US20100278684A1 - Process for manufacturing stainless steel containing fine carbonitrides, and product obtained from this process - Google Patents

Process for manufacturing stainless steel containing fine carbonitrides, and product obtained from this process Download PDF

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Publication number
US20100278684A1
US20100278684A1 US12/682,380 US68238008A US2010278684A1 US 20100278684 A1 US20100278684 A1 US 20100278684A1 US 68238008 A US68238008 A US 68238008A US 2010278684 A1 US2010278684 A1 US 2010278684A1
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Prior art keywords
stainless steel
liquid metal
titanium
nozzle
semi
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Abandoned
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US12/682,380
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English (en)
Inventor
Jean-Michel Damasse
Paul Naveau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aperam Stainless France SA
Aperam Invest France SAS
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ArcelorMittal Stainless France SA
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Assigned to ARCELORMITTAL-STAINLESS FRANCE reassignment ARCELORMITTAL-STAINLESS FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAVEAU, PAUL, DAMASSE, JEAN-MICHEL
Publication of US20100278684A1 publication Critical patent/US20100278684A1/en
Assigned to APERAM ALLOYS IMPHY reassignment APERAM ALLOYS IMPHY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ARCELORMITTAL - STAINLESS FRANCE
Assigned to APERAM STAINLESS FRANCE reassignment APERAM STAINLESS FRANCE CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY DATA AND EXECUTION DATE PREVIOUSLY RECORDED ON REEL 030756 FRAME 0886. ASSIGNOR(S) HEREBY CONFIRMS THE RECEIVING PARTY AND THE EXECUTION DATE IN THE PRESENT SUBMISSION. Assignors: ARCELORMITTAL-STAINLESS FRANCE
Assigned to APERAM INVEST FRANCE reassignment APERAM INVEST FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: APERAM STAINLESS FRANCE
Assigned to APERAM STAINLESS FRANCE reassignment APERAM STAINLESS FRANCE CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: APERAM INVEST FRANCE
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/108—Feeding additives, powders, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/005—Manufacture of stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0068—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by introducing material into a current of streaming metal
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/18—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
    • C22C38/46—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

Definitions

  • the invention relates to a process for manufacturing stabilized stainless steels for inexpensively obtaining a very fine dispersion of carbonitrides after solidification, with a minimized risk of nozzle blockage during casting.
  • the invention also relates to continuously cast stabilized stainless steels having a very fine dispersion of uniformly distributed carbonitrides.
  • stabilizing elements are carried out.
  • any precipitation of chromium carbide at the grain boundaries may lead to a local depletion of chromium and therefore to a sensitivity to intergranular corrosion.
  • Elements such as titanium, zirconium, niobium and vanadium, which form carbides, nitrides or carbonitrides that are more stable than chromium carbides, are therefore used as stabilizing elements for fixing carbon and nitrogen.
  • the continuous casting of steel is a well-known process. It consists in pouring a liquid metal from a ladle into a tundish intended to regulate the flow and then, after this tundish, in pouring the metal into the upper part of a water-cooled bottomless copper mould undergoing a vertical reciprocating movement. The solidified semi-finished product is extracted from the lower part of the mould by rollers.
  • the liquid steel is introduced into the mould by means of a tubular duct called a nozzle placed between the tundish and the mould.
  • a pouring device for additions in the mould stage, as described in the Centre deInstituts Métallurgiques patent EP 269 180.
  • the liquid metal is poured onto the top of a dome made of a refractory material of a tundish member.
  • the shape of this dome causes the metal to flow towards its periphery, the flow being deflected towards the internal wall of the nozzle or of an intermediate vertical tubular member.
  • What is thus created, in the central part of the nozzle beneath the tundish member, is a volume without any liquid metal within which it is possible to carry out additions via an injection channel.
  • the device thus described is referred to as a hollow jet nozzle.
  • patent BE 1 014 063 describes a method of adding metal powders in order to form oxides during solidification.
  • a steel having a given amount of dissolved oxygen (O 2 ) is poured from the tundish into the mould, an addition (M) of metal powder is carried out, the M/O 2 ratio is checked and the powder is mixed with the liquid metal so as to form metal oxides.
  • Patent WO 2006/096942 describes an addition of high-performance ceramic nanoparticles within a hollow jet nozzle.
  • These ceramic nanoparticles may be oxides, nitrides, carbides, borides or silicides and are characterized by a high thermal stability, so that practically no reaction occurs between them and the liquid metal.
  • this method is difficult to implement due to agglomeration of the nanoparticles, which tend to form larger particles possibly causing the abovementioned defects.
  • the application of such a technique to stainless steels is not mentioned in the above patent.
  • the object of the invention is to provide a process for manufacturing stabilized stainless steels having a fine uniform dispersion of nitrides and/or carbonitrides.
  • the aim in particular is to obtain a large number of fine precipitates, with a size of less than 2.5 microns, while still limiting the number of coarse precipitates of size greater than 10 microns.
  • Another object of the invention is to provide a process which is more to efficacious as regards the efficiency of the additions of stabilizing elements, compared with in-ladle addition processes.
  • Another object of the invention is to provide a process for minimizing the risk of nozzle blockage when continuously casting stainless steels.
  • Another object of the invention is to provide stainless steel semi-finished products of equiaxed solidification structure after the continuous casting, even without employing electromagnetic stirring techniques.
  • Another object of the invention is to provide stainless steel semi-finished products which are very uniform over a cross section in relation to the continuous casting direction.
  • the subject of the invention is a process for manufacturing a semi-finished product made of stabilized stainless steel, which includes a casting step by means of a hollow jet nozzle placed between a tundish and a continuous casting mould, said nozzle comprising, in its upper part, a distributing member for deflecting the liquid metal arriving at the inlet of the nozzle, thus defining an internal volume with no liquid metal.
  • the process is characterized in that a non-stabilized stainless steel containing no nitride, carbide and carbonitride precipitates, is delivered in liquid metal form into the tundish; then the liquid metal is cast by means of the nozzle, simultaneously carrying out an addition of metal powder into the internal volume of the hollow jet, the metal powder containing at least one element for stabilizing the stainless steel, the addition being carried out at a liquid steel temperature between T liquidus +10° C. and T liquidus +40° C.; and the liquid metal is solidified, the solidification starting less than 2 seconds after the addition, in order to obtain the semi-finished product.
  • the subject of the invention is also a process according to one of the above embodiments, characterized in that the stabilizing element is chosen from one or more of the following elements: titanium, niobium, zirconium and vanadium.
  • the stabilizing element is titanium, the titanium, carbon and nitrogen contents of the stainless steel satisfying, the contents being expressed in percentages by weight: Ti ⁇ 0.15+4(C+N).
  • the steel is a ferritic stainless steel or an austenitic stainless steel or a martensitic stainless steel or an austeno-ferritic stainless steel.
  • the subject of the invention is also a semi-finished product manufactured by a process according to one of the above embodiments, characterized in that it has a fully-equiaxed solidification structure.
  • the subject of the invention is also a stainless steel product manufactured from a semi-finished product produced by a process according to one of the above embodiments, characterized in that the stabilizing element is titanium and in that the number of titanium nitride or carbonitride precipitates of size smaller than 2.5 microns is greater than 15 000/cm 2 .
  • the number of titanium nitrides or carbonitrides of size greater than 10 microns is preferably less than 50/cm 2 .
  • the mean inter-precipitate distance is less than 15 microns.
  • FIG. 1 shows schematically an example of a device for implementing the process according to the invention.
  • the invention presented relates to a wide range of stainless steels capable of being stabilized by additions of titanium, niobium, zirconium, vanadium or other stabilizing elements, these elements being used separately or in combination.
  • the invention may be advantageously implemented in the manufacture of ferritic stainless steels of the X 3CrTi17 type, with the following composition according to standard NF.EN 10.088-1 and 2: C ⁇ 0.050%, Si ⁇ 1.00%, Mn ⁇ 1.00%, P ⁇ 0.040%, S ⁇ 0.015%, Cr:16.00-18.00%, N ⁇ 0.045%, 0.15+4(C+N) ⁇ Ti ⁇ 0.080%, the contents being expressed in percentages by weight.
  • the process according to the invention is the following:
  • the liquid metal may possibly contain a small amount of an element for stabilizing the stainless steel, no precipitation of this element occurs.
  • the principal addition of stabilizing element and its precipitation take place subsequently, as described below.
  • the composition and the temperature of the liquid metal are such that no nitride, carbide or carbonitride precipitates exist under these conditions.
  • the carbon and nitrogen contents are used to adjust the amounts of stabilizing elements that will be added subsequently.
  • the content of the ladle is poured into a tundish 1 having a bottom with a closure device 2 , the degree of sealing of which enables the flow into a pouring nozzle 3 to be regulated.
  • the temperature of the liquid steel must not be too high. This is because, as will be seen later, the additions within the hollow jet nozzle must be carried out at a temperature not too far above the liquidus temperature (denoted by T liquidus ) of the steel.
  • the process according to the invention requires the use of a hollow jet nozzle.
  • This nozzle has a distributing dome 4 made of a refractory material pierced by one or more injection channels that open into the central lower part of the dome in the form of injection tubes 5 . It is thus possible to add a metal powder conveyed by a carrier gas.
  • the injected powder 6 mixes with the liquid metal which is deflected by the upper part of the dome towards the walls of the nozzle or of an intermediate tubular member between the actual nozzle and the tundish.
  • the powder is fed by one or more tubes 7 which are themselves connected to one or more reservoirs 8 .
  • the upper part 9 of these powder reservoirs is under pressure from an inert carrier gas such as argon, enabling the powder to be protected from oxidation.
  • a suitable flow of gas forces the powder to flow into the hollow jet nozzle with a flow rate corresponding to the desired amount to be added.
  • the flow of powder may also be facilitated by a mechanical device, such as a feed screw.
  • the particle size of the powder must be chosen so as to ensure that there is easy flow between the reservoirs and the nozzle and almost immediate melting in the liquid metal. A spherical particle size between 100 and 200 microns is very suitable for these requirements.
  • This powder contains one or more metal elements intended to stabilize the stainless steel, namely:
  • Powders of these metal elements may of course be mixed together so as to produce a particular combination, such as for example a titanium-niobium two-stabilizer blend. It is also possible to blend the above powders with ferro-alloys or with iron powder for the purpose of reducing the superheating temperature at the outlet of the hollow jet nozzle so as to increase the equiaxed zone fraction of the semi-finished product after solidification.
  • the powder comprising the stabilizing element or elements is added to a liquid metal at a temperature between T liquidus +10° C. and T liquidus +40° C.
  • This particular addition temperature range makes it possible simultaneously:
  • the stabilizing element is melted by contact with the liquid metal in a few tenths of a second. Since the powder is protected from oxidation by the inert gas until its contact with the liquid metal, the effectiveness of the addition is high.
  • a sufficient amount of stabilizing elements are added in order for the nitrogen and carbon to be fully precipitated and for the solubility product corresponding to the formation of these precipitates to reach or exceed the temperature at which the addition is carried out.
  • the nitrides and/or carbonitrides then precipitate immediately in a very fine form.
  • the liquid metal starts to solidify in less than 2 seconds, solidification starting on the walls of the mould 10 .
  • This very short time in which the precipitates are maintained in the liquid metal prevents them from increasing in size.
  • a person skilled in the art will know how to adapt the various parameters at his disposal, such as the following: height of the injection device relative to the mould; injection rate; greater or lesser power of the heat exchangers; semi-finished product extraction rate; superheating temperature; complementary injection of ferro-alloy powder in order to speed up the solidification, in order for the time between addition and start of solidification to be less than 2 seconds.
  • a preferred embodiment is based on the use of titanium for the purpose of precipitating fine dispersed nitrides and/or carbonitrides.
  • the titanium, carbon and nitrogen contents of the stainless steel expressed in percentages by weight, are such that: Ti ⁇ 0.15+4(C+N). Under these conditions, the amount of titanium added enables the steel to be fully stabilized.
  • One particular feature of the stainless steels obtained according to the invention lies in the great uniformity in the dispersion of the nitrides and carbonitrides with a shorter mean inter-precipitate distance, so that any sensitivity because of a locally depleted zone is reduced.
  • the above parameters, and especially the powder injection rate and the superheating temperature are adapted so as to obtain a semi-finished product with a fully equiaxed solidification structure.
  • the term “semi-finished product” denotes for example a slab (with a thickness of around 200 mm), a thin slab (with a thickness of around 50-80 mm), a thin strip (with a thickness of around 1-3 mm) or a billet, which is not yet mechanically hot-deformed.
  • Such an equiaxed structure is particularly advantageous in the field of ferritic stainless steels in order to minimize roping defects. It is known that such defects are manifested by the formation of surface irregularities after drawing that are parallel to the rolling direction. They are due to the presence of heterogeneous structures before cold rolling and annealing, which structures themselves result from columnar solidification structures.
  • the powder addition proves to be advantageous for obtaining a fully equiaxed structure since the precipitates act as nucleation sites, thus preventing less favourable columnar or basaltic solidification.
  • the invention therefore optionally makes it possible to employ electromagnetic stirring techniques that are normally used for this purpose.
  • the semi-finished product After the semi-finished product has been manufactured, it may be hot-rolled or cold-rolled, pickled and annealed, according to conventional processes, in order to obtain as it were a product that can take various forms, such as a hot-rolled strip, thin sheet or long product of various shapes.
  • grade B titanium was added in the form of titanium sponge to the ladle.
  • the liquid metal in the tundish contained no titanium.
  • This element was added within a hollow jet nozzle in the form of a ferro-titanium powder (30% iron/70% titanium) with a particle size between 100 and 200 microns.
  • the powder addition temperature was T liquidus +35° C.
  • the metal started to solidify on the walls of the mould less than two seconds after addition.
  • Various heats were formed into slabs according to the invention without encountering any nozzle blockage problem.
  • a fine precipitate ( ⁇ 2.5 ⁇ m) density greater than 15 000/cm 2 guarantees that the titanium nitrides are very uniformly distributed. Therefore, the carbon and nitrogen are very completely and uniformly trapped.
  • a coarse precipitate (>10 ⁇ m) density less than 50/cm 2 ensures that fracture initiation does not take place prematurely during mechanical stressing.
  • the invention makes it possible to increase the number of fine precipitates by a factor of about 2 and to reduce the number of coarse precipitates by a factor of about 3.
  • the efficiency of titanium addition (the ratio of titanium present in the final product to titanium added in powder form) is 95 to 100% in the process according to the invention. This efficiency is therefore very much higher than that of the conventional process, which is around 60%.
  • the process according to the invention therefore makes it possible for stabilized stainless steel grades having a very fine dispersion of nitrides or carbonitrides to be manufactured inexpensively and reliably.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Multimedia (AREA)
  • Manufacturing & Machinery (AREA)
  • Continuous Casting (AREA)
  • Powder Metallurgy (AREA)
US12/682,380 2007-10-10 2008-09-23 Process for manufacturing stainless steel containing fine carbonitrides, and product obtained from this process Abandoned US20100278684A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07291236A EP2047926A1 (fr) 2007-10-10 2007-10-10 Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé
EP07291236.3 2007-10-10
PCT/FR2008/001320 WO2009074736A1 (fr) 2007-10-10 2008-09-23 Procede de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu a partir de ce procede

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US20100278684A1 true US20100278684A1 (en) 2010-11-04

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US12/682,380 Abandoned US20100278684A1 (en) 2007-10-10 2008-09-23 Process for manufacturing stainless steel containing fine carbonitrides, and product obtained from this process

Country Status (5)

Country Link
US (1) US20100278684A1 (ko)
EP (2) EP2047926A1 (ko)
KR (1) KR101220791B1 (ko)
ES (1) ES2690310T3 (ko)
WO (1) WO2009074736A1 (ko)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013144668A1 (en) * 2012-03-28 2013-10-03 Arcelormittal Investigacion Y Desarrollo Sl Continuous casting process of metal
CN105018761A (zh) * 2015-07-28 2015-11-04 山西太钢不锈钢股份有限公司 一种高锰高铝型奥氏体低磁钢的连铸方法
US9475120B1 (en) * 2015-04-21 2016-10-25 Ut-Battelle, Llc Apparatus and method for dispersing particles in a molten material without using a mold

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US6231807B1 (en) * 1998-02-04 2001-05-15 Sandvik Ab Dispersion hardening alloy and method for the production of the alloy
JP2000144246A (ja) * 1998-11-18 2000-05-26 Nippon Steel Corp 冷間加工性に優れたマルテンサイト系ステンレス鋼の安価製造方法
JP2000160299A (ja) * 1998-11-20 2000-06-13 Nisshin Steel Co Ltd 耐リジング性に優れたフェライト系ステンレス鋼
JP2006233281A (ja) * 2005-02-25 2006-09-07 Jfe Steel Kk 電気伝導性および耐食性に優れた通電電気部品用ステンレス鋼及びその製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013144668A1 (en) * 2012-03-28 2013-10-03 Arcelormittal Investigacion Y Desarrollo Sl Continuous casting process of metal
CN104220190A (zh) * 2012-03-28 2014-12-17 安赛乐米塔尔研发有限公司 金属的连续铸造方法
JP2015514585A (ja) * 2012-03-28 2015-05-21 アルセロルミタル・インベステイガシオン・イ・デサロジヨ・エセ・エレ 金属の連続鋳造プロセス
US20150158078A1 (en) * 2012-03-28 2015-06-11 Arcelormittal Investigación Desarrollo, S.L. Continuous casting process of metal
RU2608253C2 (ru) * 2012-03-28 2017-01-17 Арселормитталь Инвестигасьон И Десарролло Сл Процесс непрерывного литья металла
US9475120B1 (en) * 2015-04-21 2016-10-25 Ut-Battelle, Llc Apparatus and method for dispersing particles in a molten material without using a mold
CN105018761A (zh) * 2015-07-28 2015-11-04 山西太钢不锈钢股份有限公司 一种高锰高铝型奥氏体低磁钢的连铸方法

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WO2009074736A1 (fr) 2009-06-18
EP2197608A1 (fr) 2010-06-23
KR20100080928A (ko) 2010-07-13
KR101220791B1 (ko) 2013-01-11

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