EP1083241A1 - Ferritic niobium-stabilised 14% chromium steel and its use in the car industry - Google Patents

Ferritic niobium-stabilised 14% chromium steel and its use in the car industry Download PDF

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Publication number
EP1083241A1
EP1083241A1 EP00402447A EP00402447A EP1083241A1 EP 1083241 A1 EP1083241 A1 EP 1083241A1 EP 00402447 A EP00402447 A EP 00402447A EP 00402447 A EP00402447 A EP 00402447A EP 1083241 A1 EP1083241 A1 EP 1083241A1
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Prior art keywords
niobium
steel sheet
relationship
δnb
temperature
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EP00402447A
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German (de)
French (fr)
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EP1083241B1 (en
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Silke Liesert
Laurent Antoni
Pierre Olivier Santacreu
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Aperam Stainless France SA
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Ugine SA
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    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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 by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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 by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties 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 by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties 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
    • 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 by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing

Definitions

  • the invention relates to a ferritic steel said to have 14% chromium. stabilized with niobium and its use in the automotive field.
  • the steels used for these hot parts are often relatively austenitic steels expensive and with low resistance to oxidation, but having good shaping characteristics, ie bistabilised ferritic steels. Bistabilized ferritic steels have good resistance to oxidation but are relatively difficult to format.
  • the aim of the invention is to propose a ferritic steel, economical, which has very good heat resistance both to creep and oxidation, up to 1000 ° C and an improved hardness characteristic for its shaping.
  • the invention also relates to a use of sheet steel ferritic in the automotive field and in particular for the realization of exhaust line collector.
  • FIGS. 1A and 1B respectively present a microstructure of a steel according to the invention, referenced 1 in Tables I and II, and a microstructure of a comparison steel, referenced 6 in Tables I and II, after heat treatment, each of the two steels having the same ⁇ Nb of about 0.25%.
  • Figure 2 shows a microstructure of a comparison steel referenced 9 in Tables I and II, with a relatively high ⁇ Nb about 0.43% having, after heat treatment, precipitates intergranular Fe2Nb type, distributed in a disordered manner.
  • Figure 3 shows the mechanical hardness characteristics for a steel according to the invention, referenced 1 in Tables I and II, and two comparison steels, referenced 6 and 9 in Tables I and II, before and after heat treatment to form precipitates respectively Fe2Nb3 or Fe2Nb type.
  • the Laves phase Fe2Nb For a value of ⁇ Nb ⁇ 0.3%, the Laves Fe2Nb phase is completely dissolved at temperatures equal to or above 950 ° C, as shown in Figure 1 B. This explains the bad behavior of these steels to the creep behavior at or beyond 950 ° C.
  • This phase has a lower solubility than the Laves Fe2Nb phase.
  • the presence of the Fe2Nb3 phase at high temperature, in large quantity has the advantage of generating a very good creep resistance and shaping of the steels according to the invention.
  • the Laves Fe2Nb phase is an intermetallic compound, which, when it exists in a steel, precipitates intragranularly and at the joints of grains in an anarchic way and does not prevent sufficiently the displacement of grain boundaries, so the material flows. An amount significant of this intermetallic precipitate is necessary to improve the creep resistance.
  • the Si / Mn ratio greater than 1 is not respected, it is also the intermetallic Fe2Nb3 which appears.
  • Manganese increases the solubility of the intermetallic Fe2Nb3 and the formation, at high temperature, of a CrNbN type Z phase in the grains. At 950 ° C, the intermetallic Fe2Nb3 is thus dissolved. Steel has a bad creep and oxidation resistance. Silicon compensates for this effect.
  • heat treatment at a temperature of the order of 900 ° C, preferably of the order of 850 ° C, for a relatively short period, less than or equal to 30 min, after final annealing or prior to use has been carried out.
  • the treatment thermal allows very fine homogeneous precipitation at the levels of grain boundaries of the Fe2Nb3 phase. These precipitates serve as the center germination. They allow very homogeneous precipitation, at the joints of grains, of the Fe2Nb3 phase at any temperature greater than or equal to 750 ° C which is favorable for good creep resistance.
  • Table I presents the chemical analyzes of the shades studied. Shades 1 to 4 are shades according to the invention. Shades 5 to 9 are examples of comparisons.
  • Table II presents the creep results at 950 ° C. after 100 hours, cyclic oxidation at 950 ° C and 1000 ° C after 200h, hardness after annealing final and after heat treatment at 850 ° C according to the invention, as well as the ANb, the type of intermetallic present at T> 700 ° C and the presence or absence intermetallics at 950 ° C.
  • This table also shows the relationships satisfied or not by the elements of the compositions presented.
  • compositions which satisfy all relationships and which therefore have the best creep, oxidation and hardness characteristics before and after heat treatment, with the lowest ⁇ Nb, are grades 1-4 according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Catalysts (AREA)
  • Soft Magnetic Materials (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

Niobium stabilized ferritic chromium steel strip is produced from a steel having specified molybdenum, silicon and tin contents and containing a cubic iron-niobium phase as the sole intermetallic phase at high temperature. A niobium stabilized ferritic 14% chromium steel strip is produced from a steel of composition (by wt.) ≤ 0.02% C, 0.002-0.02% N, 0.05-1% Si, greater than 0 to 1% Mn, 0.2-0.6% Nb, 13.5-16.5% Cr, 0.02-1.5% Mo, greater than 0 to 1.5% Cu, greater than 0 to 0.2% Ni, greater than 0 to 0.020% P, greater than 0 to 0.003% S, greater than 0.005 to 0.04% Sn, balance Fe and impurities, the Nb, C and N contents satisfying the relationship Nb/(C + N) ≥ 9.5, by: (a) reheating before hot rolling at 1150-1250 (preferably 1175) degrees C; (b) coiling at 600-800 (preferably 600) degrees C; (c) cold rolling, optionally after pre-annealing; and (d) final annealing at 800-1100 (preferably 1050) degrees C for 1-5 (preferably 2) min. An Independent claim is also included for a niobium stabilized 14% chromium ferritic steel sheet obtained by the above process.

Description

L'invention concerne un acier ferritique dit à 14% de chrome stabilisé au niobium et son utilisation dans le domaine de l'automobile.The invention relates to a ferritic steel said to have 14% chromium. stabilized with niobium and its use in the automotive field.

Les aciers utilisés pour des pièces situées en amont d'une ligne d'échappement d'un véhicule automobile, partie chaude de la ligne, doivent présenter simultanément une bonne résistance à l'oxydation et une bonne tenue au fluage. Pour la fabrication du collecteur, une bonne caractéristique de mise en forme est également nécessaire. Les aciers utilisés pour ces parties chaudes sont souvent, soit des aciers austénitiques relativement coûteux et de faible tenue à l'oxydation, mais présentant de bonnes caractéristiques de mise en forme, soit des aciers ferritiques bistabilisés. Les aciers ferritiques bistabilisés présentent une bonne tenue à l'oxydation mais sont relativement difficiles à mettre en forme.Steels used for parts located upstream of a line of a motor vehicle, hot part of the line, must have good oxidation resistance and good creep resistance. For the manufacture of the collector, a good characteristic shaping is also required. The steels used for these hot parts are often relatively austenitic steels expensive and with low resistance to oxidation, but having good shaping characteristics, ie bistabilised ferritic steels. Bistabilized ferritic steels have good resistance to oxidation but are relatively difficult to format.

Le but de l'invention est de proposer un acier ferritique, économique, qui présente une très bonne tenue à chaud tant au fluage qu'à l'oxydation, jusqu'à 1000°C et une caractéristique en dureté améliorée pour sa mise en forme.The aim of the invention is to propose a ferritic steel, economical, which has very good heat resistance both to creep and oxidation, up to 1000 ° C and an improved hardness characteristic for its shaping.

L'invention a pour objet un procédé de réalisation d'une bande de tôle en acier ferritique dit à 14% de chrome stabilisée au niobium, caractérisée en ce que l'acier de composition pondérale suivante :
carbone ≤ 0,02%
0,002% ≤ azote ≤ 0,02%
0,05% ≤ silicium ≤ 1%
0% ≤ manganèse ≤ 1%
0,2% ≤ niobium ≤ 0,6%
13,5% ≤ chrome ≤ 16,5%
0.02% ≤ molybdène ≤ 1.5%
0% < cuivre ≤ 1,5%
0% < nickel ≤ 0.2%
0% < phosphore ≤ 0,020%
0% < soufre ≤ 0,003%
0,005% < étain ≤ 0,04%
les impuretés inhérentes à l'élaboration
la teneur en niobium, carbone, azote satisfaisant la relation:
9.5≤ Nb/(C+N)
est soumis à :

  • un réchauffage avant laminage à chaud à une température comprise entre 1150°C et 1250°C et de préférence à environ 1175°C,
  • un bobinage à une température comprise entre 600°C et 800°C et de préférence à environ 600°C,
  • un laminage à froid de la bobine avec ou sans recuit préalable,
  • un recuit final de la bande de tôle à une température comprise entre 800°C et 1100°C pendant une durée comprise entre 1 mn et 5 mn et de préférence à une température d'environ 1050°C pendant un temps d'environ 2 mn,
    Les autres caractéristiques de l'invention sont :
  • après recuit final ou préalable à l'utilisation, la tôle est soumise à un traitement thermique à une température comprise entre 800°C et 1000°C pendant un temps compris entre 1mn et 100h et de préférence à une température d'environ 850°C pendant un temps égal ou inférieur à 30mn. L'invention concerne également une tôle en acier ferritique dit à 14% de chrome stabilisé au niobium obtenue pour la mise en oeuvre du procédé qui se caractérise en la composition pondérale suivante :
    carbone ≤ 0,02%
    0,002% ≤ azote ≤ 0,02%
    0,05% ≤ silicium ≤ 1%
    0% < manganèse ≤ 1%
    0,2% ≤ niobium ≤ 0,6%
    13,5% ≤ chrome ≤ 16,5%
    0.02% ≤ molybdène ≤ 1.5%
    0% < cuivre ≤ 1,5%
    0% < nickel ≤ 0.2%
    0% < phosphore ≤ 0,020%
    0% < soufre ≤ 0,003%
    0,005% < étain ≤ 0,04%
    les impuretés inhérentes à l'élaboration
    la teneur en niobium, carbone, azote satisfaisant la relation:
    9.5≤ Nb/(C+N)
Les autres caractéristiques de l'invention sont:
  • la teneur en Nb satisfait la relation 0.1 ≤ ΔNb ≤ 0.5 avec ΔNb = Nb - 7(C+N) et de préférence 0.2 ≤ ΔNb ≤ 0.3
  • les teneurs en niobium, silicium, molybdène satisfont la relation:
    ΔNb/(Si+Mo) ≤ 0.9
  • les teneurs pondérales en niobium et étain satisfont la relation :
    ΔNb/Sn ≤ 50
  • les teneurs en manganèse et en Silicium satisfont la relation :
    Si/Mn ≥ 1.
    Les teneurs en niobium, titane, zirconium, aluminium satisfont la relation:
    N/(Ti+Zr+Al) ≥ 0,16
  • l'acier comporte, après traitement thermique, au niveau des joints des grains, un intermétallique de maille quadratique de type Fe2Nb3.
The subject of the invention is a process for producing a strip of ferritic steel sheet said to be 14% chromium stabilized with niobium, characterized in that the steel of the following composition by weight:
carbon ≤ 0.02%
0.002% ≤ nitrogen ≤ 0.02%
0.05% ≤ silicon ≤ 1%
0% ≤ manganese ≤ 1%
0.2% ≤ niobium ≤ 0.6%
13.5% ≤ chromium ≤ 16.5%
0.02% ≤ molybdenum ≤ 1.5%
0% <copper ≤ 1.5%
0% <nickel ≤ 0.2%
0% <phosphorus ≤ 0.020%
0% <sulfur ≤ 0.003%
0.005% <tin ≤ 0.04%
the impurities inherent in the preparation
the niobium, carbon, nitrogen content satisfying the relationship:
9.5≤ Nb / (C + N)
is subject to:
  • reheating before hot rolling at a temperature between 1150 ° C and 1250 ° C and preferably at around 1175 ° C,
  • winding at a temperature between 600 ° C and 800 ° C and preferably at around 600 ° C,
  • cold rolling of the coil with or without prior annealing,
  • a final annealing of the sheet metal strip at a temperature between 800 ° C and 1100 ° C for a time between 1 min and 5 min and preferably at a temperature of about 1050 ° C for a time of about 2 min ,
    The other characteristics of the invention are:
  • after final annealing or prior to use, the sheet is subjected to a heat treatment at a temperature between 800 ° C and 1000 ° C for a time between 1mn and 100h and preferably at a temperature of about 850 ° C for a time equal to or less than 30 minutes. The invention also relates to a ferritic steel sheet said to be 14% chromium stabilized with niobium obtained for the implementation of the process which is characterized in the following weight composition:
    carbon ≤ 0.02%
    0.002% ≤ nitrogen ≤ 0.02%
    0.05% ≤ silicon ≤ 1%
    0% <manganese ≤ 1%
    0.2% ≤ niobium ≤ 0.6%
    13.5% ≤ chromium ≤ 16.5%
    0.02% ≤ molybdenum ≤ 1.5%
    0% <copper ≤ 1.5%
    0% <nickel ≤ 0.2%
    0% <phosphorus ≤ 0.020%
    0% <sulfur ≤ 0.003%
    0.005% <tin ≤ 0.04%
    the impurities inherent in the preparation
    the niobium, carbon, nitrogen content satisfying the relationship:
    9.5≤ Nb / (C + N)
The other characteristics of the invention are:
  • the Nb content satisfies the relationship 0.1 ≤ ΔNb ≤ 0.5 with ΔNb = Nb - 7 (C + N) and preferably 0.2 ≤ ΔNb ≤ 0.3
  • the niobium, silicon, molybdenum contents satisfy the relationship:
    ΔNb / (Si + Mo) ≤ 0.9
  • the niobium and tin weight contents satisfy the relationship:
    ΔNb / Sn ≤ 50
  • the manganese and silicon contents satisfy the relationship:
    If / Mn ≥ 1.
    The niobium, titanium, zirconium and aluminum contents satisfy the relationship:
    N / (Ti + Zr + Al) ≥ 0.16
  • the steel comprises, after heat treatment, at the grain boundaries, an intermetallic quadratic mesh of Fe2Nb3 type.

L'invention concerne également une utilisation de la tôle d'acier ferritique dans le domaine automobile et notamment pour la réalisation de collecteur de ligne d'échappement.The invention also relates to a use of sheet steel ferritic in the automotive field and in particular for the realization of exhaust line collector.

La description qui suit et les figures annexées fera bien comprendre l'invention :The following description and the appended figures will make it clear the invention:

Les figures 1A et 1B présentent respectivement une microstructure d'un acier selon l'invention, référencé 1 dans les tableaux I et II, et une microstructure d'un acier de comparaison, référencé 6 dans les tableaux I et II, après traitement thermique chacun des deux aciers comportant un même ΔNb d'environ 0.25%.FIGS. 1A and 1B respectively present a microstructure of a steel according to the invention, referenced 1 in Tables I and II, and a microstructure of a comparison steel, referenced 6 in Tables I and II, after heat treatment, each of the two steels having the same ΔNb of about 0.25%.

La figure 2 présente une microstructure d'un acier de comparaison référencé 9 dans les tableaux I et II, avec un ΔNb relativement élevé d'environ 0.43% présentant après traitement thermique, des précipités intergranulaires de type Fe2Nb, répartis de manière désordonnée. Figure 2 shows a microstructure of a comparison steel referenced 9 in Tables I and II, with a relatively high ΔNb about 0.43% having, after heat treatment, precipitates intergranular Fe2Nb type, distributed in a disordered manner.

La figure 3 présente les caractéristiques mécaniques en dureté pour un acier selon l'invention, référencé 1 dans les tableaux I et II, et deux aciers de comparaison, référencé 6 et 9 dans les tableaux I et II, avant et après traitement thermique de formation de précipités respectivement de type Fe2Nb3 ou Fe2Nb.Figure 3 shows the mechanical hardness characteristics for a steel according to the invention, referenced 1 in Tables I and II, and two comparison steels, referenced 6 and 9 in Tables I and II, before and after heat treatment to form precipitates respectively Fe2Nb3 or Fe2Nb type.

Les aciers ferritiques contenant les éléments tels que titane, zirconium, aluminium, et manganèse comme il est précisé dans les compositions des aciers de référence 5-9 des tableaux I et II, présentent à toutes températures comme phase intermétallique, la phase de Laves Fe2Nb. Pour une valeur de ΔNb ≤ 0,3%, la phase de Laves Fe2Nb est complètement mise en solution à des températures égales ou supérieures à 950°C, comme le montre la figure 1 B. Ceci explique le mauvais comportement de ces aciers à la tenue en fluage à ou au-delà de 950°C.Ferritic steels containing elements such as titanium, zirconium, aluminum, and manganese as specified in the compositions of the reference steels 5-9 of Tables I and II, present at all temperatures as intermetallic phase, the Laves phase Fe2Nb. For a value of ΔNb ≤ 0.3%, the Laves Fe2Nb phase is completely dissolved at temperatures equal to or above 950 ° C, as shown in Figure 1 B. This explains the bad behavior of these steels to the creep behavior at or beyond 950 ° C.

Les éléments comme le titane, le zirconium ou l'aluminium, bien que devant être évités dans la composition de l'acier selon l'invention peuvent néanmoins être présents dans la composition dans les teneurs telles que :
titane ≤ 0,01%
zirconium ≤ 0,01%
aluminium ≤ 0,1%
et satisfaire de préférence la relation:
N/(Ti+Zr+Al) ≥ 0.16%Elements such as titanium, zirconium or aluminum, although having to be avoided in the composition of the steel according to the invention, can nevertheless be present in the composition in the contents such as:
titanium ≤ 0.01%
zirconium ≤ 0.01%
aluminum ≤ 0.1%
and preferably satisfy the relationship:
N / (Ti + Zr + Al) ≥ 0.16%

Dans les aciers concernant l'invention où les éléments molybdène, compris entre 0,02% et 1%, silicium compris entre 0,05% et 1%, étain compris entre 0,005% et 0,04%, sont présents et où les relations ΔNb/(Si+Mo) ≤ 0.9, Si/Mn ≥ 1, ΔNb/Sn ≤ 50 et N/(Ti+Zr+Al) ≥ 0.16% sont satisfaites, nous rencontrons la phase de Laves Fe2Nb seulement à basse température c'est à dire vers environ 650°C. Pour des températures plus élevées, c'est à dire égale ou au-dessus de 700°C, la phase quadratique du type Fe2Nb3 est la seule phase intermétallique observée. Cette phase présente une solubilité moins importante que la phase de Laves Fe2Nb. Pour un faible ΔNb de 0,23%, même à 950°C, une quantité importante de Fe2Nb3 reste présente comme on peut le voir sur la microstructure de la figure 1A. La présence de la phase Fe2Nb3 à haute température, en quantité importante a l'avantage de générer une très bonne tenue au fluage et mise en forme des aciers selon l'invention.In the steels relating to the invention where the molybdenum elements, between 0.02% and 1%, silicon between 0.05% and 1%, tin between 0.005% and 0.04%, are present and where relationships ΔNb / (Si + Mo) ≤ 0.9, Si / Mn ≥ 1, ΔNb / Sn ≤ 50 and N / (Ti + Zr + Al) ≥ 0.16% are satisfied, we meet the Laves Fe2Nb phase only at low temperature ie around 650 ° C. For higher temperatures high, i.e. equal to or above 700 ° C, the quadratic phase of the type Fe2Nb3 is the only intermetallic phase observed. This phase has a lower solubility than the Laves Fe2Nb phase. For a low ΔNb of 0.23%, even at 950 ° C, a large amount of Fe2Nb3 remains present as can be seen on the microstructure of the Figure 1A. The presence of the Fe2Nb3 phase at high temperature, in large quantity has the advantage of generating a very good creep resistance and shaping of the steels according to the invention.

La phase de Laves Fe2Nb est un composé intermétallique, qui, lorsqu'il existe dans un acier, précipite de façon intragranulaire et aux joints de grains de manière anarchique et n'empêche pas de façon suffisante le déplacement des joints de grains, donc le matériau flue. Une quantité importante de ce précipité intermétallique est nécessaire pour améliorer la tenue au fluage.The Laves Fe2Nb phase is an intermetallic compound, which, when it exists in a steel, precipitates intragranularly and at the joints of grains in an anarchic way and does not prevent sufficiently the displacement of grain boundaries, so the material flows. An amount significant of this intermetallic precipitate is necessary to improve the creep resistance.

La précipitation de la phase Fe2Nb3 aux joints de grains assure une diminution de la dureté de l'acier par rapport à un acier où tous les précipités intermétalliques ont été mis en solution ou ont précipité de façon intragranulaire (figure 3).The precipitation of the Fe2Nb3 phase at the grain boundaries ensures a reduction in the hardness of steel compared to steel where all intermetallic precipitates have been dissolved or precipitated intragranular (Figure 3).

Si le rapport Si/Mn supérieur à 1 n'est pas respecté, c'est également l'intermétallique Fe2Nb3 qui apparaít. Cependant, le manganèse augmente la solubilité de l'intermétallique Fe2Nb3 et la formation, à haute température, d'une phase Z du type CrNbN dans les grains. A 950°C, l'intermétallique Fe2Nb3 est ainsi dissout. L'acier présente une mauvaise tenue en fluage et en oxydation. Le silicium compense cet effet.If the Si / Mn ratio greater than 1 is not respected, it is also the intermetallic Fe2Nb3 which appears. Manganese increases the solubility of the intermetallic Fe2Nb3 and the formation, at high temperature, of a CrNbN type Z phase in the grains. At 950 ° C, the intermetallic Fe2Nb3 is thus dissolved. Steel has a bad creep and oxidation resistance. Silicon compensates for this effect.

Pour assurer une bonne mise en forme et une bonne tenue en fluage, ce qui se manifeste par une quantité élevée des précipités intermétalliques aux joints de grains, un traitement thermique à une température de l'ordre de 900°C, de préférence de l'ordre de 850°C, pendant une période relativement courte, inférieure ou égale à 30 mn, après recuit final ou préalablement à l'utilisation a été effectué. Le traitement thermique permet une précipitation homogène très fine aux niveaux des joints de grains de la phase Fe2Nb3. Ces précipités servent comme centre de germination. Ils permettent une précipitation très homogène, aux joints de grains, de la phase Fe2Nb3 à toute température supérieure ou égale à 750°C ce qui est favorable pour une bonne tenue au fluage.To ensure good formatting and good resistance creep, which manifests as a high amount of precipitates intermetallics at grain boundaries, heat treatment at a temperature of the order of 900 ° C, preferably of the order of 850 ° C, for a relatively short period, less than or equal to 30 min, after final annealing or prior to use has been carried out. The treatment thermal allows very fine homogeneous precipitation at the levels of grain boundaries of the Fe2Nb3 phase. These precipitates serve as the center germination. They allow very homogeneous precipitation, at the joints of grains, of the Fe2Nb3 phase at any temperature greater than or equal to 750 ° C which is favorable for good creep resistance.

Pour améliorer la tenue à la corrosion un ajout de cuivre dans une teneur modérée, inférieure ou égale à 1.5%, peut être effectué. To improve corrosion resistance, adding copper to a moderate content, less than or equal to 1.5%, can be made.

Le tableau I présente les analyses chimiques des nuances étudiées. Les nuances 1 à 4 sont des nuances selon l'invention. Les nuances 5 à 9 sont des exemples de comparaisons.Table I presents the chemical analyzes of the shades studied. Shades 1 to 4 are shades according to the invention. Shades 5 to 9 are examples of comparisons.

Le tableau Il présente les résultats de fluage à 950°C après 100h, de l'oxydation cyclique à 950°C et 1000°C après 200h, la dureté après recuit finale et après traitement thermique à 850°C selon l'invention, ainsi que le ANb, le type d'intermétallique présent à T>700°C et la présence ou absence des intermétalliques à 950°C. Ce tableau présente également les relations satisfaites ou non par les éléments des compositions présentées.Table II presents the creep results at 950 ° C. after 100 hours, cyclic oxidation at 950 ° C and 1000 ° C after 200h, hardness after annealing final and after heat treatment at 850 ° C according to the invention, as well as the ANb, the type of intermetallic present at T> 700 ° C and the presence or absence intermetallics at 950 ° C. This table also shows the relationships satisfied or not by the elements of the compositions presented.

Les compositions qui satisfont toutes les relations et qui présentent ainsi les meilleures caractéristiques en fluage, oxydation et dureté avant et après traitement thermique, avec le ΔNb le plus faible, sont les nuances 1-4 selon l'invention.

Figure 00070001
Figure 00080001
The compositions which satisfy all relationships and which therefore have the best creep, oxidation and hardness characteristics before and after heat treatment, with the lowest ΔNb, are grades 1-4 according to the invention.
Figure 00070001
Figure 00080001

Claims (10)

Procédé de réalisation d'une bande de tôle en acier ferritique dit à 14% de chrome stabilisé au niobium, caractérisé en ce que l'acier de composition pondérale suivante :
carbone ≤ 0,02%
0,002% ≤ azote ≤ 0,02%
0,05% ≤ silicium ≤ 1%
0% < manganèse ≤ 1%
0,2% ≤ niobium ≤ 0,6%
13,5% ≤ chrome ≤ 16,5%
0.02% ≤ molybdène ≤ 1.5%
0% < cuivre ≤ 1,5%
0% < nickel ≤ 0.2%
0% < phosphore ≤ 0,020%
0% < soufre ≤ 0,003%
0,005% < étain ≤ 0,04%
les impuretés inhérentes à l'élaboration
la teneur en niobium, carbone, azote satisfaisant la relation :
9.5 ≤ Nb/(C+N)
est soumis à : un réchauffage avant laminage à chaud à une température comprise entre 1150°C et 1250°C et de préférence à environ 1175°C, un bobinage à une température comprise entre 600°C et 800°C et de préférence à environ 600°C, un laminage à froid de la bobine avec ou sans recuit préalable, un recuit final de la bande de tôle à une température comprise entre 800°C et 1100°C pendant une durée comprise entre 1 mn et 5 mn et de préférence à une température d'environ 1050°C pendant un temps d'environ 2 mn. Process for producing a strip of ferritic steel sheet said to 14% chromium stabilized with niobium, characterized in that the steel of the following composition by weight:
carbon ≤ 0.02%
0.002% ≤ nitrogen ≤ 0.02%
0.05% ≤ silicon ≤ 1%
0% <manganese ≤ 1%
0.2% ≤ niobium ≤ 0.6%
13.5% ≤ chromium ≤ 16.5%
0.02% ≤ molybdenum ≤ 1.5%
0% <copper ≤ 1.5%
0% <nickel ≤ 0.2%
0% <phosphorus ≤ 0.020%
0% <sulfur ≤ 0.003%
0.005% <tin ≤ 0.04%
the impurities inherent in the preparation
the niobium, carbon, nitrogen content satisfying the relationship:
9.5 ≤ Nb / (C + N)
is subject to: reheating before hot rolling at a temperature between 1150 ° C and 1250 ° C and preferably at around 1175 ° C, winding at a temperature between 600 ° C and 800 ° C and preferably at around 600 ° C, cold rolling of the coil with or without prior annealing, a final annealing of the sheet metal strip at a temperature between 800 ° C and 1100 ° C for a time between 1 min and 5 min and preferably at a temperature of about 1050 ° C for a time of about 2 min . Procédé selon la revendication 1 caractérisé en ce qu'après le recuit final ou préalablement à l'utilisation, la tôle est soumise à un traitement thermique à une température comprise entre 800°C et 1000°C pendant un temps compris entre 1 mn et 100 h et de préférence à une température d'environ 850°C pendant un temps égal ou inférieur à 30 mn.Method according to claim 1 characterized in that after the final annealing or before use, the sheet is subjected to a heat treatment at a temperature between 800 ° C and 1000 ° C for a time between 1 min and 100 h and preferably at a temperature of about 850 ° C for an equal time or less than 30 min. Tôle en acier ferritique dit à 14% de chrome stabilisé au niobium, obtenue pour la mise en oeuvre du procédé selon l'une des revendications 1 ou 2, caractérisée par la composition pondérale suivante :
carbone ≤ 0,02%
0,002% ≤ azote ≤ 0,02%
0,05% ≤ silicium ≤ 1%
0% < manganèse ≤ 1%
0,2% ≤ niobium ≤ 0,6%
13,5% ≤ chrome ≤ 16,5%
0.02% ≤ molybdène ≤ 1.5%
0% < cuivre ≤ 1,5%
0% < nickel ≤ 0.2%
0% < phosphore ≤ 0,020%
0% < soufre ≤ 0,003%
0,005% < étain ≤ 0,04%
les impuretés inhérentes à l'élaboration
la teneur en niobium, carbone, azote satisfaisant la relation :
9.5 ≤ Nb/(C+N)Ferritic steel sheet, said to have 14% chromium stabilized with niobium, obtained for the implementation of the process according to one of claims 1 or 2, characterized by the following weight composition:
carbon ≤ 0.02%
0.002% ≤ nitrogen ≤ 0.02%
0.05% ≤ silicon ≤ 1%
0% <manganese ≤ 1%
0.2% ≤ niobium ≤ 0.6%
13.5% ≤ chromium ≤ 16.5%
0.02% ≤ molybdenum ≤ 1.5%
0% <copper ≤ 1.5%
0% <nickel ≤ 0.2%
0% <phosphorus ≤ 0.020%
0% <sulfur ≤ 0.003%
0.005% <tin ≤ 0.04%
the impurities inherent in the preparation
the niobium, carbon, nitrogen content satisfying the relationship:
9.5 ≤ Nb / (C + N) Tôle d'acier ferritique selon la revendication 3 caractérisée en ce que la teneur en Nb satisfait la relation 0.1 ≤ ΔNb ≤ 0.5 avec ΔNb = Nb - 7(C+N) et de préférence 0.2 ≤ ΔNb ≤ 0.3.Ferritic steel sheet according to claim 3 characterized in that the content of Nb satisfies the relationship 0.1 ≤ ΔNb ≤ 0.5 with ΔNb = Nb - 7 (C + N) and preferably 0.2 ≤ ΔNb ≤ 0.3. Tôle en acier ferritique selon l'une des revendications 3 et 4 caractérisée en ce que les teneurs en niobium, silicium et molybdène satisfont la relation :
ΔNb /(Si+Mo) < 0.9 Ferritic steel sheet according to one of claims 3 and 4 characterized in that the niobium, silicon and molybdenum contents satisfy the relationship:
ΔNb / (Si + Mo) <0.9 Tôle en acier selon l'une des revendications 3 à 5 caractérisée en ce que les teneurs pondérales en niobium et étain satisfont la relation : ΔNb/Sn > 50Steel sheet according to one of Claims 3 to 5, characterized in that the niobium and tin weight contents satisfy the relationship: ΔNb / Sn> 50 Tôle en acier selon l'une des revendications 3 à 6 caractérisée en ce que les teneurs pondérales en silicium et manganèse satisfont la relation : Si/Mn ≥ 1Steel sheet according to one of Claims 3 to 6, characterized in that the weight contents of silicon and manganese satisfy the relationship: Si / Mn ≥ 1 Tôle en acier ferritique selon l'une des revendications 3 à 7 caractérisée en ce que les teneurs en niobium, titane, zirconium, aluminium satisfont la relation : N/(Ti+Zr+Al) ≥ 0.16Ferritic steel sheet according to one of Claims 3 to 7, characterized in that the niobium, titanium, zirconium and aluminum contents satisfy the relationship: N / (Ti + Zr + Al) ≥ 0.16 Tôle en acier ferritique selon l'une des revendications 3 à 8 caractérisée en ce que l'acier comporte, après traitement thermique, au niveau des joints de grains, un composé intermétallique de maille quadratique du type Fe2Nb3.Ferritic steel sheet according to one of claims 3 to 8 characterized in that the steel comprises, after heat treatment, at the grain boundaries, a intermetallic compound of quadratic mesh of the Fe2Nb3 type. Utilisation de la tôle d'acier ferritique selon les revendications 3 à 9, obtenue par le procédé selon les revendications 1 et 2, dans le domaine de l'automobile et notamment pour la réalisation de collecteur de ligne d'échappement.Use of the ferritic steel sheet according to claims 3 to 9, obtained by the method according to claims 1 and 2, in the automotive field and in particular for the production of an exhaust line collector.
EP00402447A 1999-09-09 2000-09-06 Ferritic niobium-stabilised 14% chromium steel and its use in the car industry Expired - Lifetime EP1083241B1 (en)

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FR9911257 1999-09-09

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EP2246455A1 (en) * 2008-01-28 2010-11-03 Nippon Steel & Sumikin Stainless Steel Corporation High-purity ferritic stainless steel excellent in corrosion resistance and workability and process for production of the same
EP3670692A1 (en) 2018-12-21 2020-06-24 Outokumpu Oyj Ferritic stainless steel

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WO2004053171A1 (en) * 2002-12-12 2004-06-24 Nippon Steel & Sumikin Stainless Steel Corporation Cr-CONTAINING HEAT-RESISTANT STEEL SHEET EXCELLENT IN WORKABILITY AND METHOD FOR PRODUCTION THEREOF
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JP4624473B2 (en) 2008-12-09 2011-02-02 新日鐵住金ステンレス株式会社 High purity ferritic stainless steel with excellent weather resistance and method for producing the same
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EP3670692A1 (en) 2018-12-21 2020-06-24 Outokumpu Oyj Ferritic stainless steel
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