EP2047926A1 - Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé - Google Patents

Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé Download PDF

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Publication number
EP2047926A1
EP2047926A1 EP07291236A EP07291236A EP2047926A1 EP 2047926 A1 EP2047926 A1 EP 2047926A1 EP 07291236 A EP07291236 A EP 07291236A EP 07291236 A EP07291236 A EP 07291236A EP 2047926 A1 EP2047926 A1 EP 2047926A1
Authority
EP
European Patent Office
Prior art keywords
stainless steel
titanium
semi
nozzle
liquid metal
Prior art date
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.)
Withdrawn
Application number
EP07291236A
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German (de)
English (en)
French (fr)
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
Original Assignee
Ugine et Alz France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ugine et Alz France SA filed Critical Ugine et Alz France SA
Priority to EP07291236A priority Critical patent/EP2047926A1/fr
Priority to ES08860262.8T priority patent/ES2690310T3/es
Priority to KR1020107010145A priority patent/KR101220791B1/ko
Priority to US12/682,380 priority patent/US20100278684A1/en
Priority to EP08860262.8A priority patent/EP2197608B1/fr
Priority to PCT/FR2008/001320 priority patent/WO2009074736A1/fr
Publication of EP2047926A1 publication Critical patent/EP2047926A1/fr
Withdrawn legal-status Critical Current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 method for manufacturing stabilized stainless steels for economically obtaining a very fine dispersion of carbonitrides after solidification, with a minimized risk of nozzle clogging during casting.
  • the invention also relates to stabilized, continuously cast stainless steels having a very fine dispersion of homogeneously distributed carbonitrides.
  • stabilizing elements are made in the bag. It is known that a possible precipitation of chromium carbides at the grain boundaries can lead to a local depletion of chromium and thus to an awareness of intergranular corrosion.
  • Elements such as titanium, zirconium, niobium and vanadium which form carbides, nitrides or carbonitrides which are more stable than chromium carbides, are therefore used as stabilizing elements for fixing carbon and nitrogen.
  • Continuous casting of steel is a well known process: it consists of pouring from a pocket, a liquid metal in a tundish for regulating the flow and then, from the latter, to make a casting in the upper part of a water-cooled bottomless copper mold with vertical reciprocating motion.
  • the semi-solidified product from the lower part of the mold is extracted by means of rollers.
  • the liquid steel is introduced into the mold by means of a tubular conduit called nozzle arranged between the tundish and the mold.
  • the liquid metal is poured on the top of a refractory material dome of a distributor body.
  • the shape of this dome causes a flow of the metal towards its periphery, the flow being deflected towards the inner wall of the nozzle or an intermediate vertical tubular member.
  • a volume without liquid metal is created in which it is possible to carry out additions via an injection channel.
  • the device thus described is called a hollow jet nozzle or "Hollow Jet Nozzle".
  • the patent BE1014063 discloses a method of adding metal powders to form oxides during solidification.
  • a steel having a dissolved oxygen level (O 2 ) given from the distributor to the mold is cast, an addition (M) of metal powder is carried out, the M / O 2 ratio is controlled and the mixture is mixed. the powder to the liquid metal so as to form metal oxides.
  • O 2 dissolved oxygen level
  • the patent WO2006096942 discloses an addition of technical ceramic nanoparticles in a hollow jet nozzle.
  • These ceramic particles may be oxides, nitrides, carbides, borides or silicides. These particles are characterized by a high thermal stability, so that no reaction occurs substantially between them and the liquid metal. However, this process is difficult to implement due to agglomeration of the nanoparticles which tend to form larger particles possibly causing the aforementioned defects. Again, the application of such a technique to stainless steels is not mentioned in the patent.
  • the object of the invention is to provide a process for the manufacture of stabilized stainless steels having a fine and regular dispersion of nitrides and / or carbonitrides.
  • it seeks to obtain a large number of fine precipitates, less than 2.5 microns in size, while limiting the number of coarse precipitates larger than 10 microns.
  • Another object of the invention is to propose a process having a better efficiency with regard to the yield of the additions of stabilizing elements, compared with the methods of addition in the bag.
  • Another object of the invention is to provide a method for minimizing the risk of plugging nozzles in continuous casting of stainless steels.
  • Another object of the invention is to provide stainless steel semi-finished products having an equiaxed solidification structure at the end of the continuous casting, even without the use of electromagnetic stirring techniques.
  • Another object of the invention is to provide stainless steel semi-finished products having a good homogeneity on a cross section relative to the direction of continuous casting.
  • the subject of the invention is thus a process for producing a stabilized stainless steel semi-finished product comprising a casting step using a hollow jet nozzle disposed between a tundish and a continuous casting mold, the nozzle comprising in its upper part a distributor member for deflecting the liquid metal arriving at the inlet of the nozzle, thus defining an interior volume without liquid metal.
  • the method is characterized by supplying, in the form of liquid metal in the tundish, an unstabilized stainless steel containing no precipitates of nitrides, carbides and carbonitrides, and then pouring the liquid metal by means of the nozzle simultaneously performing an addition of metal powder in the interior 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 temperature of the liquid steel between T liquidus + 10 ° C and T liquidus + 40 ° C, and solidified said semi-finished product.
  • the invention also relates to a process characterized in that the solidification of the liquid metal begins less than 2 seconds from the addition to obtain the semi-finished product.
  • the subject of the invention is also a process according to one of the above modes, characterized in that the stabilizing element is chosen from one or more of the following elements: titanium, niobium, zirconium, vanadium.
  • the stabilizing element is titanium, the titanium, carbon and nitrogen contents of the stainless steel, expressed in mass percentage, satisfying: Ti ⁇ 0,15 + 4 (C + N)
  • the steel is a ferritic stainless steel, or austenitic stainless, or martensitic stainless or austenitic ferritic stainless.
  • the invention also relates to a semi-finished product manufactured by a method according to one of the above modes, characterized in that its solidification structure is completely equiaxed.
  • the invention also relates to a stainless steel product made from a semi-finished product produced by a method according to one of the above modes, characterized in that the stabilizing element is titanium and that the number of precipitates of nitrides or titanium carbonitrides smaller than 2.5 microns, is greater than 15000 / cm 2 .
  • the number of titanium nitrides or carbonitrides greater than 10 microns in size is preferably less than 50 / cm 2 .
  • the average interprecipitated distance is less than 15 micrometers.
  • the invention to be described is directed to a wide range of stainless steels capable of being stabilized by additions of titanium, niobium or zirconium, vanadium or other stabilizing elements, these elements being used alone or in combination.
  • the invention is advantageously used in the manufacture of ferritic stainless steels of the X 3CrTi17 type, of composition according to 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 as a percentage by mass.
  • a liquid metal containing a content of nitrogen N and carbon C present in the form of dissolved elements is poured from the ladle into the distribution basket: the composition and the temperature of the liquid metal are such that it does not exist precipitates of nitrides, carbides, carbonitrides, under these conditions.
  • the carbon and nitrogen contents make it possible to adjust the amounts of stabilizing elements which will be added later.
  • the ladle is poured into a tundish 1 comprising a bottom with a closure device 2 whose more or less complete closure makes it possible to regulate the flow towards a casting nozzle 3.
  • a tundish 1 comprising a bottom with a closure device 2 whose more or less complete closure makes it possible to regulate the flow towards a casting nozzle 3.
  • the temperature of the liquid steel must not be too important. It will be seen later that the additions made in the hollow jet nozzle must be carried out at a temperature having a limited distance from the liquidus temperature (referred to as T liquidus ) of the steel.
  • the process according to the invention requires the use of a hollow jet nozzle.
  • This nozzle comprises a distribution dome 4 made of refractory material pierced with one or more injection channels which open into the central lower part of the dome in the form of injection tubes 5. It is thus possible to add a metallic powder entrained by a vector gas.
  • the injected powder 6 mixes with the liquid metal which has been deflected by the upper part of the dome towards the walls of the nozzle or of an intermediate tubular member between the nozzle proper and the tundish.
  • the powder supply is carried out by one or more tubes 7 themselves connected to one or more tanks 8.
  • the upper part 9 of these powder reservoirs is pressurized with a carrier neutral gas such as argon, which helps protect the powder from oxidation.
  • a flow adapted gas forces the powder to flow to the hollow jet nozzle with a flow rate corresponding to the amount that it is desired to add.
  • the flow of the powder can also be facilitated by a mechanical device such as a worm.
  • the particle size of the powder must be chosen so as to ensure easy flow between the tanks and the nozzle and a near-immediate melting in the liquid metal. A spherical particle size of between 100 and 200 micrometers is well adapted to these requirements.
  • Powders of these metal elements can be naturally mixed so as to achieve a particular combination such as, for example, titanium-niobium bi-stabilization. It is also possible to mix the above powders with ferroalloys or iron powder in order to reduce the overheating 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 stabilizing element Upon addition to the hollow jet nozzle, the stabilizing element is melted by contacting the liquid metal within a few tenths of a second. Since the powder is protected from oxidation by the neutral gas until it comes into contact with the liquid metal, the yield of the addition is high.
  • Sufficient stabilizing elements are added so that nitrogen and carbon are completely precipitated and the solubility product corresponding to the formation of these precipitates is reached or exceeded at the temperature at which the addition is made.
  • the nitrides and / or carbonitrides then immediately precipitate in a very fine form.
  • the solidification of the liquid metal is begun in less than 2 seconds, the latter starting on the walls of the mold 10.
  • This very limited hold time of the precipitates in the liquid metal makes it possible to avoid an increase in their size.
  • Those skilled in the art will be able to adapt the various parameters at their disposal such as: height of the injection device with respect to the mold, injection flow rate, more or less significant implementation of the heat exchangers, extraction speed of the half -product, overheating temperature, complementary injection of ferroalloy powder to accelerate the solidification, so that the delay between the addition and the beginning of the solidification is less than 2 seconds.
  • a particularity of the stainless steels obtained according to the invention lies in the great homogeneity of the dispersion of the nitrides and carbonitrides with a smaller mean inter-precipitate distance, so that possible awareness due to a depleted area locally is reduced.
  • the above parameters, and in particular the powder injection rate and the superheating temperature are adapted so as to obtain a completely equiaxed semi-finished solidification structure.
  • This last term designates for example a slab (thickness of the order of 200mm), a slab (thickness of the order of 50-80mm), a thin strip (thickness of the order of 1-3 mm), a slab billet, not yet mechanically deformed hot.
  • Such an equiaxed structure is particularly advantageous in the field of ferritic stainless steels to minimize the ragging defect. It is known that this defect is manifested by the formation of surface irregularities after stamping parallel to the rolling direction. It is due to the presence of heterogeneous structures before cold rolling and annealing, themselves resulting from columnar solidification structures.
  • the addition of powder proves to be advantageous for obtaining a totally equiaxed structure because the precipitates act as germination sites, thus preventing the formation of a less favorable columnar or basaltic type solidification.
  • the invention thus makes it possible to avoid possibly implementing electromagnetic stirring techniques which are usually used for this purpose.
  • the semi-finished product After manufacture of the semi-finished product, it can be hot-rolled or cold-rolled, pickled, annealed, according to conventional methods, to thereby obtain a product which can take various forms such as hot strip, thin sheet, or long product of various forms.
  • grade B the addition of titanium was carried out in pocket, in the form of a titanium sponge.
  • the liquid metal in the tundish does not contain titanium.
  • This element was added in a hollow jet nozzle in the form of ferro-titanium powder (titanium 70% -fer 30%) with a particle size of between 100 and 200 microns.
  • the addition temperature of the powder is T liquidus + 35 ° C.
  • the solidification of the metal begins less than two seconds after addition, on the walls of the mold.
  • Different slab-shaped castings have been made according to the invention without encountering a problem of nozzle plugging. This is a consequence of the characteristic late precipitation of the process, the low retention time of the precipitates within the liquid metal and an advantage over conventional addition processes.
  • a density of fine precipitates ( ⁇ 2.5 ⁇ m) greater than 15000 / cm 2 guarantees a very homogeneous distribution of titanium nitrides. In this way, the trapping of carbon and nitrogen is ensured in a very complete and uniform manner.
  • a density of coarse precipitates (> 10 ⁇ m) less than 50 / cm 2 makes it possible to ensure that failure initiation does not occur prematurely during mechanical stressing.
  • the invention makes it possible to multiply by a factor of about 2 the number of fine precipitates and to divide the number of coarse precipitates by a factor of about 3.
  • the yield of the addition of titanium (ratio of the titanium present in the final product to the titanium added in the form of a powder) is 95 to 100% in the process according to the invention. This yield is therefore much higher than that of the conventional process, of the order of 60%.
  • the method according to the invention thus makes it possible to economically and reliably produce stabilized stainless steel grades having a very fine dispersion of nitrides or carbonitrides.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
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  • Continuous Casting (AREA)
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EP07291236A 2007-10-10 2007-10-10 Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé Withdrawn EP2047926A1 (fr)

Priority Applications (6)

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
ES08860262.8T ES2690310T3 (es) 2007-10-10 2008-09-23 Procedimiento de fabricación de aceros inoxidables de carbonitruros finos, y del producto obtenido a partir de este procedimiento
KR1020107010145A KR101220791B1 (ko) 2007-10-10 2008-09-23 미세 탄질화물을 포함하는 스테인리스 강 제조 방법 및 이 방법에 의해 얻어진 제품
US12/682,380 US20100278684A1 (en) 2007-10-10 2008-09-23 Process for manufacturing stainless steel containing fine carbonitrides, and product obtained from this process
EP08860262.8A EP2197608B1 (fr) 2007-10-10 2008-09-23 Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé
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

Applications Claiming Priority (1)

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

Publications (1)

Publication Number Publication Date
EP2047926A1 true EP2047926A1 (fr) 2009-04-15

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Application Number Title Priority Date Filing Date
EP07291236A Withdrawn 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
EP08860262.8A Active EP2197608B1 (fr) 2007-10-10 2008-09-23 Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé

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EP08860262.8A Active EP2197608B1 (fr) 2007-10-10 2008-09-23 Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé

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)

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CN104220190B (zh) * 2012-03-28 2018-08-28 安赛乐米塔尔研发有限公司 金属的连续铸造方法
US9289820B1 (en) * 2015-04-21 2016-03-22 Ut-Battelle, Llc Apparatus and method for dispersing particles in a molten material without using a mold
CN105018761B (zh) * 2015-07-28 2017-01-11 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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WO2007074970A1 (en) * 2005-12-28 2007-07-05 Posco Method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it

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BE1014063A3 (fr) * 2001-03-22 2003-03-04 Ct De Rech S Metallurg Ass San Procede et dispositif pour couler en continu de l'acier presentant des oxydes fins.
KR20040059785A (ko) * 2002-12-30 2004-07-06 주식회사 포스코 등축정율이 향상된 페라이트계 스테인레스강의 제조방법
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WO2007074970A1 (en) * 2005-12-28 2007-07-05 Posco Method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it

Also Published As

Publication number Publication date
ES2690310T3 (es) 2018-11-20
EP2197608B1 (fr) 2018-07-11
US20100278684A1 (en) 2010-11-04
WO2009074736A1 (fr) 2009-06-18
EP2197608A1 (fr) 2010-06-23
KR20100080928A (ko) 2010-07-13
KR101220791B1 (ko) 2013-01-11

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