EP1558776B1 - Alliages haute temperature - Google Patents

Alliages haute temperature Download PDF

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EP1558776B1
EP1558776B1 EP03775499A EP03775499A EP1558776B1 EP 1558776 B1 EP1558776 B1 EP 1558776B1 EP 03775499 A EP03775499 A EP 03775499A EP 03775499 A EP03775499 A EP 03775499A EP 1558776 B1 EP1558776 B1 EP 1558776B1
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max
hafnium
alloy
chromium
nickel
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EP1558776A2 (fr
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Dominique Marianne Lucienne Flahaut
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PARALLOY Ltd
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Paralloy Ltd
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Priority claimed from GB0324859A external-priority patent/GB0324859D0/en
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    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
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    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
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    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • C—CHEMISTRY; METALLURGY
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    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • 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
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
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    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum

Definitions

  • This invention relates to high temperature alloys, and more particularly to oxide dispersion strengthened alloys having improved creep resistance and carburisation resistance at high temperatures.
  • high temperature alloys used for example, in the manufacture of alloy tubes for steam methane reforming, suffer from insufficient creep resistance.
  • high temperature alloys for example, alloy tubes used in ethylene pyrolysis, the alloys suffer from insufficient carburisation resistance and, in consequence, insufficient creep resistance.
  • INCOZOY ® alloy 803 (UNS S 35045), which is an iron-nickel-chromium alloy specifically designed for use in petrochemical, chemical and thermal processing applications.
  • the composition of INCOLOY 803, by weight, is 25%Cr, 35%Ni, 1%Mn, 0.6%Ti, 0.5%Al, 0.7%Si, 0.07%C and balance Fe. Relatively unsuccessful efforts have been made to improve the properties of this alloy by the addition of further alloying components and also by cladding.
  • alloy creep resistance can be considerably improved by adding a fine dispersion of oxide particles into a metallic matrix, yielding a so-called oxide dispersion strengthened (ODS) alloy.
  • ODS oxide dispersion strengthened
  • Such alloys exhibit a creep threshold, that is to say, below a certain stress their creep rate is very low. This behaviour is commonly explained by interfacial pinning of the moving dislocations at the oxide particle; Bartsch, M., A. Wasilkowska, A. Czyrska-Filemonowicz and U. Messerschmidt Materials Science & Engineering A 272, 152-162 (1999 ). It has recently been proposed to provide oxide dispersion strengthened clad tubes based on INCOLOY 803, but to date no entirely successful commercial product is available
  • the nickel-chromium-iron alloys in the ethylene pyrolysis market which have been produced to have good corrosion resistance and acceptable creep resistance mainly develop an oxide coating layer based on chromium oxide (with in some cases admixed silica).
  • This layer under excessively carburising service conditions high temperature, high carbon activity, low oxygen pressure
  • Alumina is known to be a very stable oxide and ideally it would be desirable to create an alumina layer on the surface of the nickel-chromium-iron alloy, for example, by adding aluminium to the melt.
  • aluminium has two highly detrimental effects on the mechanical properties of such alloys and especially on the creep resistance. Firstly, addition of aluminium to the melt can produce a dispersion of alumina in the alloy that can drastically reduce the creep resistance properties. Secondly, aluminium can form brittle Ni-Al phases in the alloy.
  • EP-A-0050408 describes iron-chromium-nickel alloys having aluminium and an optional hafnium addition.
  • JP-A-05001355 describes a heat resistant cast steel containing Nb and Hf for improved creep fracture strenght.
  • EP-A-0391381 describes nickel-chromium-iron alloys having an optional addition of hafnium.
  • US 5851318 describes nickel-chromium-iron alloys containing from 0.05 to 0.2% hafnium.
  • the invention provides a method of making an improved creep resistant nickel-chromium-iron alloy comprising up to about 5% by weight of hafnium-containing particles.
  • the invention provides an improved oxide dispersion strengthened nickel-chromium-iron alloy which comprises up to about 5% by weight of hafnium, with at least part of the hafnium being present as finely divided oxidised particles.
  • the invention provides a corrosion resistant nickel-chromium-iron-aluminium alloy comprising up to about 15%, preferably up to about 10%, by weight of aluminium and up to about 5% by weight of hafnium-containing particles.
  • the alloys of the invention are castable and can be formed into tubes and coils.
  • a method of making a nickel-chromium-iron alloy having a dispersion of finely divided hafnium oxide particles to deliver a dispersion strengthening effect the alloy having a composition comprising, by weight: Carbon 0.01 - 0.7% Silicon 0.1 - 3.0% Manganese 0 - 3.0% Nickel 15 - 90% Chromium 5 - 40% Molybdenum 0 - 3.0% Niobium 0 - 2.0% Tantalum 0 - 2.0% Titanium 0 - 2.0% Zirconium 0 - 2.0% Cobalt 0 - 2.0% Tungsten 0 - 4.0% Hafnium 0.01 - 4.5% Aluminium 0 - 15% Nitrogen 0.001 - 0.5% Oxygen 0.001 - 0.7% balance iron and incidental impurities, the alloy composition having the proviso, that at least one carbide forming element whose carbide is more stable than chromium carbide selected from niobium, tungsten, tantalum and zir
  • a preferred embodiment of the method of making an oxide dispersion strengthened nickel-chromium-iron castable alloy according to the invention comprises a composition, by weight: Carbon 0.01 - 0.5% Silicon 0.01 - 2.5% Manganese 0 - 2.5% Nickel 15 - 50% Chromium 20 - 40% Molybdenum 0 - 1.0% Niobium 0 - 1.7% Titanium 0 - 0.5% Zirconium 0 - 0.5% Cobalt 0 - 2.0% Tungsten 0 - 1.0% Hafnium 0.01 - 4.5% Aluminium 0 - 15% Balance iron and incidental impurities.
  • Preferred alloy compositions according to the method of the present invention include the following compositions: Carbon 0.3 to 0.7% Silicon 0.1 to 2.5% Manganese 2.5% max Nickel 30 to 40% Chromium 20 to 30% Molybdenum 3.0% max Niobium 2.0% max Hafnium 0.01% to 4.5% Titanium 0.5% max Zirconium 0.5% max Cobalt 2.0% max Tungsten 1.0% max Nitrogen 0.001 - 0.5% Oxygen 0.001 - 0.7% Balance iron and incidental impurities. Carbon 0.03 to 0.2% Silicon 0.1 to 0.25% Manganese 2.5% max. Nickel 30 to 40% Chromium 20 to 30% Molybdenum 3.0% max. Niobium 1.7% max. Hafnium 0.01 to 4.5% Titanium 0.5% max. Zirconium 0.5% max.
  • nickel-chromium-iron castable alloys include the following compositions, where all percentages are given by weight: Carbon Silicon Manganese Nickel Chromium Molybdenum A 0.3-0.5 0.1-2.5 2.5 max 30-40 20-30 1.0max B 0.03-0.2 0.1-2.5 2.5 max 30-40 20-30 1.0 max C 0.3-0.6 0.1-2.5 2.5 max 40-60 30-40 1.0 max D 0.03-0.2 0.1- 2.5 2.5 max 40-60 30-40 1.0 max E 0.30-0.5 0.1-2.5 2.5 max 19-22 24-27 1.0 max F 0.03-0.2 0.1-2.5 2.5 max 30-45 19-22 1.0 max Niobium Hafnium Optional Aluminium Titanium Zirconium Cobalt Tungste A 2 max 0.025 - 4.5 6.0 max 0.5 max 0.5 max 2.0 max 1.0 max B 2 max 0.025 - 4.5 6.0 max 0.5 max 0.5 max 2.0 max 1.0 max C 2 max 0.025 - 4.5 6.0 max 0.5 max 0.5 max 2.0 max 1.0 max D 2 max 0.025 -
  • the amount of hafnium in the alloy, by weight, is preferably from 0.05 to 3.0%, more preferably from 0.1% to 1.0% and most preferably from 0.2 to 0.5% for the high carbon alloy (0.3 - 0.6% carbon), and more than 1% for the low carbon alloy (0.03 - 0.2% carbon), preferably from 1% to 4.5%.
  • Hafnium is present in the alloy in the form of finely divided oxidised particles having an average particle size of less than 50 microns in the solidified metal.
  • Examples of particularly preferred alloy compositions according to the method of invention consist essentially of the following components, by weight: Carbon 0.45% Silicon 1.3% Manganese 0.9% Nickel 33.8% Chromium 25.7% Molybdenum 0.03% Niobium 0.85% Hafnium 0.25% Titanium 0.1% Zirconium 0.01% Cobalt 0.04% Tungsten 0.01% Nitrogen 0.1% Iron balance. Carbon 0.07% Silicon 1.0% Manganese 0.98% Nickel 32.5% Chromium 25.8% Molybdenum 0.20% Niobium 0.04% Hafnium 1.1% Titanium 0.12% Zirconium 0.01% Cobalt 0.04% Tungsten 0.08% Nitrogen 0.1% Iron balance.
  • Incidental impurities in the alloys of the invention can comprise, for example, phosphorus, sulphur, vanadium, zinc, arsenic, tin, lead, copper and cerium, up to a total amount of about 1.0%.
  • the invention provides a method of manufacturing an oxide dispersion strengthened nickel-chromium-iron alloy which comprises adding finely divided hafnium particles to a melt of the alloy before pouring, under conditions such that at least part of the hafnium is converted to oxide in the melt. To manufacture the alloys of the invention, it is important to provide conditions in the melt which permit oxidation of the hafnium particles without allowing detrimental reactions which would result in the hafnium (with or without aluminium) being taken up in the slag.
  • the correct oxidising conditions can be achieved by appropriate adjustment or additions of the components, for example, silicon and/or manganese, and by ensuring that unwanted contaminants are absent or kept to a minimum. If the slag is able to react with the oxidised hafnium particles this of course removes them detrimentally from the melt.
  • the level of oxygen in the melt can be varied by additions of, for example, one or more of silicon, niobium, titanium, zirconium, chromium, manganese, calcium and the optimum free oxygen level necessary to react with the hafnium particles can readily be found by routine experimentation.
  • any such micro-additions are made after the addition of hafnium.
  • alloying amounts of titanium and/or zirconium may be added, up to the specified limits of 0.5% by weight in each case.
  • the substantial removal of available free oxygen from the melt helps to ensure that any such titanium and/or zirconium additions do not form oxides, which could react detrimentally with the hafnium particles and reduce the yields of titanium, zirconium and hafnium present in the alloy.
  • hafnium is added to the melt as finely divided particles and that it is oxidised in situ .
  • hafnium added to nickel/chromium alloys in non-particulate form does not disperse, or reacts only with the carbon/nitrogen present resulting in a decrease of the alloy properties.
  • Attempts to add large pieces of hafnium to nickel/chromium micro-alloys have revealed that the hafnium does not disperse, but settles to the bottom of the alloy melt, and so is not present in the final casting.
  • hafnia hafnium oxide particles directly to the melt does not provide the desired dispersion strengthening either. Hafnia added in this way simply goes into the slag. According to the invention it has been found that it is necessary to carry out the oxidation of the hafnium particles in the melt in order to obtain the desired improvements.
  • the charge make up can be a virgin charge (pure metals), a mixture of virgin charge and reverts, a mixture of virgin charge and ingots, or a mixture of virgin charge and reverts and ingots.
  • the ingots can be made from argon/oxygen decarburisation (AOD) revert alloy treatment or from in-house reverts treated, for example, by argon purging.
  • AOD argon/oxygen decarburisation
  • the chemical composition of the melt should be carefully monitored to avoid contaminants and the formation of unwanted slag. Special care should be taken to deslag the bath, and the maximum amount of slag is preferably removed from the surface of the bath. It is possible to improve slag removal by the use of a neutral deslag powder.
  • the melt can be maintained in an argon atmosphere, but this is not essential.
  • the melt temperature is in the range of from 1500°C to 1700 °C, preferably from 1610 °C to 1670 °C for nickel-chromium-iron, and 1630°C to 1690C for nickel-chromium-iron-aluminium.
  • Hafnium particles are preferably added to the melt just before pouring the molten alloy into the mould. If a ladle is used, the hafnium is preferably added in the ladle. To improve the hafnium dispersion, the molten alloy is preferably stirred before pouring. Any type of hafnium can be used, but electrolytic hafnium is preferred.
  • the hafnium particles are preferably reduced in size as much as possible, for example, by grinding to a fine powder in a suitable mill.
  • the hafnium particles have a particle size of less than 5 mm, preferably less than 4 mm, with an average particle size of from 1 to 2 mm. When dispersed in the melt, the hafnium particles are further reduced in size.
  • the high carbon alloys of the invention (0.3 - 0.6% carbon) have a primary carbide network similar to the corresponding alloys without the oxide dispersion.
  • the primary carbides are mainly composed of chromium and/or iron carbo-nitrides, optionally with niobium, titanium and/or zirconium carbo-nitrides also present.
  • the invention also provides the possibility of obtaining a dispersion of secondary carbides after the alloy has been brought to a high temperature.
  • These secondary carbides are mainly chromium (or other elements such as iron) carbo-nitrides and optionally niobium, titanium (and/or zirconium) carbo-nitrides.
  • the low carbon alloys of the invention (0.03 - 0.2% carbon) can contain a dispersion of carbides, carbo-nitrides, or nitrides, for example, titanium nitrides, titanium carbo-nitrides, niobium carbides, niobium carbo-nitrides, niobium nitrides, zirconium nitrides, zirconium carbo-nitrides, zirconium carbides, tantalum carbides, tantalum carbo-nitrides, tantalum nitrides, tungsten carbides, tungsten nitrides, and/or tungsten carbo-nitrides.
  • the invention provides for the formation of a hafnia / hafnium oxide dispersion (the hafnium can be oxidised to form HfO 2 but it can be expected that there will also be formed an oxide HfO x with x as a variable).
  • alloys containing more than a trace of niobium and titanium for example, high carbon nickel-chromium-iron alloys, hafnium/niobium/titanium carbo-nitrides and (rarely) oxides mixtures (wherein the quantities of niobium and titanium are variable as well as the quantities of nitrogen and oxygen) can be expected to be present.
  • more numerous titanium nitride (and/or carbide) dispersions may be observed in the alloy, some of which may also contain hafnia particles. It is also possible that some hafnium carbo-nitrides may be formed.
  • an oxide dispersion strengthened nickel-chromium-iron alloy which comprises up to about 5% by weight of hafnium, with at least part of the hafnium being present as finely dispersed oxidised particles, the alloy having a carbon content of from 0.3% to 0.5% by weight and having improved high temperature creep resistance, leading to an improved service life expectancy.
  • the creep resistance of such high carbon alloys in the substantial absence of aluminium, derives from the ability of the particle dispersion to delay the motion of the dislocations in the alloy lattice.
  • the invention provides an oxide dispersion strengthened nickel-chromium-iron alloy, which comprises up to about 5% of hafnium, with at least part of the hafnium being present as finely dispersed oxidised particles, the alloy having a carbon content of from 0.03% - 0.2%, preferably 0.03% - 0.1%, more preferably 0.03% - 0.08%, for example, about 0.05% - 0.07%, and a significantly increased service temperature, preferably greater than 1150°C.
  • the improved high temperature performance of the new low carbon alloys of this further aspect of the invention is due to the replacement of the strengthening carbide dispersion by a hafnia dispersion which is more stable than the carbide at high temperature.
  • An example of a low carbon oxide dispersion strengthened alloy is alloy B in Table 1 (wherein aluminium is absent).
  • the nickel-chromium-iron alloy of the invention also comprises aluminium
  • the aluminium is preferably present in an amount of from 0.1% to 10% by weight, more preferably from 0.5% to 6% by weight and most preferably from.1.0 to 5% by weight.
  • a method of manufacturing a carburisation resistant nickel-chromium-iron alloy which comprises adding sequentially finely divided hafnium particles and aluminium to a melt of the alloy before pouring.
  • the aluminium is added to the melt immediately before pouring the molten alloy into the mould.
  • hafnium limits the amount of available oxygen in the alloy able to react with the aluminium and minimises or eliminates the formation of a detrimental dispersion of alumina particles.
  • the alloys of the invention can be formed into tubes, for example, by rotational moulding, and such rotationally moulded tubes are a further aspect of the invention.
  • the rotational moulding process can provide a non-uniform particle distribution in the tube wall, with the greater concentration of particles being towards the outer surface of the tube wall, and this can be beneficial in some cases.
  • the internal bore of the tube is machined, removing 4-5 mm of material; this gradient of concentration ensures that the hafnium/hafnia reinforcement is kept in the useful part of the tube.
  • Other components that can be manufactured from the new alloys include fittings, fully fabricated ethylene furnace assemblies, reformer tubes and manifolds.
  • hafnium addition For high chromium content (more than 10%) alloys, a further advantage of the hafnium addition is that it can tend to improve the oxide layer adherence at the surface of an alloy tube.
  • nickel-chromium-iron alloys are used in ethylene furnaces, they are able to develop an oxide layer on the surface that protects the alloy against corrosion by carburisation.
  • This protective oxide layer is formed ideally of chromium/manganese/silicon oxides, but can also include iron and nickel oxides.
  • the oxide layer has a tendency to spall during the tube service life (because of differences of coefficients of expansion with the alloy, compressive stresses in the oxide, etc). Spalling leaves the alloy unprotected against corrosion from the gaseous and particulate reactants of the ethylene cracking process. It has surprisingly been found that the addition of hafnium as described herein can tend to delay the spalling of the protective oxide layer.
  • the following melt composition is produced in a clean furnace: Nickel 35% Chromium 25% Carbon 0.4% Niobium 0.8 - 0.9% Silicon 1.6 - 1.8% Manganese 1.1 - 1.3% Iron balance.
  • the temperature of the melt is raised to a tap temperature of from 1640°C to 1650°C and the silicon content checked to obtain the correct oxidising conditions.
  • the furnace is then de-slaged, removing as much slag as possible.
  • 100kg of alloy are then tapped into a ladle and 0.35% hafnium particles of particle size maximum 5 mm, average 1 to 2 mm, are added to the tap stream. After the hafnium addition, 0.18% titanium, in the form of FeTi is added to the ladle.
  • the alloy in the ladle is stirred and immediately poured into a tube mould.
  • the creep resistance properties of the alloy thus produced were compared with the properties of an otherwise identical commercial alloy without hafnium.
  • Example 1 The procedure of Example 1 is repeated using the same melt composition except that the titanium addition is omitted.
  • the creep resistance properties of the alloy thus produced were compared with the properties of an otherwise identical commercial alloy from which the hafnium addition was omitted.
  • the results of a Larson-Miller plot of the stress-rupture properties of the commercial alloy derived from the regression analysis of numerous creep tests gave a typical figure of 16.2 MPa at a temperature of 1100°C.
  • the commercial alloy is expected to fail after a minimum of 100 hours, with a mean value failure of 202 hours.
  • the alloy according to the invention had a minimum failure time of rupture of 396 hours, a mean value failure of 430 hours and a maximum failure time of rupture of 629 hours.
  • This example describes the production of a low carbon oxide dispersion strengthened alloy according to the invention.
  • the following melt composition is produced in a clean furnace: Nickel 33% - 35% Chromium 24% - 26% Carbon 0.04% - 0.08% Silicon 1.0% - 1.2% Manganese 1.0% - 1.2% Molybdenum 0.14% - 0.3% Iron balance.
  • the temperature of the melt is raised to a tap temperature of from 1640°C to 1650°C and the silicon content checked.
  • the furnace is then de-slaged, removing as much slag as possible.
  • 100kg of alloy are then tapped into a ladle and 0.75% hafnium particles of particle size maximum 5 mm, average 1 - 2 mm, are added to the tap stream.
  • 0.25% titanium, in the form of FeTi is added to the ladle.
  • the alloy in the ladle is stirred and immediately poured into a tube mould.
  • FIG. 5 A photomicrograph of the alloy is shown in Figure 5 .
  • the dispersed oxidised particles can clearly be seen.
  • Example 3 The procedure of Example 3 is repeated using the same melt composition except that the hafnium addition is 0.5%.
  • a photomicrograph of the alloy is shown in Figure 6 .
  • the dispersed oxidised particles can clearly be seen.
  • Examples 3 and 4 show a higher solidus than the high carbon alloys of Examples 1 and 2, indeed their solidus is 1344°C instead of 1260°C for the high carbon alloys.
  • This Example describes the production of an oxide dispersion strengthened nickel-chromium-iron alloy according to the invention comprising both hafnium and aluminium.
  • a nickel-chromium-iron alloy melt having the following constituents by weight is formed in a clean furnace and brought to tapping temperature.
  • Example 5 has been tested to confirm that aluminium can improve the carburisation resistance of a hafnium-containing alloy according to the invention.
  • a very severe pack-carburisation test was performed, the results of which are shown in Figure 9 .
  • the creep resistance of the alloy was found to be substantially maintained compared to an identical alloy without hafnia and aluminium additions. Indeed only a decrease of maximum 20% in creep resistance was observed compared to an identical alloy without hafnium and aluminium additions.
  • an identical alloy with an aluminium addition, but without hafnium showed a decrease in creep resistance of 80%.

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Claims (22)

  1. Procédé pour réaliser un alliage nickel-chrome-fer, ayant une dispersion de particules oxyde Hf divisées finement, pour réaliser un effet de renforcement de dispersion, l'alliage ayant une composition comprenant, en poids : Carbone 0.01 - 0.7% Silicium 0.1 - 3.0% Mn 0-3.0% Nickel 15-90% Chrome 5-40% Mo 0-3.0% Nb 0-2.0% Tantale 0-2.0% Titanium 0-2.0% Zr 0-2.0% Co 0-2.0% Tungstène 0-4.0% Hf 0.01-4.5% Aluminium 0-15% Azote 0.001 - 0.5% Oxygène 0.001 - 0.7%
    le reste de fer et d'impuretés incidentes,
    la composition d'alliage étant telle qu'au moins un élément, formant un carbure dont le carbure est plus stable que le carbure de chrome, et choisi parmi Nb, titanium, tungstène, tantale, et Zr, est présent,
    le procédé comprenant les étapes de :
    - préparer une charge de métal ayant une composition requise ;
    - mélanger ladite charge de métal excepté pour la teneur en l'Hf et l'aluminium et/ou titane et/ou Zr, si de l'aluminium et/ou du titane et/ou du Zr est présent ;
    - porter le mélange à une température dans la gamme de 1500 à 1700°C ;
    - ajouter des particules de métal Hf finement divisées dans une quantité de 0,01 à 4,5 % en poids et ayant une taille inférieure à 5 mm, au mélange fondu, peu de temps avant le versement pour réagir avec l'oxygène libre ;
    - ajouter l'aluminium et/ou le titane et/ou le Zr, si présent, après l'addition de Hf ; et
    - verser le métal fondu dans un moule pour former un alliage découlée solidifié ayant une dispersion de particules oxyde Hf finement divisées, les particules ayant une de taille de particules moyenne inférieure à 50 microns dans le métal solidifié.
  2. Procédé selon la revendication 1, caractérisé en ce que le Hf est ajouté à un courant de piquée à partir d'un fourneau de fusion avant le versement dans un moule.
  3. Procédé selon la revendication 1, caractérisé en ce que les particules de Hf sont ajoutées à l'alliage fondu dans une poche de coulée.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le Hf est du Hf électrolytique.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le niveau d'oxygène dans le la partie fondue varie en fonction des additions de l'un ou plusieurs de Nb, titane et Zr.
  6. Procédé selon revendications 5, caractérisé en ce que le titane est ajouté sous la forme de TiFe après l'addition de Hf.
  7. Procédé fabrication d'un alliage résistants à la corrosion nickelchrome -- fer, selon l'une des revendications précédentes, caractérisé en ce qu'il comporte l'étape additionnelle d'ajouter des particules de Hf finement divisées avant l'aluminium à l'ensemble fondu de l'alliage avant le versement.
  8. Procédé selon la revendication 7, caractérisé en ce que le l'aluminium est ajouté au mélange fondue immédiatement avant versement de l'alliage fondu dans un moule.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'alliage est formé dans un tube par moulage rotatif.
  10. Procédé de réalisation d'un alliage à dispersion renforcée oxyde nickel-Cr-fer selon la revendication 1, comprenant en poids : Carbone 0.01 à 0.05% Silicium 0.01 à 2.5% Mn 0 à 2.5% Nickel 15 à 50% Chrome 20 à 40% Mo 0 à 1.0% Nb 0 à 1.7% Titane 0 à 0.5% Zr 0 à 0.5% Co 0 à 2.0% Tungstène 0 à 1.0% Hf 0.01 à 4.5% Aluminium 0 à 15%
    le reste étant du fer et des impuretés incidentes, et l'alliage étant tel qu'au moins un l'un parmi Nb, titane et Zr est présent.
  11. Procédé de réalisation d'un alliage selon la revendication 1, ayant la composition suivante en poids : Carbone 0.3 à 0.7% Silicium 0.1 à 2.5% Mn 2.5% max. Nickel 30 à 40% Chrome 20 à 30% Mo 3.0% max. Nb 2.0% max. Hf 0.01 à 4.5% Titane 0.5% max. Zr 0.5% max. Co 2.0% max. Tungstène 1.0% max. Azote 0.001- 0.5% Oxygène 0.001 - 0.7%
    le reste étant du fer et des impuretés incidentes.
  12. Procédé de fabrication d'alliage selon la revendication 1, ayant l'une des compositions suivantes, en poids : Carbone 0.3 à 0.7% Silicium 0.01 à 2.5% Mn 2.5% max. Nickel 40 à 60% Chrome 30 à 40% Mo 3.0% max. Nb 2.0% max. Hf 0.01 à 4.5% Titane 1.0% max. Zr 1.0% max. Co 2.0% max. Tungstène 1.0% max AI 0-15.0% Azote 0.001 - 0.5% Oxygène 0.001 - 0.7%
    le reste étant du fer et des impuretés incidentes, ou Carbone 0.3 à 0.7% Silicium 0.01 à 2.5% Mn 2.5% max. Nickel 19 à 22% Chrome 24 à 27% Mo 3.0% max. Nb 2.0% max. Hf 0.01 à 4.5% Co 2.0% max. Tungstène 1.0% max. Al 0 - 15.0% Azote 0.001 - 0.5% Oxygène 0.001 - 0.7%
    le reste étant du fer et des impuretés incidentes.
  13. Procédé pour fabriquer un alliage selon l'une des revendications 1 et 10 à 12, et ayant une teneur en carbone de 0,3 jusqu'à 0,5 % en poids.
  14. Procédé pour fabriquer un alliage selon l'une des revendications 1 ou 10, ayant une teneur en carbone de 0,03 jusqu'à 0,2 % en poids.
  15. Procédé de fabrication d'un alliage selon la revendication 1, ayant l'une des compositions suivantes, en poids : Carbone 0.03 à 0.2% Silicium 0.1 à 0.25% Mn 2.5% max. Nickel 30 à 40% Chrome 20 à 30% Mo 3.0% max. Nb 1.7% max. Hf 0.01 à 4.5% Titane 0.5% max. Zr 0.5% max. Co 2.05% max. Tungstène 1.0% max. Al 0-15.0% Azote 0.001-0.5% Oxygène 0.001-0.7%
    le reste étant du fer et des impuretés incidentes, ou Carbone 0.03 à 0.2% Silicium 0.1 à 2.5% Mn 2.5% max. Nickel 30 à 45% Chrome 30 à 40% Mo 3.0% max. Nb 2.0% max. Hf 0.01 à 4.5% Co 2.0% max. Tungstène 1.0% Al 0-15.0% Azote 0.001 - 0.5% Oxygène 0.001 - 0.7%
    le reste étant du fer et des impuretés incidentes, ou Carbone 0.03 à 0.2% Silicium 0.1 à 2.5% Mn 2.5% max. Nickel 30 à 45% Chrome 19 à 22% Mo 3.0% max. Nb 2.0% max. Hf 0.01 à 4.5% Titane 0.5% max. Zr 0.5% max. Co 2.0% max. Tungstène 1.0% max. Al 0-15.0% Azote 0.001 - 0.5% Oxygène 0.001 - 0.7%
    le reste étant du fer et des impuretés incidentes.
  16. Procédé de fabrication d'un alliage selon la revendication 1, dans lequel la quantité de carbone dans l'alliage, en poids, est de 0,3 à 0,6 % et la quantité de Hf en poids est de 0,01 jusqu'à 3,0 %.
  17. Procédé pour réaliser un alliage selon la revendication 16, dans lequel la quantité de Hf est en poids de 0,1 % à 1,0 %.
  18. Procédé pour réaliser un alliage selon revendications 17, dans lequel la quantité de Hf est en poids de 0,2 jusqu'à 0,5 % en poids.
  19. Procédé pour réaliser un alliage selon l'une des revendications 1,12 et 15 à 18, dans lequel la quantité d'aluminium en poids est de 0,1 % à 10 %, la quantité de Hf en poids est de 0,01 % à 4,5 %.
  20. Procédé de réalisation d'un alliage selon la revendication 19, dans lequel la quantité d'aluminium en poids est de 0,1 à 6 % et la quantité de Hf en poids est de 0,1 % à 1,0 %.
  21. Procédé de réalisation d'un alliage selon la revendication 19 août 20, dans lequel la quantité d'aluminium est en poids de 0,1 % à 4,5 % et la quantité de Hf en poids est de 0,2 % à 0,5 %.
  22. Procédé de régression un alliage selon la revendication 1, ayant l'une des compositions suivantes, en poids : Carbone 0.45% Silicium 1.3% Mn 0.9% Nickel 33.8% Chrome 25.7% Mo 0.03% Nb 0.85% Hf 0.25% Titane 0.1% Zr 0.01% Co 0.04% Tungstène 0.01% Azote 0.1%
    le reste étant du fer et des impuretés incidentes, ou Carbone 0.07% Silicium 1.0% Mn 0.98% Nickel 32.5% Chrome 25.8% Mo 0.20% Nb 0.04% Hf 1.1% Titane 0.12% Zr 0.01% Co 0.04% Tungstène 0.08% Azote 0.1%
    le reste étant du fer et des impuretés incidentes, ou Carbone 0.34% Silicium 1.68% Mn 1.10% Nickel 32.0% Chrome 21.3% Mo 0.01% Nb 0.80% Hf 0.25% Titane 0.12% Zr 0.01% AI 3.28% Co 0.04% Tungstène 0.01 %
    le reste étant du fer et des impuretés incidentes, ou Carbone 0.42% Silicium 1.79% Mn 1.17% Nickel 33.2% Chrome 23.3% Mo 0.02% Nb 0.77%
EP03775499A 2002-11-04 2003-10-30 Alliages haute temperature Expired - Lifetime EP1558776B8 (fr)

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GB0225648A GB2394959A (en) 2002-11-04 2002-11-04 Hafnium particle dispersion hardened nickel-chromium-iron alloys
GB0225648 2002-11-04
GBGB0228576.5A GB0228576D0 (en) 2002-11-04 2002-12-09 High temperature alloys
GB0228576 2002-12-09
GB0324859A GB0324859D0 (en) 2002-11-04 2003-10-24 High temperature alloys
GB0324859 2003-10-24
PCT/GB2003/004665 WO2004042100A2 (fr) 2002-11-04 2003-10-30 Alliages haute temperature

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AU2003283525A8 (en) 2004-06-07
GB0325297D0 (en) 2003-12-03
EP1558776A2 (fr) 2005-08-03
EP1935996A1 (fr) 2008-06-25
JP2006505694A (ja) 2006-02-16
EP1558776B8 (fr) 2009-04-29
US20070144622A1 (en) 2007-06-28
WO2004042100A3 (fr) 2004-08-19
GB2394960A (en) 2004-05-12
GB2394960B (en) 2007-04-25
AU2003283525A1 (en) 2004-06-07

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