EP1312691A1 - Austenitische hitzebeständige Legierung mit verbesserter Vergiessbarkeit und Transformation, Verfahren zur Herstellung von Brammen und Drähten - Google Patents

Austenitische hitzebeständige Legierung mit verbesserter Vergiessbarkeit und Transformation, Verfahren zur Herstellung von Brammen und Drähten Download PDF

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Publication number
EP1312691A1
EP1312691A1 EP02292531A EP02292531A EP1312691A1 EP 1312691 A1 EP1312691 A1 EP 1312691A1 EP 02292531 A EP02292531 A EP 02292531A EP 02292531 A EP02292531 A EP 02292531A EP 1312691 A1 EP1312691 A1 EP 1312691A1
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European Patent Office
Prior art keywords
alloy
composition
content
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solidification
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP02292531A
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English (en)
French (fr)
Inventor
Jean-Michel Hauser
Christophe Bourgin
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Ugitech SA
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USINOR SA
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Publication of EP1312691A1 publication Critical patent/EP1312691A1/de
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Classifications

    • 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
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • C22C38/40—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
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Definitions

  • the present invention relates to an austenitic alloy for heat resistance to improved flowability and transformation.
  • Steels for mechanical strength when hot include martensitic steels usable up to about 550 ° C, austenitic stainless steels with a hardening of intermetallic phase, which can be used up to 650 ° C about.
  • Nickel or cobalt alloys are also used, generally hardened by precipitation of intermetallics.
  • Austenitic stainless steels for mechanical resistance to heat such as steel referenced n ° 1.4980, according to European standard EN10269, also referenced AISI 660 according to ASTM A453, are frequently used in bolts and struck parts, in particular in fasteners for automobile exhaust elements, such as as turbochargers or upstream exhaust downpipes. We meet them also, in the form of drawn wires, in knits for the mechanical setting of the catalysts exhaust. We also know applications of these steels in the field of hot springs or exhaust hoses made up of rolled tubes - welded then corrugated, and on the other hand sheaths of woven metal wires.
  • composition of AISI 660 steel has a moderate chromium content of about 15%, about 1% molybdenum, 0.3% vanadium.
  • the character austenitic, necessary for keeping hot, is ensured by a massive addition of nickel, that is to say of the order of 24%.
  • the hardening and the creep resistance are ensured by an addition of approximately 2% of titanium, which combines between 600 ° C and 750 ° C with part of the nickel to form intermetallics of the Ni 3 Ti type.
  • the composition of the steel may also contain elements such as Mo, V, Al which also contribute to hardening and to keeping hot by replacing the titanium atoms in the Ni 3 Ti compound.
  • the alloy according to the IMPHY patent is solidifying austenitic, as we will demonstrate later. It is therefore prone to problems casting and rolling linked to segregation.
  • the composition of the alloy according to the NIPPON KOKAN patent has a low nickel content associated with a chromium content of between 13% and 20%.
  • the nickel content may not be sufficient to cure and hold effective creep at 650 ° C and above.
  • the very low carbon content less than 0.010% makes it unsuitable for production in air. It does not solidify probably not in all ferrite cases.
  • the object of the invention is to propose an alloy of the austenitic stainless type for mechanical resistance to heat, which can be produced economically and particularly suitable for continuous casting and hot processing.
  • a fifth object of the invention consists of the alloy parts which can be obtained by machining or hot or cold forming, or knitting, from a billet, wire or bar obtained by one of the processes according to the invention.
  • Figures 1a and 1b are micrographs on the solid state of solidification showing the phases formed at the start of solidification, with on the one hand, in FIG. 1a, in a example of invention 13605, the presence of ferrite in the dendrite axis, in plain text on the figure, and on the other hand, in figure 1b, corresponding to a counter example on steel IMPHY of the prior art, the presence of dendrites with an austenitic axis.
  • Figures 2, 3 and 4 show hot ductility curves of the compositions of Table 1; the burn points, estimated by the temperature at which the ductility is maximum, are shown in Table 2.
  • the invention presented relates to an alloy austenitic for heat resistance with flowability and improved transformation.
  • composition 2 of the invention the manganese content is greater than 2%.
  • the relationships allow the compositions to be selected. ferritic solidification, without residual ferrite and not forming a sigma phase.
  • Table 1 shows examples of casting carried out under vacuum for the production of the alloy according to the invention, as well as counter-examples of castings not responding to the invention, and compositions according to the cited prior art.
  • the solidification takes place first in the form of dendritic ferritic axes, which contain residual ferrite after cooling, as shown in the figure 1a, unlike the known and observed cases of AISI 660 reference steel and the alloy according to the IMPHY patent, the solidification of which begins by forming austenite, as shown in Figure 1b.
  • Figures 2, 3 and 4 show hot ductility curves of the compositions studied; ductility is measured by delta ⁇ , which is the diametral necking at break; that is to say the relative variation in diameter at the level of the rupture; the points of burn estimated by the temperature at which the ductility is maximum, are reported on table 2.
  • Solidification in ferritic mode allows to reheat and laminate ingots or semi-finished products at normal speed between 1100 and 1200 ° C, preferably between 1120 and 1180 ° C, in a range of usual temperatures for stainless steels and compatible with furnaces reheating and mechanical dimensions of rolling mills.
  • the presence of the sigma phase is known to decrease the resilience and toughness of austenitic steels.
  • a criterion was determined to ensure the absence of the sigma phase in the aged state: Cr + 1.5 x Si + 1.5 x V + 1.2 x Mo ⁇ 22.
  • the above criterion therefore makes it possible to ensure a level of resilience sufficient to the treated state as well as after hot use.
  • Creep rupture tests at 650 ° C under 385 MPa were carried out on the flows 13468 Imphy and 13605.
  • the requirements usually required for hot fixings, especially more than 100 breaking hours, and more than 5% elongation at break are respected.
  • a minimum carbon content of 0.010% is necessary for allow the preparation "under air” in installations such as electric oven more refining at AOD and in the bag, without using vacuum or vacuum.
  • a maximum carbon content of 0.040% is necessary to avoid lowering strongly the liquidus of the alloy and increase the solidification interval of the alloy, making continuous casting impossible.
  • the carbon combines with a part of the titanium in the form of carbides of the TiC type, which is no longer available to harden the alloy in the aged state in the form of Ni 3 Ti. This phenomenon should be minimized by limiting the carbon content.
  • a maximum nitrogen content of 0.010% is the result of the reaction, in the liquid metal, titanium added in large quantities with the nitrogen already present: there are formation and decantation of TiN nitrides in ladles and tundish, and the nitrogen content of the cast product cannot exceed the previous value.
  • Silicon is generally present in the composition, at least in trace amounts whose order of magnitude is 0.001% in steel products.
  • Silicon contributes to the formation of ferrite and sigma phase. A content maximum of 2.0% is necessary to avoid accelerated formation of the latter weakening phase.
  • Silicon contributes to improving resistance to oxidation and the hot environment, by the formation of more or less continuous layers of silica or silicates under the other oxides.
  • a significant addition for example more than 1% is therefore useful when solidification takes place in ferritic mode.
  • a minimum content of 0.001% manganese is generally present as a residue originating in particular from ferroalloys.
  • manganese oxidizes easily during blowing oxygen intended to bring the carbon to the required level and; a maximum content of 8% is necessary to allow ripening under yield conditions correct addition of manganese.
  • manganese has the specific interest of promoting the ferritic solidification mode, while on the contrary favoring the elimination of the residual ferrite during annealing between 900 ° C and 1200 ° C, especially on product hot processed. It does not cause sigma phase formation.
  • manganese causes an increase in the thickness of the calamines on hot rolled or annealed products or during use.
  • a maximum content of 19.9% nickel is imposed for reasons especially economic.
  • nickel can be brought above 18%. In these conditions, the hardening that occurs during aging at 720 ° C reaches practically already its maximum.
  • chromium is required to counteract the formation effect of nickel austenite and obtain a ferritic solidification, in particular when the other ferrite-forming elements, such as Si, Mo, Mn, Ti, Al, V, are at a low level or close to their minimum content.
  • a content limited to a maximum of 21% of chromium is necessary to avoid the formation of weakening sigma phase during treatments at 720 ° C or during use in the range between 600 ° C and 700 ° C.
  • a minimum content of 1.8% of titanium is necessary to obtain sufficient hardening during aging treatments or when used in the range between 600 ° C and 750 ° C.
  • a fine precipitation based on Ni 3 Ti then occurs, which contributes to the mechanical resistance to heat, in particular under creep conditions.
  • Titanium is also present in the alloy in the form of titanium nitride, titanium carbide and titanium phosphide.
  • a content limited to 3.0% is necessary to avoid the lowering of the liquidus and the formation, during solidification, of coarse intermetals which can harm the tréfilact.
  • a minimum content of 0.010% molybdenum is generally present in the state traces during industrial processing.
  • Molybdenum contributes to the formation of ferrite during solidification and to the formation of hardening intermetallics, replacing titanium atoms.
  • the addition of molybdenum improves the heat resistance of the alloy, in thereby increasing the precipitate content and the shear strength.
  • a maximum content of 3% is necessary to avoid phase formation sigma in association with chromium as well as the presence of residual ferrite.
  • a minimum content of 0.010% copper is generally present as processing residue.
  • Copper contributes to the formation of austenite and helps reduce the rate of residual ferrite, just like nickel.
  • a maximum content of 3% is imposed to avoid strong segregation during of the casting and the formation of a copper-rich phase greatly lowering the point of burn.
  • a minimum content of 0.0005% aluminum is generally present as that processing residue.
  • aluminum can be used to increase the ferritic character of the alloy during solidification, without the disadvantage of generating the sigma phase weakening when maintained at temperatures in the range between 550 ° C. and 700 ° C.
  • a maximum content of 1.5% aluminum is necessary to avoid depletion of nickel during the formation of intermallics and the presence of ferrite residual.
  • a minimum content of 0.0001% of boron is generally present in the state of traces.
  • boron at a rate of 10 to 30 ppm, for example, allows a slight improvement of hot ductility in the temperature range between 800 ° C and 1100 ° C.
  • a maximum content of 0.01% is necessary to avoid excessive lowering of the solidus and the burn point it causes.
  • a minimum content of 0.01% vanadium is generally present as that processing residue.
  • Vanadium, ferritizing element and sigma phase former can be added to contribute to the hardening by substitution of the titanium atoms in the intermetallic compounds.
  • a maximum content of 2% vanadium is necessary to avoid the formation sigma phase, in combination with the chromium present.
  • a minimum content of 0.0001% sulfur is generally present as refining residue.
  • Sulfur can be maintained voluntarily, or preferably added more 0.030%, to improve the machinability of the alloy, thanks to the presence of sulfides and titanium carbosulfides formed during solidification, which improve fragmentation shavings.
  • This addition is made possible by the ferritic solidification mode, because the addition of sulfur does not significantly degrade the hot ductility during rolling, unlike the prior art, with austenitic solidification and marked segregations.
  • a maximum content of 0.2% is necessary to avoid the risks of opening length of the semi-finished products, along the elongated sulphides, during rolling at hot.
  • a minimum content of 0.001% phosphorus is generally present as that processing residue.
  • a maximum content of 0.040% phosphorus is necessary to avoid the presence of large particles of titanium phosphides formed during solidification and which may adversely affect wire drawing.
  • Other elements such as cobalt, tungsten, niobium, zirconium, tantalum, hafnium, oxygen, magnesium, calcium, may be present as residues from processing or deoxidation; other elements can be added voluntarily in quantities not exceeding 0.5% to improve properties specific, such as resistance to oxidation by micro - addition of yttrium, cerium, lanthanum and other rare earths.
  • the same operations were carried out on several castings of the AISI 660 grade, which gave rise to many faults (cracks on blooms, cracks on billets, straws and scales on wire rod).
  • the AISI grade 660 is cast in the form of ingots without using the continuous casting process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
EP02292531A 2001-11-16 2002-10-15 Austenitische hitzebeständige Legierung mit verbesserter Vergiessbarkeit und Transformation, Verfahren zur Herstellung von Brammen und Drähten Withdrawn EP1312691A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0114818 2001-11-16
FR0114818A FR2832425B1 (fr) 2001-11-16 2001-11-16 Alliage austentique pour tenue a chaud a coulabilite et transformation ameliorees

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2503012A1 (de) * 2011-03-21 2012-09-26 Daido Steel Co.,Ltd. Ausscheidungsgehärteter, hitzebeständiger Stahl
WO2014139890A1 (fr) * 2013-03-13 2014-09-18 Areva Np Acier inoxydable pour forgeage à chaud et procédé de forgeage à chaud utilisant cet acier
CN114934228A (zh) * 2022-05-18 2022-08-23 湖南华菱涟源钢铁有限公司 一种热成形钢板及其生产方法
CN117960829A (zh) * 2024-03-29 2024-05-03 攀钢集团研究院有限公司 Al-Si镀层钢板的制备方法、热冲压构件及其制备方法

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Publication number Priority date Publication date Assignee Title
JP4839193B2 (ja) * 2006-12-01 2011-12-21 株式会社神戸製鋼所 ソリッドワイヤ
US8461485B2 (en) * 2006-12-29 2013-06-11 Kobe Steel, Ltd. Solid wire
DE102008017821A1 (de) * 2008-04-08 2009-10-22 Continental Automotive Gmbh Befestigungselement und Abgasturbolader mit variabler Turbinengeometrie
WO2014103728A1 (ja) * 2012-12-27 2014-07-03 昭和電工株式会社 成膜装置
WO2014103727A1 (ja) * 2012-12-27 2014-07-03 昭和電工株式会社 ＳｉＣ膜成膜装置およびＳｉＣ膜の製造方法
US10669601B2 (en) 2015-12-14 2020-06-02 Swagelok Company Highly alloyed stainless steel forgings made without solution anneal
GB2546809B (en) * 2016-02-01 2018-05-09 Rolls Royce Plc Low cobalt hard facing alloy
GB2546808B (en) * 2016-02-01 2018-09-12 Rolls Royce Plc Low cobalt hard facing alloy
CN114941055B (zh) * 2022-03-28 2024-07-23 江苏武进不锈股份有限公司 集成电路及ic产业制备装置用超高洁净度不锈钢无缝管的制备方法和不锈钢无缝管

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EP0669405A2 (de) * 1994-02-24 1995-08-30 Daido Tokushuko Kabushiki Kaisha Wärmebeständiger Stahl
FR2727982A1 (fr) * 1994-12-13 1996-06-14 Imphy Sa Acier inoxydable austenitique pour emploi a chaud

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GB675809A (en) * 1949-04-22 1952-07-16 Electric Furnace Prod Co Improvements in iron base alloys for high-temperature service
GB686766A (en) * 1949-10-14 1953-01-28 Westinghouse Electric Int Co Improvements in or relating to austenitic alloys
US3065067A (en) * 1959-01-21 1962-11-20 Allegheny Ludlum Steel Austenitic alloy
US3201233A (en) * 1962-06-13 1965-08-17 Westinghouse Electric Corp Crack resistant stainless steel alloys
US3563729A (en) * 1968-04-16 1971-02-16 Crucible Inc Free-machining corrosion-resistant stainless steel
US3865581A (en) * 1972-01-27 1975-02-11 Nippon Steel Corp Heat resistant alloy having excellent hot workabilities
JPS6029453A (ja) * 1983-07-29 1985-02-14 Hitachi Ltd 蒸気タ−ビン動翼用Ｃｒ−Νｉ合金
EP0669405A2 (de) * 1994-02-24 1995-08-30 Daido Tokushuko Kabushiki Kaisha Wärmebeständiger Stahl
FR2727982A1 (fr) * 1994-12-13 1996-06-14 Imphy Sa Acier inoxydable austenitique pour emploi a chaud

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2503012A1 (de) * 2011-03-21 2012-09-26 Daido Steel Co.,Ltd. Ausscheidungsgehärteter, hitzebeständiger Stahl
US9145600B2 (en) 2011-03-21 2015-09-29 Daido Steel Co., Ltd. Precipitation hardened heat-resistant steel
WO2014139890A1 (fr) * 2013-03-13 2014-09-18 Areva Np Acier inoxydable pour forgeage à chaud et procédé de forgeage à chaud utilisant cet acier
FR3003271A1 (fr) * 2013-03-13 2014-09-19 Areva Np Acier inoxydable pour forgeage a chaud et procede de forgeage a chaud utilisant cet acier
CN114934228A (zh) * 2022-05-18 2022-08-23 湖南华菱涟源钢铁有限公司 一种热成形钢板及其生产方法
CN117960829A (zh) * 2024-03-29 2024-05-03 攀钢集团研究院有限公司 Al-Si镀层钢板的制备方法、热冲压构件及其制备方法

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US6896747B2 (en) 2005-05-24
FR2832425B1 (fr) 2004-07-30
US20030103859A1 (en) 2003-06-05
FR2832425A1 (fr) 2003-05-23

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