EP2480695B1 - Procédé de fabrication une alliage de fe-cr - Google Patents

Procédé de fabrication une alliage de fe-cr Download PDF

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EP2480695B1
EP2480695B1 EP10760237.7A EP10760237A EP2480695B1 EP 2480695 B1 EP2480695 B1 EP 2480695B1 EP 10760237 A EP10760237 A EP 10760237A EP 2480695 B1 EP2480695 B1 EP 2480695B1
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semi
finished product
alloy
max
temperature
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EP2480695A1 (fr
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Heike Hattendorf
Osman Ibas
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VDM Metals International GmbH
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VDM Metals International GmbH
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    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/02—Hardening by precipitation
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum

Definitions

  • the invention relates to a method for producing a component from a Laves phase and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides ausscheidenden, iron-chromium alloy.
  • a ferritic Cr-containing steel which has the following composition: C ⁇ 0.03%, Mn ⁇ 5.0%, Cr 6 - 40%, N ⁇ 0.03%, Si ⁇ 5%, W 2.0 - 6.0%, balance iron and manufacturing impurities.
  • the material has a mean thermal expansion coefficient in the temperature range of 20 to 800 ° C in the range ⁇ 12.6 x 10 -6 / ° C.
  • the molten steel is formed into semi-finished products, which are then hot-rolled and annealed in the temperature range of 950 to 1150 ° C.
  • the hot-rolled and annealed sheets are then cold-formed and subjected to a final annealing treatment in the temperature range of 1020 to 1200 ° C.
  • a high temperature material comprising comprising a chromium oxide-forming iron alloy with up to 2 wt .-% of at least one oxygen-affinity element from the group Y, Ce, Zr, Hf and Al, up to 2 wt .-% of an element M from the group Mn , Ni and Co, which forms with chromium oxide at high temperatures a spinel phase of the type MCr 2 O 4 , up to 2 wt .-% of another element from the group Ti, Hf, Sr, Ca and Zr, which is the electrical conductivity of oxides increased on Cr basis.
  • the chromium content should be present in a concentration range between 12 and 28%. Areas of application for this high-temperature material are bipolar plates in a high-temperature fuel cell.
  • the EP 1 298 228 A1 relates to a steel for a high temperature fuel cell having the following composition: not more than 0.2% C, not more than 1 % Si, not more than 1% Mn, not more than 2% Ni, 15-30% Cr, not more than 1% Al, not more than 0.5% Y, not more than 0.2% SE and not more as 1% Zr, balance iron and manufacturing impurities.
  • a creep-resistant ferritic steel comprising precipitates of an intermetallic phase of the type Fe 2 (M, Si) or Fe 7 (M, Si) 6 with at least one metallic alloying element M formed by the elements niobium, molybdenum, tungsten or tantalum can be.
  • the steel should preferably be used for a bipolar plate in a fuel cell stack.
  • a metallic material for fuel cells including C ⁇ 0.2%, 0.02 to 1% Si, ⁇ 2% Mn, 10 to 40% Cr, 0.03 to 5% Mo, 0.1 to 3% Nb, at least one of the elements of the group Sc, Y, La, Ce, Pr, Nd, Pm, Sn, Zr and Hf ⁇ 1%, the remainder being iron and unavoidable impurities, the composition satisfying the following equation: 0.1 ⁇ Mo / Nb ⁇ 30.
  • the EP 1 882 756 A1 describes a ferritic chrome steel, in particular usable in fuel cells.
  • the chromium steel has the following composition: C max. 0.1%, Si 0.1-1%, Mn max. 0.6%, Cr 15-25%, Ni max. 2%, Mo 0.5-2%, Nb 0.2-1.5%, Ti max. 0.5%, Zr max. 0.5%, SE max. 0.3%, Al max. 0.1%, N max. 0.07%, remainder Fe and impurities caused by melting, the content of Zr + Ti being at least 0.2%.
  • interconnector steel of a high-temperature fuel cell are, in addition to the above-mentioned creep resistance, a very good corrosion resistance, a good conductivity of the oxide layer and a low chromium evaporation.
  • the requirements of the reformer and the heat exchanger for the high-temperature fuel cell are as good as possible creep resistance, a very good corrosion resistance and low chromium evaporation.
  • the oxide does not have to be conductive for these components.
  • the requirements for components for example, for the exhaust system of an internal combustion engine or for steam boilers, superheated, turbines, and other parts of a power plant are the best possible creep resistance, a very good corrosion resistance.
  • the chromium evaporation does not produce any poisoning phenomena here, as in the fuel cell, and the protective oxide does not have to be conductive for such components.
  • the excellent corrosion resistance is achieved by forming a chromium oxide topcoat. Due to the fact that a spinel with Mn, Ni, Co or Cu is additionally formed on the chromium oxide topcoat, less volatile chromium oxides or chromium oxyhydroxides form, which poison the cathode. By stably bonding Si in the Laves phase Fe 2 (M, Si) or Fe 7 (M, Si) 6 , no non-conductive underlayer of silicon oxide also forms under the chromium oxide topcoat. The corrosion resistance is further improved by keeping the Al content low and thus avoiding the increase of corrosion by the internal oxidation of the aluminum.
  • a low addition of Ti additionally solidifies the surface and prevents bulging of the oxide layer and the inclusion of metallic areas in the oxide layer, which increases the oxidation.
  • oxygen-affine elements such as La, Ce, Y, Zr or the like further increases the corrosion resistance.
  • a sample is subjected to a constant static tension at a constant temperature. For reasons of comparability, this tensile force is given as the initial tensile stress in relation to the initial sample cross-section.
  • the time to break t B - the break time - of the sample is measured in the simplest case. The test can then be carried out without strain measurement on the sample during the test. The elongation at break is then measured after the end of the experiment.
  • the sample is installed in the creeping machine at room temperature and heated to the desired temperature with no tensile force. After reaching the test temperature, the sample is held for one hour without temperature load for temperature compensation. Thereafter, the sample is loaded with the tensile force and the test time begins.
  • the break time can be taken as a measure of the creep resistance. The greater the break time at a given temperature and initial tensile stress, the more creep resistant the material is. Breaking time and creep resistance decrease with increasing temperature and increasing initial tensile stress (see eg "Bürgel" page 100)
  • the deformability is determined in a tensile test according to DIN 50145 at room temperature.
  • the yield strength R p0.2 , the tensile strength R M and the elongation to breakage are determined.
  • the elongation at break is provided with indices: A 5 .
  • the amount of elongation A in the tensile test at room temperature can be taken as a measure of the deformability.
  • the Laves phase (s) or the Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides can be visualized on a metallographic grinding by etching with V2A pickling or electrolytic etching with oxalic acid do.
  • V2A pickling When etching with V2A pickling, the grains or grain boundaries are additionally visibly etched.
  • metallography is only used as an aid in explaining that the effectiveness of a measure is conveniently evaluated by break time or creep resistance.
  • a process for producing a sheet of ferritic stainless steel having good processability and lower anisotropy comprising the steps of providing a ferritic stainless steel consisting of up to 0.03% C, up to 0.03% N, up to 2.0% Si, up to 2.0% Mn, up to 0.6% Ni, 9-35% Cr, 0.15-0.80% Nb, optionally up to 0.5% Ti, up to 3% Mo, up to 2% Cu and up to 6% Al, balance Fe and unavoidable impurities.
  • This stainless steel is subjected to precipitation heating at a temperature in the range of 700 to 850 ° C for a period of ⁇ 25 hours.
  • the stainless steel is tempered in the temperature range between 900 and 1100 ° C for a period of ⁇ 1 minute.
  • a sheet-shaped semi-finished product is produced.
  • the sheet is to be used for motor vehicles and other parts.
  • the EP 1 698 711 A1 a production process for a ferritic Cr-containing steel.
  • the chemical composition of the molten steel includes ⁇ 0.03% C, ⁇ 5.0% Mn, 6-40% Cr, ⁇ 0.03% N, ⁇ 5% Si, 2-6% W, balance iron and unavoidable impurities ,
  • This steel is formed into plates, which are then subjected to a hot rolling process.
  • the hot-rolled sheets produced in this way are then subjected to an annealing treatment in the temperature range between 950 and 1150 ° C.
  • the sheet is subjected to a cold rolling process and a final annealing process in the temperature range between 1020 and 1200 ° C subjected.
  • This semifinished product can then be further processed and used in the area of a vehicle (exhaust gas guidance system).
  • the EP 1 176 220 A1 discloses a ferromagnetic stainless steel sheet of the following composition: C ⁇ 0.02%, Si 0.2-1.0%, Mn ⁇ 1.5%, Cr 11-20%, Ni 0.05-2.0%, Mo 1.0-2.0%, Al ⁇ 1.0%, Nb 0.2 - 0.8%, N ⁇ 0.02%, balance Fe.
  • the invention has for its object to provide a method for producing a precipitation hardened iron-chromium alloy component, by means of which, while maintaining an acceptable ductility at room temperature, the high heat resistance or creep resistance of a precipitation-hardened ferritic alloy over the prior art further increase.
  • This object is achieved by methods for producing a component, of a Laves phases and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides ausscheidenden, iron-chromium alloy of the following composition (in% by weight) Cr 12 - 30% Mn 0.001 - 2.5% Nb 0.1 - 2% W 0.1 - 5% Si 0.05 - 1% C 0.002 - 0.1% N 0.002 - 0.1% S Max.
  • the alloy may optionally contain the following elements: La 0.02 - 0.3% Ti 0.01-0.5%, one or more of the elements Ce, Pr, Ne, Sc, Y, Zr, Hf 0.02 - 0.3% al 0.001-0.5% or 2.0-6.0%, one or more of the elements mg 0.0001 - 0.07% Ca 0.0001 - 0.07% P 0.002-0.03%, one or more of the elements Ni, Co, Cu 0.01 - 3.0% B up to 0.005%, V Max. 0.2% and / or S Max. 0.005% O Max. 0.01% Zn Max. 0.01% sn Max. 0.01% pb Max. 0.01% se Max. 0.01% Te Max. 0.01% Bi Max. 0.01% sb Max.
  • the W content can, if necessary, be replaced in whole or in part by at least one of the elements Mo and / or Ta, Fe rest as well as the usual impurities caused by melting by subjecting a semi-finished product made of the alloy to a thermomechanical treatment, wherein in a first step the alloy is at temperatures ⁇ the solution annealing temperature, at a temperature ⁇ 1050 ° C for more than 6 minutes or at a temperature ⁇ 1060 ° C for more than 1 minute, solution annealing, followed by cooling in inert gas or air, agitated (blown) inert gas or air or in water, in a second step mechanical deformation of the semi-finished product in the range of 0.05 to 99% and in a subsequent step Laves phases Fe 2 (M, Si) or Fe 7 (M, Si) 6 and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing Particles and / or carbides are deliberately and finely dispersed thereby excreted, that the manufactured
  • the temperatures for the creep test preferably being in the range between 500 and 1000 ° C.
  • a semi-finished product made of an alloy of the following composition is treated thermomechanically: Cr 12 to 30% Mn 0.001 to 2.5% Nb 0.1 to 2% W 0.1 to 5% Si 0.05 to 1% C 0.002 to 0.03% N 0.002 to 0.03% S Max. 0.01% Fe rest as well as the usual smelting-related impurities.
  • the method according to the invention makes it possible to produce semi-finished products in the form of sheets, strips, rods, forgings, pipes or wire and to manufacture components in a wide variety of shapes required for the respective application.
  • the solution annealing temperature preferably ⁇ 1050 ° C for more than 6 minutes, respectively> 1060 ° C for more than 1 minute, followed by cooling in static inert gas or air, moving (blown ) Inert gas or air or water in the initial state prior to deformation in the semi-finished product only a few or no Laves phases Fe 2 (M, Si) or Fe 7 (M, Si) 6 and / or Fe-containing particles and / or Cr -containing particles or Si-containing particles and / or carbides are present in the alloy.
  • the deformation of the semifinished product can be done by hot working. Alternatively, however, the deformation can also be brought about by cold working.
  • the semi-finished product with a starting temperature> 1070 ° C is thermoformed, the last 0.05 to 95% of mechanical deformation between 1000 ° and 500 ° C are applied, advantageously the last 0.5 to 90% between 1000 ° C and 500 ° C.
  • the degree of cold working of the semifinished product is 0.05 to 99%, advantageously 0.05 to 95% or 0.05 to 90%.
  • alloy already mentioned is to be used as an interconnector for a solid oxide fuel cell, a content of 0.001-0.5% aluminum is advantageous.
  • a content of 2 to 6% aluminum is advantageous, since then can form a closed aluminum oxide, compared to a chromium oxide layer again a much lower growth rate and in addition still has lower Chromoxidabdampfung than a chromium-manganese spinel.
  • both variants can be considered. It should be remembered in particular that with increasing aluminum content, the processability and weldability of the alloy deteriorates, resulting in higher costs. Therefore, if an oxide layer consisting of a chromium oxide and a chromium-manganese spinel, sufficient oxidation resistance can be ensured by using 0.001-0.5% aluminum. If a higher oxidation resistance is required, as is ensured, for example, by the formation of an aluminum oxide layer, a content of 2.0-6.0% aluminum is advantageous. These two alloy variants can be used for example as components for the exhaust system of an internal combustion engine or for steam boilers, superheated, turbines and other parts of a power plant.
  • a preferred aluminum range is in particular the range of 2.5% to 5.0%, which is still characterized by good processability.
  • the following elements can additionally be introduced individually or in combination into the alloy already mentioned: La 0.02 to 0.3% Ti 0.01 to 0.5% mg 0.0001 to 0.07% Ca 0.0001 to 0.07% P 0.002 to 0.03% Ni / Co / Cu 0.01 to 3% B up to 0.005%.
  • the contents of the additional elements which can be introduced in the alloy can be set as follows: Mg 0.0001 to 0.05%, Ca 0.0001 to 0.03%, P 0.002 to 0.03%.
  • the alloy (in% by weight) of one or more of the elements Ce, La, Pr, Ne, Sc, Y, Zr or Hf may contain, in contents, 0.02-0.3%.
  • the alloy (in% by weight) of one or more of the elements Ce, Pr, Ne, Sc, Y, Zr or Hf may contain in amounts 0.02-0.2%.
  • the Nb content is 0.3 to 1.0% and the Si content is 0.15 to 0.5%.
  • the element tungsten may be wholly or partly replaced by at least one of the elements Mo or Ta.
  • the alloy can also max. 0.2% V and / or max. 0.005% S included.
  • the oxygen content should not be greater than 0.01%.
  • the alloy can also max. Containing 0.003% boron.
  • the alloy should each have a maximum of 0.01% of the following elements: Zn, Sn, Pb, Se, Te, Bi, Sb.
  • Components / semi-finished products which consist on the one hand of the mentioned alloy composition and on the other hand produced by the method according to the invention can preferably be used as an interconnector in a fuel cell or as a material in a component, such as a reformer or a heat exchanger in an auxiliary unit of the fuel cell.
  • the component / semifinished product produced by the method according to the invention, or the alloy itself is also possible to use as a component in the exhaust system of an internal combustion engine or for steam boilers, superheaters, turbines and other parts of a power plant or in the chemical process industry.
  • Laves phases can be excreted selectively and finely distributed at the dislocations of the microstructure by means of the method according to the invention.
  • the first step of a Laves phase and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides ausschenden iron-chromium alloy in the thermomechanical treatment must have a Annealing above the solution annealing temperature, so that the Laves phases and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides are brought into solution and the elimination for subsequent thermomechanical treatment available stand.
  • the solution annealing temperature is alloy-dependent, but is preferably above 1050 ° C for more than 6 minutes, or above 1060 ° C for more than 1 minute, followed by quenching in inert gas or air, moving (blown) inert gas, or Air or in water.
  • the exact temperature control above this solution annealing temperature is not decisive for the properties.
  • the annealing can be done in air or under inert gas. It should be below the melting temperature, preferably ⁇ 1350 ° C. For reasons of cost, the annealing times should preferably be ⁇ 24 hours, but may also be longer depending on the performance.
  • the solution annealing is followed by cooling in inert gas or air, moving (blown) inert gas or air or in water, in which only a small Laves phase forms new.
  • an increased dislocation density must be introduced into the material.
  • Increased dislocation densities have reshaped structures or recovered microstructures, where the dislocations are located in small-angle grain boundaries.
  • the second step must therefore be a transformation, so that the dislocations are introduced into the material, which then in the subsequent annealing for a uniform distribution of Laves phases and / or Fe-containing particles and / or Cr-containing particles and / or Si -containing particles and / or carbides provide.
  • This deformation can be a cold forming, but also a hot forming, whereby the hot working must ensure that the structure is not fully recrystallized during rolling. This is done by limiting the deformation range for the last forming and the temperature at which it takes place. In the case of deformations above 1000 ° C., the material already tends to recrystallise or recover during the deformation, so that the transformation must preferably take place below 1000 ° C. At temperatures below 500 ° C are in the range occurring in ferrites 475 ° C embrittlement. There it has a lower elongation and an increased resistance to deformation, which makes a transformation less advantageous and reduces the efficiency.
  • the dislocation density generated by the deformation must not be too high, because then very many but too weak precipitates arise and the excess dislocations can move freely and thus the pre-deformation is harmful. That Preferably, the highest deformation is 90% for the part of hot working ⁇ 1000 ° C and 90% for cold working.
  • One way of introducing the Laves phases and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides into the formed material is to produce the required components from the semifinished product and then To bring the manufactured component by heating with from 0.1 ° C / min to 1000 ° C / min to the application temperature between 550 ° C and 1000 ° C.
  • the Laves phases and / or Fe-containing particles and / or Cr-containing particles and / or Si-containing particles and / or carbides excreted excreted in the microstructure.
  • the fine distribution is produced by nucleation in the lower temperature range, followed by some growth of the nuclei at the higher temperatures. Therefore, the heating rate must not be faster than 1000 ° C / min, otherwise the time for this process is too low. Heating rates less than 0.1 ° C / minute are uneconomical.
  • the annealing can take place under protective gas (argon, hydrogen and similar atmospheres with reduced oxygen partial pressure).
  • protective gas argon, hydrogen and similar atmospheres with reduced oxygen partial pressure.
  • the cooling takes place for economic reasons in inert gas or air, moving (blown) inert gas or air or in water, especially for temperatures above 800 ° C, a furnace cooling should be avoided, at temperatures ⁇ 800 ° C, this is also possible.
  • the chromium content determines the oxidation resistance and the thermal expansion coefficient of the material.
  • the oxidation resistance of the material is based on the formation of a closed chromium oxide layer. Below 12%, especially at higher operating temperatures, iron-containing oxides are increasingly formed which impair the oxidation resistance.
  • the chromium content is therefore set to ⁇ 12%. Above 30% chromium, the workability of the material and its serviceability is impaired by increased formation of embrittling phases, in particular the sigma phase. The chromium content is therefore limited to ⁇ 30%. As the chromium content increases, the expansion coefficient decreases.
  • the coefficient of expansion can thus be set in a range which matches the ceramics in the fuel cell.
  • These are chromium contents around 22 to 23%.
  • this restriction does not exist.
  • manganese causes the formation of a chromium-manganese spinel on the chromium oxide layer that forms on the material for lower aluminum contents of less than 2%.
  • This chromium manganese spinel reduces chromium evaporation and improves contact resistance. It is necessary for at least a manganese content of 0.001%. More than 2.5% manganese adversely affects the oxidation resistance by forming a very thick chromium-manganese spinel layer.
  • Niobium, molybdenum, tungsten or tantalum may be involved in the formation of precipitates in iron-containing alloys, such as carbides and / or M in the Laves phases Fe 2 (M, Si) or Fe 7 (M, Si) 6 , Molybdenum, tungsten or tantalum are also good mixed crystal hardeners and thus contribute to the improvement of creep resistance.
  • the lower limit is determined in each case by the fact that a certain amount must be present in order to be effective; the upper limit is determined by the processability. This is the preferred range of Nb 0.1 - 2% W: 0.1 - 5% W can also be completely or partially replaced by Mo and Ta: 0.1 - 5%
  • Silicon may be involved in the formation of precipitates in iron-containing alloys, for example in the Laves phase Fe 2 (M, Si) or Fe 7 (M, Si) 6 . It ensures the increased precipitation and stability of these Laves phases and thus contributes to creep resistance. Upon formation of the Laves phase, it is completely set in these. Thus, the formation of a silicon oxide layer below the chromium oxide layer no longer occurs. At the same time, the incorporation of M into the oxide layer is reduced, which reduces the negative influence of M on the Oxidation resistance is prevented. At least 0.05% Si must be present for the desired effect to occur. If the content of Si is too large, the negative effect of Si may occur again. The Si content is therefore limited to 1%.
  • Aluminum deteriorates the oxidation resistance at levels below 1% because it leads to internal oxidation.
  • an aluminum content greater than 1% leads to the formation of an aluminum oxide layer below the chromium oxide layer, which is not electrically conductive and thus reduces the contact resistance. Therefore, the aluminum content is limited to ⁇ 0.5% when a chromium oxide generator is desired or its oxidation resistance is sufficient.
  • An example of this is, for example, for use as interconnector plate.
  • a certain aluminum content of at least 0.001% is necessary for deoxidizing the melt.
  • the alloy can form a closed aluminum oxide layer by an aluminum content of at least 2% ( DE 101 20 561 ). Aluminum contents above 6.0% lead to processing problems and thus to increased costs
  • the carbon content should be ⁇ 0.1%, so as not to affect the processability. However, it should be> 0.002% for an effect to occur.
  • the nitrogen content should not exceed 0.1% in order to avoid the formation of processability deteriorating nitrides. It should be greater than 0.002% to ensure the workability of the material.
  • the levels of sulfur should be as low as possible, since this surfactant affects the oxidation resistance. It will therefore max. 0.01% S set.
  • Oxygen-affinity elements such as Ce, La, Pr, Ne, Sc, Y, Zr, Hf improve oxidation resistance by reducing oxide growth and improving adhesion of the oxide layer. It is useful to have a minimum content of 0.02% of one or more of Ce, La, Pr, Ne, Sc, Y, Zr, Hf to obtain the oxidation resistance-enhancing effect of Y.
  • the upper limit is set for cost reasons at 0.3 wt .-%.
  • Titanium like any oxygen-affine element, is incorporated into the oxide layer during oxidation. In addition, it still causes internal oxidation. However, the resulting oxides are so small and finely divided that they cause hardening of the surface, thus preventing bulging of the oxide layer and the inclusion of metallic areas during oxidation (see DE 10 2006 007 598 A1 ). These bulges are unfavorable because the resulting cracks cause an increase in the oxidation rate. Thus, Ti contributes to the improvement of the oxidation resistance. For Ti content to be effective, at least 0.01% Ti must be present, but not more than 0.5%, since this no longer improves the effect, but increases the cost.
  • the content of phosphorus should be less than 0.030% since this surfactant affects the oxidation resistance. A too low P content increases the costs. The P content is therefore ⁇ 0.002%.
  • the contents of magnesium and calcium are set in the spread range of 0.0001 to 0.05 wt .-%, respectively 0.0001 to 0.03 wt .-%.
  • Table 1 shows the analyzes of the batches used for the following examples. These charges were melted in an electric arc furnace in an amount of about 30 t, then poured into a pan and subjected to a decarburization and deoxidation treatment and a vacuum treatment in a VOD plant and cast into blocks. These were then hot rolled and cold rolled with intermediate annealing, depending on the final thickness. After hot rolling, the oxide layer was removed by pickling
  • a material with an analysis as given in Table 1 precipitates mainly Laves phases Fe 2 (M, Si) or Fe 7 (M, Si) 6 and in significantly reduced amounts of carbides.
  • material from the charge 161061 shown in Table 1 was hot rolled after a solution annealing above 1070 ° C for a period of more than 7 minutes followed by cooling in still air to 12 mm thick sheet, the mechanical working with a starting temperature> 1070 ° C was started and the last 78% of mechanical deformation between 500 ° C and 1000 ° C were applied by rolling.
  • Figure 1 shows the typical appearance of such a deformed structure.
  • the etched sections by means of electrolytic etching with oxalic acid it can be clearly seen that only a few Laves phases have been excreted microscopically.
  • the hot rolled material which is equivalent to a pre-forming, prepared a sample for a creep test as a simulation for a component and then heated at about 60 ° C / minute to an application temperature of 750 ° C and then a creep test with a Surprisingly, the sample tears only after 255 hours at an elongation A of 29%, which means an increase in the time to breakage by 20 times the initial stress of 35 MPa at a temperature of 750 ° C.
  • the production of the component is very easy, since the hot formed state, as described above, in the tensile test at room temperature has an elongation of 19%, which is a good value and makes the material easy to process.
  • the structure Up to 850 ° C (the maximum of the break time), the structure has the typical appearance of a deformed structure. From about 900 ° C, a clear recovery can be seen, but this means that the dislocation density compared to a globular recrystallized structure is still increased. In a recovered structure, the dislocations have partially rearranged into small-angle grain boundaries. It has a similar effect as a pre-forming. In the etched with electrolytic etching with oxalic acid grindings can be clearly seen that from about 750 ° C the Laves phase is excreted microscopically visible, being excreted up to 850 ° C (the maximum of the fracture time) more dense and uniform.
  • the sheet annealed for 20 minutes at all temperatures between 600 ° C and 950 ° C has an elongation of at least 13%, which is still considered satisfactory for a ferritic alloy and makes the material processable.
  • the elongation is lowest in the range of 700 ° C to 800 ° C and improves in each case to the lower or higher annealing temperatures, because at the lower temperatures, although Laves phase has been eliminated, which is microscopically not yet visible and thus has a lower volume fraction, but is very finely distributed.
  • a larger volume fraction is eliminated, but a bit coarser and recognizable on the small-angle grain boundaries and grain boundaries.
  • the annealing at 1000 ° C is with an annealing time of 20 minutes in the invention range and serves as a reference.
  • the break time is also only 10.4 hours.
  • the annealing time of 20 minutes at temperatures between 600 ° C and 950 ° C are within the range of the invention.
  • the fracture time was significantly more than a factor of 7 compared to the coarse-grained, globularly recrystallized state of Example 1 after annealing of 1075 ° C / 20 minutes followed by cooling in still air arises, increased.
  • material from the batch 161061 indicated in Table 1 was hot rolled to a 12 mm thick sheet after a solution annealing of more than 1070 ° C for a period of more than 7 minutes followed by quiescent air cooling, forming with a starting temperature> 1070 ° C was started and the last 60% of mechanical deformation between 1000 ° C and 500 ° C are applied by rolling.
  • a tensile test sample made from this material has a creep test with an initial stress of 35 MPa at a temperature of 750 ° C. a break time of 391 hours at an elongation A of 38% (Table 4).
  • the structure is not globular recrystallized but recovered. It has precipitates in the grain and on the small-angle grain boundaries or grain boundaries (Fig. 4).
  • the fracture time is 30 times the time, which was achieved in Example 1 after annealing of 1075 ° C for 20 min with a globular recrystallized coarse grain with a grain size of 137 microns.
  • the annealing at 920 ° C is with an annealing time of 28 minutes in the range according to the invention.
  • the sheet thus treated has a very good elongation of 18%, a yield strength of 475 MPa, and a tensile strength of 655 MPa (See Table 4), which makes the material well formable.
  • material from lot 161061 and lot 161995 is after a solution anneal of more than 1070 ° C for a period of more than 7 minutes, followed by cooling in blown inert gas and hot rolling, and removing the oxide layer to 1.5 mm thick sheet cold rolled, with a cold working of 53% was applied. This was followed by annealing at 1050 ° C. for 3.4 minutes under protective gas in a continuous furnace with subsequent cooling in the cold inert gas stream.
  • Both Lot 161061 ( Figure 5) and Lot 161995 show a recovered texture with elongated grains ( Figure 7) and excretion of Laves phase, albeit much less than Figure 4.
  • Tables 5a and 5b show the results of creep tests and tensile tests at room temperature. After annealing at 1050 ° C. for 3.4 minutes, batch 161061 in a creep test at 750 ° C. with an initial load of 35 MPa has a break time of 25.9 hours at an elongation A of 50% the additional annealing at 1050 ° C for 20 minutes, the very coarse grain produces a one-third break time of 7.9 hours at an elongation A of 83%.
  • the annealing at 1050 ° C for 20 minutes is not in the invention range with an annealing time of 20 minutes and serves as a reference as well as the annealing at 1075 ° C for 20 min.
  • the annealing at 1050 ° C for 3.4 minutes is with an annealing time of 3.4 minutes in the range according to the invention and shows according to the invention a significantly increased fracture time in the creep test.
  • material from batch 161061 is followed by a solution anneal above 1070 ° C for a period of more than 7 minutes followed by a Cooling in still air to 12 mm thick sheet was rolled hot, the forming was started with a starting temperature> 1070 ° C and the last 70% of mechanical deformation between 1000 ° C and 500 ° C were rolled.
  • the Laves phase is distributed in the microstructure. (Picture 10). If the creep test is then carried out at 700 ° C. with an initial stress of 40 MPa, the sample travels already after 104 hours, at an elongation A of 72.6%, ie a considerably shorter time than after the solution annealing of 1075 ° C. 22 minutes. If the creep test is carried out with 60 MPa, the sample breaks after 6.3 hours, with an elongation A of 63%, ie also after a much shorter time than after the solution annealing of 1075 ° C. for 22 minutes.
  • Example 2 with the hot rolled material of Example 1 anneals between 750 ° C and 1000 ° C for 20 min and for some temperatures also 120 min, 240 min, 480 min, 960 min, 1440 or 5760 min, in air, followed by cooling in still air.
  • samples were prepared from the sheets, and then the creep test was carried out at a tension of 40 MPa at 750 ° C as described above.
  • the higher voltage compared to Example 2 was chosen to shorten the experimental time.
  • the aim was to determine the heat treatment times suitable for the annealing. The results are summarized in Table 7.
  • an at least 10-fold increased break time of more than 100 hours is achieved at an elongation A of greater than 27%.
  • the highest break time for annealing with 20 minutes is achieved at 850 ° C with 296 hours.
  • the highest break time for 120 minute anneals is achieved at 800 ° C with 227 hours.
  • the highest break time for the 240 minute anneals is achieved at 750 ° C for 182 hours, with no value for 700 ° C.
  • the highest break time for the 480 minute anneals is 800 ° C reached with 169 hours. For 960 minutes, only a break time of 750 ° C would be determined, with a value of 139 hours at an elongation of 24.2%.
  • Example 2 For the structure after 20 minutes of annealing, the same applies in Example 2, since these are the same anneals. Even at the higher stress of 40 MPa in the creep test, the maximum of the fracture time occurs in the deformed microstructure, with dense uniformly precipitated Laves phase.
  • the sheet annealed for 20 minutes at all temperatures as in Example 2 between 600 ° C and 900 ° C has an elongation of at least 13%, which is still considered to be satisfactory for a ferritic alloy and makes the material processable.
  • a sample for a creep test is produced as a simulation for a component from the material formed after 1050 ° C / 2.8 min and then heated to an application temperature of 750 ° C at about 60 ° C / minute and then a creep test with a Starting stress of 35 MPa carried out at a temperature of 750 ° C, the elongation at break decreases in transformations between 5 and 40% to values around 10 hours with elongations at break greater than 45%.
  • a sample for a creep test is produced from the material formed after 1050 ° C./10 min.
  • a simulation for a component and then heated to an application temperature of 750 ° C. at about 60 ° C./minute and then a creep test with an initial stress of 35 MPa at a temperature of 750 ° C "so increases the elongation at break during forming between 2.9 and 40% to values between 49 and 137 hours, which an increase in breaking time over that after 1050 ° C / 2.8 min formed Material by more than means the factor 4, with a maximum occurs at 10% and the elongation at break between 18.9 and 60%.

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Claims (23)

  1. Procédé de fabrication d'un élément de construction à partir d'un alliage fer-chrome précipitant des phases de Laves et/ou des particules contenant du Fe et/ou des particules contenant du Cr et/ou des particules contenant du Si et/ou des carbures, l'alliage comprenant la composition suivante (en % en poids) : Cr 12 - 30 % Mn 0,001 - 2,5 % Nb 0,1 - 2 % W 0,1 - 5 % Si 0,05 - 1 % C 0,002 - 0,1 % N 0,002 - 0,1 % S max. 0,01 %
    l'alliage pouvant encore contenir facultativement les éléments suivants : La 0,02 - 0,3 % Ti 0,01 - 0,5 %
    l'un ou plusieurs des éléments Ce, Pr, Ne, Sc, Y, Zr, Hf 0,02 - 0,3 % Al 0,001 - 0,5 % ou 2,0 - 6,0 %,
    l'un ou plusieurs des éléments Mg 0,0001 - 0,07 % Ca 0,0001 - 0,07 % P 0,002 - 0,03 %,
    l'un ou plusieurs des éléments Ni, Co, Cu 0,01 - 3,0 % B jusqu'à 0,005 % V max. 0,2 % et/ou S max. 0,005 % O max. 0,01 % Zn max. 0,01 % Sn max. 0,01 % Pb max. 0,01 % Se max. 0,01 % Te max. 0,01 % Bi max. 0,01 % Sb max. 0,01 %
    la teneur en W pouvant, en cas de besoin, être complètement ou partiellement remplacée par au moins l'un des éléments Mo et/ou Ta,
    Fe reste
    ainsi que les impuretés usuelles liées à l'élaboration,
    en soumettant un produit semi-fini fabriqué à partir de l'alliage à un traitement thermomécanique, dans une première étape l'alliage étant soumis à un recuit de mise en solution à des températures de ≥ la température de recuit de mise en solution, à une température de ≥ 1050°C pendant plus de 6 minutes ou à une température de ≥ 1060°C pendant plus d'une minute, suivi d'un refroidissement dans un gaz protecteur ou l'air calme, un gaz protecteur ou l'air déplacé (soufflé) ou dans l'eau, dans une deuxième étape une déformation mécanique du produit semi-fini dans une gamme comprise entre 0,05 et 99 % étant effectuée et dans une étape suivante des phases de Laves Fe2(M, Si) ou Fe7(M, Si)6 et/ou des particules contenant du Fe et/ou des particules contenant du Cr et/ou des particules du Si et/ou des carbures étant précipitées de manière ciblée et finement dispersée, en ce que l'élément de construction fabriqué à partir du produit semi-fini déformé est amené à une température d'application comprise entre 550°C et 1000°C par un chauffage de 0,1 °C/min à 1000°C/min.
  2. Procédé selon la revendication 1, dans lequel le produit semi-fini comprend, à température ambiante, une déformabilité mécanique, mesurée comme déformation élastique dans l'essai de traction, de > 13 %.
  3. Procédé selon la revendication 1 ou la revendication 2, caractérisé en ce qu'après le recuit de mise en solution à des températures de ≥ la température de recuit de mise en solution, de préférence à ≥ 1050°C pendant plus de 6 minutes respectivement à ≥ 1060°C pendant plus d'une minute, suivi d'un refroidissement dans un gaz protecteur ou l'air calme, un gaz protecteur ou l'air déplacé (soufflé) ou dans l'eau, dans l'état initial avant la déformation du produit semi-fini il n'y a plus que peu de ou aucunes phases de Laves Fe2(M, Si) ou Fe7(M, Si)6 et/ou de particules contenant du Fe et/ou de particules contenant du Cr et/ou de particules du Si et/ou de carbures dans l'alliage.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la déformation du produit semi-fini s'effectue par une déformation à chaud.
  5. Procédé selon la revendication 4, caractérisé en ce que la déformation à chaud du produit semi-fini commence à une température initiale de > 1070°C, les derniers 0,05 à 90 % de la déformation mécanique étant réalisés entre 1000°C et 500°C.
  6. Procédé selon la revendication 4 ou 5, caractérisé en ce que la déformation à chaud du produit semi-fini commence à une température initiale de > 1070°C, les derniers 0,05 à 95 % de la déformation mécanique étant réalisés entre 1000°C et 500°C.
  7. Procédé selon l'une des revendications 4 à 6, caractérisé en ce que la déformation à chaud du produit semi-fini commence à une température initiale de > 1070°C, les derniers 0,5 à 90 % de la déformation mécanique étant réalisés entre 1000°C et 500°C.
  8. Procédé selon l'une des revendications 4 à 7, caractérisé en ce que la déformation à chaud du produit semi-fini est suivie par une déformation à froid.
  9. Procédé selon l'une des revendications 4 à 7, caractérisé en ce que la déformation du produit semi-fini s'effectue par une déformation à froid.
  10. Procédé selon la revendication 9, caractérisé en ce que le degré de la déformation à froid du produit semi-fini est compris entre 0,05 et 99 %.
  11. Procédé selon l'une des revendications 9 ou 10 caractérisé en ce que la déformation à froid du produit semi-fini est comprise entre 0,05 et 95 %.
  12. Procédé selon l'une des revendications 9 à 11 caractérisé en ce que la déformation à froid du produit semi-fini est comprise entre 0,05 et 90 %.
  13. Procédé selon l'une des revendications 1 à 12, dans lequel l'alliage contient (en % en poids) 2,5 à 5,0 % d'Al.
  14. Procédé selon l'une des revendications 1 à 13, dans lequel l'alliage contient (en % en poids) 0,02 à 0,2 % de l'élément La.
  15. Procédé selon l'une des revendications 1 à 14, dans lequel l'alliage contient (en % en poids) 0,02 à 0,2 % de Ti.
  16. Procédé selon l'une des revendications 1 à 15, dans lequel l'alliage contient (en % en poids) 0,02 à 0,2 % de l'un ou plusieurs des éléments Ce, Pr, Ne, Sc, Y, Zr ou Hf.
  17. Procédé selon l'une des revendications 1 à 16, dans lequel l'alliage contient supplémentairement l'un ou plusieurs des éléments (en % en poids) 0,0001 à 0,05 % de Mg, 0,0001 à 0,03 % de Ca, 0,002 à 0,03 % de P.
  18. Procédé selon l'une des revendications 1 à 17, dans lequel l'alliage contient en outre (en % en poids) jusqu'à 0,003 % de B.
  19. Procédé selon l'une des revendications 1 à 18, dans lequel la teneur en Nb (en % en poids) est 1,0 % et la teneur en Si est comprise entre 0,15 % et 0,5 %.
  20. Procédé selon l'une des revendications 1 à 19, dans lequel l'alliage fer-chrome traité de manière thermomécanique et précipitant des phases de Laves sous forme finement dispersée comprend la composition suivante (en % en poids) Cr 12 - 30% Mn 0,001 - 2,5 % Nb 0,1 - 2% W 0,1 - 5 % Si 0,05 - 1 % C 0,002 - 0,03 % N 0,002 - 0,03 % S max. 0,005 % Fe reste
    ainsi que les impuretés usuelles liées à l'élaboration.
  21. Procédé selon l'une des revendications 1 à 20, caractérisé en ce que le produit semi-fini est formé par une tôle, une bande, une tige, une pièce forgée, un tuyau ou un fil de fer.
  22. Procédé selon l'une des revendications 1 à 21, caractérisé en ce que le traitement thermique n'est effectué qu'après la réalisation de l'élément de construction.
  23. Procédé selon l'une des revendications 1 à 22, caractérisé en ce que grâce au traitement thermomécanique du produit semi-fini on obtient une résistance au fluage particulièrement élevée du produit semi-fini et/ou de l'élément de construction avec simultanément un allongement de > 13 % dans l'essai de traction à température ambiante.
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AU2010291651B2 (en) 2016-04-28
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AU2010291651A1 (en) 2012-02-23
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CA2773708C (fr) 2015-03-17
DE102009039552A1 (de) 2011-03-24

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