterized by a coating or bonding of an ordered, crystalline, synthetic alloy of nickel and iron.
  • novel coated industrial metals have a very long life-time because they exhibit high corrosion resistance (substantially exceeding the corrosion resistance of the industrial metal(s) per se) to a wide variety of chemical and hydrothermal conditions which are generally associated in marine, underground, atmospheric and man-made environments.
  • the ordered, crystalline nickel-iron alloy while synthetically made, essentially has the properties of the naturally occurring iron-nickel mineral awaruite (produced under thermodynamically stable conditions within serpentine- type rocks) and a composition in the range exhibited by the mineral awaruite.
  • the synthetic alloys used in the practice of the invention(s) are within the range which consists essentially of from about 64 to about 83 atomic percent nickel and from about 36 to about 17 atomic percent iron and are within the single-phase y' region of the,phase diagram ( Figure 1) of the work by V. T. Heumann and G. Karsten (1963).
  • the synthetic alloys are within the range which consists essentially of from about 72.5 to about 78 atomic percent nickel and from about 275 to about 22 atomic percent iron and are within the single-phase y' region of the phase diagram ( Figure 2) of the work by L. M. Viting (1957). It is preferred to employ synthetic alloys in which the atomic percent ratio of nickel to iron is approximately 75:25. At this ratio relatively fast cooling rates can be used to bring a melt of FeNi 3 to an ordered crystalline state. Small amounts of cobalt or copper, or both, can be contained in the synthetic alloy, e.g., up to about 5 atomic percent cobalt, copper, or mixture of both. Desirably, the synthetic nickel-iron alloy will not contain more than about 2 atomic percent of Co and/or Cu.
  • corrosion represents the undesirable deterioration of a metal, i.e., an interaction of the metal with its environment which adversely affects those properties of the metal which it is desired to preserve( 5 ).
  • synthetic alloy per se or coated with the synthetic alloy are steam turbine components, boiler tubes, radiators, convertors, heat exchanger components, rivets, buoys, sheets, plates, ship hull components, bearing seals, oil well "Christmas trees", marine and surface piping, signs, antennae, cables, bolts, shafts, propellers, metallic markers and reflectors, towers, bridge components, I-beams, girders, concrete reinforcing bars, building panels and other components, components and parts of vehicles, e.g., automobile, train, motorcycle, boat, etc., especially exterior parts such as bumpers, fenders; frames, chassis and other body portions of an automobile.
  • Such fabricated or coated industrial metal products or components can be used as a material of construction in, for example, drilling rigs, rock mining equipment, paper mills, sulfate processing plants, power plants, petroleum cracking and refining plants, radioactive processing plants, fertilizer plants, diffusion plants, and desalination plants.
  • novel coated articles of commerce as illustrated above which are characterized by a higher resistance to corrosion as compared to the corrosion resistance of the corresponding uncoated article of commerce.
  • the novel coated article or component is characterized by high corrosion resistance which represents a difference in kind compared to the corrosion resistance of the corresponding uncoated article or component.
  • the synthetic nickel-iron alloys of the invention are particularly applicable as a coating for the various industrial metals including the well-known metals and alloys of construction, to improve their corrosion resistance in a wide variety of (corrosive) environments illustrated previously.
  • Industrial metals include, in particular, the various so-called ferrous metals, alloys, and other common "metals of construction," e.g., cast iron, steel, etc.
  • the synthetic nickel-iron alloy can be prepared by melting in a furnace, preferably in an inert atmosphere, a mixture of nickel and iron in the proper proportion, e.g., 75 atomic % Ni and 25 atomic % Fe, followed by slowly cooling the melt. At approximatey 500°C the single-phase y' forms. Slow cooling is continued, preferably with annealing at about 490°C to 400°C for several hours, until there is obtained the syntehtic ordered FeNi 3 alloy at room temperature, e.g., about 20°C.
  • the synthetic alloy of the invention can be coated on industrial ferrous metals and other metals by various conventional techniques including, for example, hot-dipping, arc-plasma spraying, hot-pressing and rolling, or any other method which does not significantly alter the composition of the FeNi 3 alloy.
  • the coating or bonding of the synthetic alloy on the industrial metal substrate greatly enhances the resistance of the metal substrate against the corrosive effects of the various environments illustrated previously.
  • the thickness of such coating or bond on the metal substrate can be in the range of several angstroms to several microns, and thicker, e.g., several mils.
  • the novel product or article may consist essentially of the synthetic Ni-Fe alloy per se.
  • a sample of artificial awaruite was prepared by melting a mixture of 25 weight % Fe and 75 weight % Ni. This melt was produced and cooled in an inert atmosphere in an induction furnace. The melt was cooled slowly to room temperature. An ingot about 1" x 3" was produced. Samples of this ingot were used for Debye-Scherrer X-ray deffraction analysis and electron microprobe analysis.
  • the results of the electron microprobe analyses establish that the artificial awaruite and the natural awaruite have essentially the same chemical composition. Therefore, the behavior of the natural and artificial awaruite in various geochemical environments, and indeed, various "corrosive" environments, would be the same.
  • Various geologic occurrences of natural awaruite demonstrate the remarkable chemical stability of this mineral over very long intervals of time, exceeding millions of years( 6 ). Artificial awaruite would behave the same as natural awaruite in such various geochemical environments.
  • the naturally occurring iron-nickel mineral awaruite can be used in the practice of the invention(s) described herein.
  • the question of economics with respect to the mineral awaruite is dependent mainly on its availability and size of its deposits which are limited at this time.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
EP83110885A 1983-11-02 1983-11-02 Alliages nickel-fer et leurs emplois et applications Withdrawn EP0139784A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP83110885A EP0139784A1 (fr) 1983-11-02 1983-11-02 Alliages nickel-fer et leurs emplois et applications

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83110885A EP0139784A1 (fr) 1983-11-02 1983-11-02 Alliages nickel-fer et leurs emplois et applications

Publications (1)

Publication Number Publication Date
EP0139784A1 true EP0139784A1 (fr) 1985-05-08

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1762730A (en) * 1926-10-30 1930-06-10 Bell Telephone Labor Inc Heat treatment of magnetic materials
FR720331A (fr) * 1930-10-18 1932-02-18 Commentry Alliages additionnés de bore et leur traitement thermique
DE867006C (de) * 1950-07-06 1953-02-12 Vacuumschmelze Ag Verfahren zur Verbesserung der magnetischen Eigenschaften von kupferhaltigen Nickel-Eisen-Legierungen
FR2104808A1 (fr) * 1970-07-27 1972-04-21 Bbc Brown Boveri & Cie
DE2402827A1 (de) * 1973-01-30 1974-08-01 Cockerill Verfahren zur erzeugung einer nichtrostenden beschichtung auf eisenerzeugnissen
US4055447A (en) * 1976-05-07 1977-10-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Directionally solidified eutectic γ-γ' nickel-base superalloys
US4337167A (en) * 1978-02-15 1982-06-29 Bird John M Container for radioactive nuclear waste materials
US4433033A (en) * 1982-08-30 1984-02-21 Bird John M Industrial metals coated with awaruite-like synthetic nickel/iron alloys

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1762730A (en) * 1926-10-30 1930-06-10 Bell Telephone Labor Inc Heat treatment of magnetic materials
FR720331A (fr) * 1930-10-18 1932-02-18 Commentry Alliages additionnés de bore et leur traitement thermique
DE867006C (de) * 1950-07-06 1953-02-12 Vacuumschmelze Ag Verfahren zur Verbesserung der magnetischen Eigenschaften von kupferhaltigen Nickel-Eisen-Legierungen
FR2104808A1 (fr) * 1970-07-27 1972-04-21 Bbc Brown Boveri & Cie
DE2402827A1 (de) * 1973-01-30 1974-08-01 Cockerill Verfahren zur erzeugung einer nichtrostenden beschichtung auf eisenerzeugnissen
US4055447A (en) * 1976-05-07 1977-10-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Directionally solidified eutectic γ-γ' nickel-base superalloys
US4337167A (en) * 1978-02-15 1982-06-29 Bird John M Container for radioactive nuclear waste materials
US4433033A (en) * 1982-08-30 1984-02-21 Bird John M Industrial metals coated with awaruite-like synthetic nickel/iron alloys

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