EP2027300A2 - Steel compositions for special uses - Google Patents

Steel compositions for special uses

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Publication number
EP2027300A2
EP2027300A2 EP07788846A EP07788846A EP2027300A2 EP 2027300 A2 EP2027300 A2 EP 2027300A2 EP 07788846 A EP07788846 A EP 07788846A EP 07788846 A EP07788846 A EP 07788846A EP 2027300 A2 EP2027300 A2 EP 2027300A2
Authority
EP
European Patent Office
Prior art keywords
steel composition
steel
composition according
weight
chromium
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.)
Granted
Application number
EP07788846A
Other languages
German (de)
French (fr)
Other versions
EP2027300B8 (en
EP2027300B1 (en
Inventor
Annnie Fouquet
Catheline Petelot
Emilie Petelot
Adeline Petelot
Viviane Lepingle
Ghislain Louis
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.)
Vallourec Tubes France SAS
Original Assignee
V&M France SAS
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
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Application filed by V&M France SAS filed Critical V&M France SAS
Priority to PL07788846T priority Critical patent/PL2027300T3/en
Publication of EP2027300A2 publication Critical patent/EP2027300A2/en
Application granted granted Critical
Publication of EP2027300B1 publication Critical patent/EP2027300B1/en
Publication of EP2027300B8 publication Critical patent/EP2027300B8/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C22C38/22—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
    • C22C38/40—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/902—Metal treatment having portions of differing metallurgical properties or characteristics
    • Y10S148/909—Tube

Definitions

  • the invention relates to a new steel composition for special purposes, in particular high performance in the presence of corrosion by oxidizing media such as, for example, fumes or water vapor, under high pressure and / or temperature.
  • oxidizing media such as, for example, fumes or water vapor
  • the generation, conditioning (including overheating and reheating) and transport of water vapor are done using steel elements, especially seamless tubes.
  • the present invention improves the situation.
  • the invention provides a steel composition for special applications, which is in the zone comprising, in content by weight, about 1.8 to 11% of chromium (and preferably between about 2.3 and 10% of chromium), less than 1% silicon, and between 0.20 and 0.45% manganese. It has been found possible to adjust the contents of the composition according to a predetermined pattern chosen to obtain substantially optimal corrosion characteristics under given high performance conditions. temperature. This model can involve as addition or as residual at least one element selected from molybdenum, tungsten, cobalt, and nickel.
  • the composition has a silicon content by weight of between about 0.20 and 0.50%, preferably between about 0.30 and 0.50%. It may also comprise a manganese content by weight of between about 0.25 and 0.45%, and more preferably between about 0.25 and 0.40%.
  • said model comprises at least one contribution term of chromium, and a contribution term of manganese alone.
  • the manganese contribution term alone may include a second degree polynomial function of the manganese content.
  • the term chromium contribution may include a quadratic term in inverse of the chromium content, and a term in inverse of a quantity containing the chromium content.
  • the steel composition comprises between 2.3 and 2.6% by weight of chromium, approximately, the steel composition comprises between 8.9 and 9 , 5% to 10%, by weight of chromium, approximately.
  • the invention also covers a seamless tube or its accessory, consisting essentially of a proposed steel composition, the application of the steel composition to seamless tubes and accessories, intended to generate, convey or condition water vapor under high pressure and temperature, as well as the technique described for optimizing the properties of special steel compositions, in particular for their application to seamless tubes and accessories, intended to generate, convey or condition water vapor under high pressure and temperature.
  • FIG. 1 schematically illustrates the time course of a first oxidation mechanism, referred to herein as ⁇ type 1>;
  • FIG. 2 diagrammatically illustrates the time course of a second oxidation mechanism, referred to herein as ⁇ type 2>;
  • FIG. 3 is an illustrative graph of the properties of steel compositions;
  • FIG. 4 is a table of steel compositions having been subjected to long-term corrosion measurements at 650 ° C., which are shown in the last column of the table;
  • Fig. 5 is a graph showing a correspondence between measured data and calculated data.
  • Figure 6 is a partial detail graph of Figure 5.
  • ASTM American Society for Testing and Materials
  • ⁇ hot oxidation> includes two types of phenomena:
  • the oxidation phenomena by the oxidizing fumes occur outside the tubes and more particularly outside the superheater tubes taking into account the flow of fumes that see these tubes.
  • a metal having slow oxidation kinetics and capable of forming fine and adherent calamines is therefore highly desirable.
  • a characteristic of identical creep resistance, a steel tube resistant to oxidation by steam can thus superheat steam at a higher temperature than a steel tube less resistant to oxidation by steam.
  • the boiler calculation codes do not take into account the characteristics of resistance to hot oxidation (empirical rules are used which define too pessimistically an extra thickness for hot oxidation by both smoked only by water vapor).
  • This composition is commercially designated VMI 2. It surprised the inventors with regard to resistance to hot oxidation by steam at 600 ° C. and 65 ° C., which is much higher than that of the 9% Cr steels. equal or superior to that of X 20 Cr Mo V 12-1 steel also containing 12% Cr and almost as good as that of TP 347 FG austenitic grade containing 18% Cr.
  • Figure 1 illustrates the mechanism conventionally governing the hot oxidation of 9-12% Cr steels. As can be seen, the oxide germs homogeneously over the entire surface.
  • the mechanism of FIG. 2 relates to the grade VM 12, to certain compositions of X20 Cr Mo V 12-1 steel and to the austenitic grade TP 347 FG with fine grains: here, the oxide is born in the form of isolated seeds. which must develop on the surface before forming a layer and develop in depth. This mechanism leads to slow oxidation kinetics and adherent calamines.
  • Si and Co have a beneficial influence that extends the field of action of Cr.
  • the Applicant has sought to do better, and in particular to obtain quantitative elements to improve existing steels, including those with 9% Cr whose resistance to oxidation is considered until now insufficient and those to 2.25 % Cr.
  • the autoimmune des Mines de Douai first developed, on the occasion of a study contract with the Applicant, a formula for predicting the loss of metal thickness (determined after etching of the oxide formed without metal attack) over one year from a modeling of the influence of all elements of the chemical composition.
  • LPL Lower Protective Layer of Scale
  • FIG. 4 is a composition table of the steels tested with, in the last column, the values of the corrosion measurements corresponding to the loss of metal thickness over one year (Vcor corrosion rate) for these steels.
  • the Applicant has performed on these experimental results a multivariate statistical analysis. It is based on a plurality of terms reflecting a reasoned empirical approach of certain mechanisms or influences, which determine the Vcor corrosion rate.
  • the formula [21] gives the average loss of metal thickness (in mm) over one year of exposure to water vapor at 650 ° C. This average loss of thickness is it even deduced from a weight loss of the metal after selective etching of the oxide, under standard conditions.
  • Formula [21] has various terms as follows:
  • FIGS. 5 and 6 illustrate how this new Vcor-ordinate formula (Vcor predicted) compares with the experimental results known to the Applicant on the abscissa (Vcor measured). It follows:
  • FIG. 5 right-hand part
  • FIG. 5 left-hand part
  • FIG. 6 which is a detail of the part on the left of FIG. 5
  • the correspondence is also excellent for chromium contents close to 9% and 12%.
  • the invention is not limited to the expression of the formula [21], which is known to write equivalents of different appearance.
  • the formula [21] was set at 650 ° C, it is naturally valid for other temperatures, lower or higher. For example, a steel grade having a rather high corrosion rate at 650 ° C may be acceptable at lower temperatures, if it has interesting properties from any point of view, including a lower manufacturing cost.
  • the Applicant has found a strong detrimental influence of the Mn content above about 0.25%, according to the indications of the formula [21] (grade range studied: 0.2 - 0.53% ). It also found that the Si content plays little when Si is greater than or equal to 0.20% (grade range studied: 0.09-0.47%). It also noted the absence of significant influence of the carbon content within the limits studied (0.1-0.2%).
  • the Applicant was then interested in searching among the ferritic performance grades of the specifications ASTM, A213 and A335 for use in boilers (T91, P91, T92, P92, T23, P23, T24, P24) particular areas of chemical composition that lead with thin and very adherent calamines to make the tubes work better at steam temperatures of the order of 600 ° or 650 ° C and vapor pressures of the order of 300 bar.
  • the steel grades proposed here for seamless tubes for conveying water vapor under high pressure and temperature include (by weight) 1.8 to 13% chromium (Cr), less than 1% silicon (Si) and between 0.10 and 0.45% manganese (Mn).
  • the steel comprises an addition of at least 1 element chosen from molybdenum (Mo), tungsten (W), cobalt (Co), vanadium (V), niobium (Nb), titanium ( Ti), boron (B) and nitrogen (N).
  • ASTM standards A213 and A335 define grades T22 and P22 respectively as containing:
  • ElO grades allow a gain of between 18% (for ElO-ax) and 42% (for ElO-min), compared to the corrosion rate of the composition "reference" RIO.
  • the steel has between 2.3 and 2.6% Cr.
  • the steel of the ElO mode comprises an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%.
  • the steel comprises an Mn content of between 0.30 and 0.45%.
  • ElO preferably comprises between 0.87 and 1% Mo. It does not include a voluntary addition of W, tungsten being a residual steel and its content of about 0.01% .
  • the steel according to the mode ElO has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.9 mm / year, preferably 0.85 mm / year. Better results are obtained for Vcor at most equal to about 0.7 mm / year.
  • Embodiment EIl T23 and P23 steels
  • ASTM standards A213 and A335 define grades T23 and P23 respectively as containing: - 0.10 to 0.60% Mn
  • the steel has between 2.3 and 2.6% Cr.
  • the steel of mode EI 1 has an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%.
  • the steel comprises an Mn content of between 0.25 and 0.45%.
  • the steel according to this mode El 1 preferably comprises between 1.45% and 1.60% W and between 0.05 and 0.20% Mo.
  • the steel according to the mode El 1 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is less than about 1.4 mm / year. preferably at most equal to about 1.25 mm / year. Better results are obtained for Vcor at most equal to about 0.9 mm / year.
  • Embodiment E 12 T24 / P24 steels
  • These steels contain according to ASTM A213 0.30 to 0.70% Mn 0.15 to 0.45% Si 2.20 to 2.60% Cr 0.70 to 1.10% Mo 0.04 to 0.10% C at most 0.020% P at most 0.010% S 0.20 to 0.30% V 0.06 to 0 , 10% Ti 0.0015 to 0.0020% B at most 0.012% N at most 0.020% Al
  • Table Tl 2 is constructed similarly to Tables T10 and TI1.
  • the gain is more limited on the selection according to the invention: from 9% (E12-max) to 30% (E12-min). It is believed that this is mainly because the margin on the Cr content is lower than for the embodiments El 0 or El 1.
  • the steel comprises between 2.4 and 2.6% Cr.
  • the steel has an Si content of between 0.20 and 0.45% and very preferably between 0.30 and 0.45%.
  • the steel comprises an Mn content of between 0.30 and 0.45%.
  • the steel according to this mode E12 does not include any addition of W (residual tungsten content of the order of 0.01%); its Mo content is preferably between 0.70 and 0.9%.
  • the steel according to this mode El 2 has contents of Cr,
  • Vcor Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.8 mm / year and preferably at most equal to about 0.75 mm / year. Better results are obtained for Vcor at most equal to about 0.7 mm / year.
  • ASTM standards A213 and A335 define grades T9 and P9, respectively, as containing:
  • the steels according to embodiment E20 do not contain microadditions of V, Nb, N or B.
  • Formula [21] has been derived from the indications for different grades of steel of this embodiment E20. These grades are represented by three examples, denoted E20-max, E20-med, and E20-min, according to the corrosion rate obtained.
  • the selection of the grades E20 allows a gain of between 16% (for E20-max) and 89% (for E20-min), relative to the corrosion rate of the "reference" composition R20.
  • the steel has between 9.2 and 10.00% Cr.
  • the steel of the mode E20 has an Si content of between 0.25 and 0.50% and very preferably between 0.30 and 0.40%.
  • the steel comprises an Mn content of between 0.30 and 0.45%.
  • the steel according to this mode E20 preferably comprises between 0.90 and 1.00% Mo. It does not include a voluntary addition of W, the tungsten being a residual of the steel and its content of the order of 0, 01%.
  • the steel according to the mode E20 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.09 mm / year, preferably 0.06 mm / year. Better results are obtained for Vcor at most equal to about 0.04 mm / year.
  • Embodiment E21 T91 / P91 steels
  • Table T21 below is constructed similarly to Table T10.
  • E21 ranges from 10% (E21-max) to 80% (E21-min). It is remarkable that for E21-min, the value obtained is five times lower than the reference value.
  • the steel comprises between 8.9 and 9.5% Cr.
  • the steel comprises an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%.
  • the steel comprises a Mn content of between 0.30 and
  • the steel according to embodiment E21 comprises at most 0.2% Ni (and very preferably at most 0.1%), and practically no tungsten (residual of the order of 0.01%).
  • the steel according to the mode E21 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is less than about 0.1 mm / year. Better results are obtained for Vcor at most equal to about 0.07 mm / year.
  • Embodiment E22 T92 / P92 steels
  • Table T22 below is constructed similarly to Table T10.
  • the gain on the selection of these embodiments E22 ranges from 2% (E22- max) to 52% (E22-min).
  • the steel comprises between 8.9 and 9.5% Cr.
  • the steel of mode E22 has an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%.
  • the steel of mode E22 comprises an Mn content of between 0.30 and 0.45% and more preferably between 0.30 and 0.40%.
  • the steel according to the mode E22 preferably comprises between 0.30% and 0.45% Mo. It comprises between 1.50 and 1.75% W. Preferably, the steel according to the mode E22 comprises at most 0.2% Ni and very preferably at most 0.1%.
  • the steel according to the mode E22 has contents of Cr, Mn, Si, Mo, W, Ni, Co which, according to the equation [21], give a value Vcor at most equal to about 0.11 mm / year. Better results are obtained for Vcor at most equal to about 0.08 mm / year.
  • the modes E21 and E22 are quite similar in terms of chromium, manganese and silicon content.
  • the other contents of Cr, Mn and / or Si of one of these modes E2 can be applied at least partially to the other.
  • ASTM A213 and A335 define T5 and P5, respectively, as containing: - 0.30 to 0.60% Mn
  • Formula [21] has been derived from the indications for different grades of steel of this embodiment E30. These grades are represented by three examples, noted E30-max, E30-med, and E30-min, according to the corrosion rate obtained.
  • grades E30 allows a gain of between 15% (for E30-max) and 55% (for E30-min), compared to the corrosion rate of the composition "reference" R30.
  • the steel has between 5.2 and 6.00% Cr.
  • the steel of the E30 mode comprises an Si content of between 0.25 and 0.50% and very preferably between 0.30 and 0.45%.
  • the steel comprises an Mn content of between 0.30 and 0.45%.
  • the steel according to this mode E30 preferably comprises between 0.45 and 0.60%
  • Mo is a residual steel and its content of the order of 0.01%.
  • the steel according to the mode E30 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.23 mm / year, preferably 0.20 mm / year. Better results are obtained for Vcor at most equal to about 0.17 mm / year.
  • the model used leads to increase the content of some alphagenic elements such as Cr, Si and to reduce the content of some gammagenic elements such as Mn and Ni 5 which can promote the appearance of delta ferrite.
  • the proposed technique for optimizing special steels includes the following elements. It starts from a known steel grade or grade with known properties other than hot corrosion, which we want to optimize from the point of view of hot corrosion. A long-term corrosion property is calculated according to a model such as that of formula [21] on a reference composition. In the vicinity of the known steel, a particular range of composition of the steel grade is sought, leading to a better value of the corrosion property according to the same model.
  • the steel according to the invention can also be used without the list being exhaustive as sheet to manufacture welded tubes, fittings, reactors, boiler parts, as molded part for manufacturing turbine bodies or valve bodies as forging for making turbine shafts and rotors, fittings, as metal powder for making various components in powder metallurgy, as solder metal and other similar applications.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
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Abstract

The invention concerns steels having excellent resistance over time, in a corrosive atmosphere due to oxidizing environments such as, for example, fumes or water vapor, under high pressure and/or temperature. The invention concerns a steel composition for special applications, said composition containing, by weight, about 1.8 to 11% of chromium (and preferably between about 2.3 and 10% of chromium), less than 1% of silicon, and between 0.20 and 0.45% of manganese. It has been found that it is possible to adjust the contents of the composition based on a predetermined model, selected to obtain substantially optimal properties with respect to corrosion in specific conditions of high temperature performances. Said model can involve as additive of as residue at least one element selected among molybdenum, tungsten, cobalt, and nickel.

Description

Compositions d'aciers pour usages spéciaux Steel compositions for special purposes
L'invention concerne une nouvelle composition d'acier pour usages spéciaux, en particulier à hautes performances en présence de corrosion par des milieux oxydants tels que, par exemple, des fumées ou la vapeur d'eau, sous pression et/ou température élevées.The invention relates to a new steel composition for special purposes, in particular high performance in the presence of corrosion by oxidizing media such as, for example, fumes or water vapor, under high pressure and / or temperature.
Des ambiances de pression et température élevées en présence de vapeur d'eau existent notamment en production industrielle de l'électricité. La génération, le conditionnement (notamment la surchauffe et la resurchauffe) et le transport de la vapeur d'eau se font à l'aide d'éléments en acier, en particulier des tubes sans soudure.High atmospheres of pressure and temperature in the presence of water vapor exist in particular in the industrial production of electricity. The generation, conditioning (including overheating and reheating) and transport of water vapor are done using steel elements, especially seamless tubes.
Malgré une longue histoire de solutions envisagées ou mises en œuvre, sur laquelle on reviendra, de sérieux problèmes demeurent en termes de tenue dans l'ambiance concernée, de même que dans le temps.Despite a long history of solutions envisaged or implemented, to which we will return, serious problems remain in terms of keeping in the environment concerned, as well as in time.
Ces problèmes sont particulièrement difficiles à résoudre, du fait notamment de la variabilité significative des propriétés des aciers en fonction de leurs constituants, et de la lourdeur des essais de corrosion à chaud sur une longue période.These problems are particularly difficult to solve, in particular because of the significant variability of the properties of the steels according to their constituents, and the heaviness of the hot corrosion tests over a long period.
Dans la suite du présent document on emploiera le terme « corrosion » ou « corrosion à chaud » pour désigner les phénomènes de perte de métal par oxydation à chaud.In the rest of this document, the term "corrosion" or "hot corrosion" will be used to denote the phenomena of loss of metal by hot oxidation.
La présente invention vient améliorer la situation.The present invention improves the situation.
L'invention propose une composition d'acier pour applications spéciales, qui se situe dans la zone comprenant, en teneur en poids, environ 1,8 à 11 % de Chrome (et préférentiellement entre environ 2,3 et 10 % de Chrome), moins de 1 % de Silicium, et entre 0,20 et 0,45 % de Manganèse. Il s'est avéré possible d'ajuster les teneurs de la composition selon un modèle prédéterminé, choisi pour obtenir des caractéristiques de corrosion sensiblement optimales dans des conditions données de performances à haute température. Ce modèle peut faire intervenir comme addition ou comme résiduel au moins un élément choisi parmi le molybdène, le tungstène, le cobalt, et le nickel.The invention provides a steel composition for special applications, which is in the zone comprising, in content by weight, about 1.8 to 11% of chromium (and preferably between about 2.3 and 10% of chromium), less than 1% silicon, and between 0.20 and 0.45% manganese. It has been found possible to adjust the contents of the composition according to a predetermined pattern chosen to obtain substantially optimal corrosion characteristics under given high performance conditions. temperature. This model can involve as addition or as residual at least one element selected from molybdenum, tungsten, cobalt, and nickel.
Plus particulièrement, la composition comporte une teneur de silicium en poids comprise entre environ 0,20 et 0,50 %, de préférence entre environ 0,30 et 0,50%. Elle peut comporter aussi une teneur de manganèse en poids comprise entre 0,25 et 0,45 % environ, et plus préférentiellement entre 0,25 et 0,40% environ.More particularly, the composition has a silicon content by weight of between about 0.20 and 0.50%, preferably between about 0.30 and 0.50%. It may also comprise a manganese content by weight of between about 0.25 and 0.45%, and more preferably between about 0.25 and 0.40%.
Selon un autre aspect de l'invention, ledit modèle comporte au moins un terme de contribution du chrome, et un terme de contribution du manganèse seul. Le terme de contribution du manganèse seul peut comprendre une fonction polynomiale du second degré de la teneur en manganèse. Le terme de contribution du chrome peut comprendre un terme quadratique en inverse de la teneur en chrome, et un terme en inverse d'une quantité contenant la teneur en chrome.According to another aspect of the invention, said model comprises at least one contribution term of chromium, and a contribution term of manganese alone. The manganese contribution term alone may include a second degree polynomial function of the manganese content. The term chromium contribution may include a quadratic term in inverse of the chromium content, and a term in inverse of a quantity containing the chromium content.
Selon des modes de réalisation préférentiels, que l'on décrira plus en détail : la composition d'acier comporte entre 2,3 et 2,6 % en poids de Chrome, environ, la composition d'acier comporte entre 8,9 et 9,5 % à 10 %, en poids de Chrome, environ.According to preferred embodiments, which will be described in more detail: the steel composition comprises between 2.3 and 2.6% by weight of chromium, approximately, the steel composition comprises between 8.9 and 9 , 5% to 10%, by weight of chromium, approximately.
L'invention couvre également un tube sans soudure ou son accessoire, essentiellement constitué d'une composition d'acier proposée, l'application de la composition d'acier à des tubes sans soudure et accessoires, destinés à générer, à véhiculer ou à conditionner de la vapeur d'eau sous pression et température élevées, ainsi que la technique décrite pour optimiser les propriétés des compositions d'aciers spéciaux, en particulier pour leur application à des tubes sans soudure et accessoires, destinés à générer, à véhiculer ou à conditionner de la vapeur d'eau sous pression et température élevées.The invention also covers a seamless tube or its accessory, consisting essentially of a proposed steel composition, the application of the steel composition to seamless tubes and accessories, intended to generate, convey or condition water vapor under high pressure and temperature, as well as the technique described for optimizing the properties of special steel compositions, in particular for their application to seamless tubes and accessories, intended to generate, convey or condition water vapor under high pressure and temperature.
D'autres caractéristiques et avantages de l'invention apparaîtront mieux à la lecture de la description détaillée ci-après, faite en référence aux dessins annexés, sur lesquels : La figure 1 illustre schématiquement le déroulement dans le temps d'un premier mécanisme d'oxydation, dit ici de <type 1> ;Other characteristics and advantages of the invention will appear better on reading the detailed description below, made with reference to the appended drawings, in which: FIG. 1 schematically illustrates the time course of a first oxidation mechanism, referred to herein as <type 1>;
La figure 2 illustre schématiquement le déroulement dans le temps d'un second mécanisme d'oxydation, dit ici de <type 2> ; - La figure 3 est un graphe illustratif de propriétés de compositions d'acier ;FIG. 2 diagrammatically illustrates the time course of a second oxidation mechanism, referred to herein as <type 2>; FIG. 3 is an illustrative graph of the properties of steel compositions;
La figure 4 est un tableau de compositions d'acier, ayant fait l'objet de mesures de corrosion à long terme à 650°C, lesquelles figurent dans la dernière colonne du tableau ;FIG. 4 is a table of steel compositions having been subjected to long-term corrosion measurements at 650 ° C., which are shown in the last column of the table;
La figure 5 est un graphe représentant une correspondance entre des données mesurées et des données calculées ; etFig. 5 is a graph showing a correspondence between measured data and calculated data; and
La figure 6 est un graphe formant détail partiel de la figure 5.Figure 6 is a partial detail graph of Figure 5.
Les dessins, la description ci-après et ses annexes contiennent, pour l'essentiel, des éléments de caractère certain. Ils pourront donc non seulement servir à mieux faire comprendre la présente invention, mais aussi contribuer à sa définition, le cas échéant.The drawings, the description below and its annexes contain, for the most part, elements of a certain character. They can therefore not only serve to better understand the present invention, but also contribute to its definition, if any.
On examine maintenant les conditions dans lesquelles l'invention peut s'appliquer.The conditions under which the invention can be applied are now examined.
On considère par exemple le cas d'une centrale thermique à combustible fossile, qui comprend une chaudière de puissance délivrant de la vapeur d'eau surchauffée à une turbine à vapeur accouplée à un alternateur. On connaît le bon rendement thermique de ce genre de centrales thermiques, que l'on cherche par ailleurs à rendre de moins en moins polluantes, en limitant les rejets tant de fumées que de gaz nocifs tels que le SO2, les NOx et le CO2, ce dernier étant plus particulièrement responsable de l'effet de serre. Or la réduction de la quantité relative de CO2 produite lors de la combustion passe par l'augmentation du rendement de la chaudière, laquelle est liée à la température et à la pression de la vapeur délivrée à la turbine.Consider for example the case of a fossil fuel power plant, which includes a power boiler delivering superheated steam to a steam turbine coupled to an alternator. We know the good thermal efficiency of this kind of thermal power plants, which we also try to make less and less polluting, by limiting the emissions of both fumes and harmful gases such as SO 2 , NO x and CO 2 , the latter being more particularly responsible for the greenhouse effect. But the reduction in the relative amount of CO 2 produced during the combustion passes through the increase of the efficiency of the boiler, which is related to the temperature and the pressure of the steam delivered to the turbine.
La vapeur d'eau étant essentiellement confinée dans des tubes sans soudure en acier, on a cherché depuis de nombreuses années à améliorer les caractéristiques de résistance à long terme des tubes à la pression intérieure de fluide à haute température en améliorant leur résistance au fluage et notamment leur résistance à la rupture par fluage en 100 000 heures.Since water vapor is essentially confined in seamless steel tubes, attempts have been made for many years to improve the long-term strength characteristics of the tubes at the high temperature internal pressure of the fluid. by improving their resistance to creep and in particular their resistance to creep rupture in 100,000 hours.
Le groupe dit American Society for Testing and Materials ("ASTM") a établi des normes ou spécifications dans lesquelles puisent les hommes du métier pour le choix de leurs aciers. S 'agissant d'aciers spéciaux pour usage à haute température, ce sont :The so-called American Society for Testing and Materials ("ASTM") has established standards or specifications from which the skilled person draws for the selection of their steels. In the case of special steels for high temperature use, these are:
la spécification A213, intitulée "Standard Spécification for Seamless Ferritic and Austenitic Alloy-Steel Boiler, Superheater and Heat-Exchanger Tubes", et la spécification A335 : "Standard Spécification for Seamless Ferritic Alloy-Steel Pipe for High-Temperature Service".Specification A213, entitled "Standard Specification for Seamless Ferritic and Austenitic Alloy-Steel Boiler, Superheater and Heat-Exchanger Tubes", and Specification A335: "Standard Specification for Seamless Ferritic Alloy-Steel Pipe for High-Temperature Service".
Les chaudières des années 1960 mettaient en œuvre des aciers non alliés pour les panneaux d'écran de la chaudière et des nuances à 2,25 % Cr et 1 % Mo (nuances T22 de l'ASTM A213 et P22 de l'ASTM A335) pour les parties chaudes des tubes de surchauffeurs et les conduites de vapeur surchauffée (160 bars - 560° C).The 1960s boilers used unalloyed steels for boiler screen panels and grades of 2.25% Cr and 1% Mo (ASTM A335 ASTM A213 and P22 grades T22). for the hot parts of the superheater tubes and the superheated steam lines (160 bar - 560 ° C).
Les aciers inoxydables austénitiques à 18 % Cr et 10 % Ni possèdent intrinsèquement de meilleures caractéristiques de résistance au fluage que les nuances plus faiblement alliées à structure ferritique mais possèdent de graves inconvénients du fait qu'une même chaudière doit alors comprendre des parties en acier à structure austénitique et d'autres à structure ferritique : il en découle d'une part des différences de coefficients de dilatation thermique, et d'autre part la nécessité de réaliser des jonctions soudées entre tubes de structure métallurgique différente.Austenitic stainless steels at 18% Cr and 10% Ni intrinsically have better creep characteristics than the lower alloyed grades with a ferritic structure, but have serious drawbacks because the same boiler must then comprise parts made of carbon steel. austenitic structure and others ferritic structure: it follows on the one hand differences in coefficients of thermal expansion, and on the other hand the need to make welded joints between tubes of different metallurgical structure.
La tendance a donc été à l'amélioration des matériaux à structure ferritique.The trend has therefore been to improve materials with a ferritic structure.
L'acier X 20 Cr Mo V 12 - 1 à 12 % Cr selon la norme allemande DIN 17.175 n'est plus très en vogue car sa mise en œuvre est très délicate et ses caractéristiques de fluage sont dépassées. Les années 1980 ont vu l'apparition dans les normes de nuances à 9 % Cr microalliées (T91 et P91, T92 et P92 selon ASTM A213 et A335) possédant à la fois une bonne résistance au fluage et d'excellentes propriétés de mise en œuvre.The X 20 Cr Mo V 12 - 1 to 12% Cr steel according to the German standard DIN 17.175 is no longer very popular because its implementation is very delicate and its creep characteristics are exceeded. The 1980s saw the emergence in the standards of microalloyed 9% Cr grades (T91 and P91, T92 and P92 according to ASTM A213 and A335) with both good creep resistance and excellent properties of implementation. .
En parallèle, sont apparues dans les années 1990, des nuances à 2,25 % Cr microalliées (T23, P23, T24, P24) pour améliorer les performances des panneaux d'écrans et/ou de certaines parties des surchauffeurs.In parallel, appeared in the 1990s, grades to 2.25% Cr microallied (T23, P23, T24, P24) to improve the performance of the display panels and / or parts of the superheaters.
Se sont alors posés des problèmes de tenue à l'oxydation à chaud, notamment dans le cas des aciers à 9 % Cr en comparaison à l'acier X 20 Cr Mo V 12 - 1 contenant 12 % Cr. On sait en effet que le Cr et également Si et Al sont des éléments qui réduisent l'oxydation à chaud.Then there were problems of resistance to hot oxidation, especially in the case of 9% Cr steels in comparison with X 20 Cr Mo V 12 - 1 steel containing 12% Cr. It is known that Cr and also Si and Al are elements that reduce hot oxidation.
Le terme <oxydation à chaud> regroupe 2 types de phénomènes :The term <hot oxidation> includes two types of phenomena:
l'oxydation par les fumées oxydantes, et l'oxydation par la vapeur d'eau.oxidation by oxidizing fumes, and oxidation by water vapor.
Oxydation sur Ia surface extérieure des tubesOxidation on the outer surface of the tubes
Les phénomènes d'oxydation par les fumées oxydantes se produisent à l'extérieur des tubes et plus particulièrement à l'extérieur des tubes de surchauffeurs compte-tenu des flux de fumées que voient passer ces tubes.The oxidation phenomena by the oxidizing fumes occur outside the tubes and more particularly outside the superheater tubes taking into account the flow of fumes that see these tubes.
Ils se traduisent par une perte d'épaisseur de métal et de ce fait par une augmentation de la contrainte tangentielle σ dans le tube que l'on peut écrire par la relation [11] annexée, où D est le diamètre extérieur, e est l'épaisseur et P la pression intérieure de vapeur à l'intérieur des tubes.They result in a loss of thickness of metal and thus by an increase of the tangential stress σ in the tube that can be written by the attached relation [11], where D is the outside diameter, e is the thickness and P internal vapor pressure inside the tubes.
La cinétique d'oxydation est d'autant plus rapide que la couche d'oxyde (ou calamine) est mince. On pourrait donc croire qu'elle s'autolimite avec la croissance de la couche de calamine. Malheureusement, lorsque la couche de calamine est épaisse, elle perd de l'adhérence et se détache en feuilles (exfoliation). Il en découle que l'oxydation reprend à grande vitesse là où le métal est à nu.The kinetics of oxidation is even faster than the oxide layer (or calamine) is thin. One might think that it is self-limiting with the growth of the calamine layer. Unfortunately, when the calamine layer is thick, it loses adhesion and breaks off into leaves (exfoliation). It follows that the oxidation resumes at high speed where the metal is exposed.
Un métal ayant une cinétique d'oxydation lente et apte à former des calamines fines et adhérentes est donc hautement souhaitable.A metal having slow oxidation kinetics and capable of forming fine and adherent calamines is therefore highly desirable.
Oxydation sur la surface intérieure des tubesOxidation on the inner surface of the tubes
II en est de même pour d'autres raisons pour les phénomènes d'oxydation par la vapeur d'eau qui se manifestent à l'intérieur des tubes et qui ont été plus récemment étudiés. En effet, la calamine formée à l'intérieur des tubes de surchauffeurs constitue un isolant thermique entre les fumées (source de chaleur) et la vapeur d'eau à surchauffer. Et une calamine épaisse côté vapeur (intérieur du tube) se traduit par une température plus élevée du métal que lorsque la calamine est mince. Or l'influence négative de la température sur la résistance au fluage est exponentielle.It is the same for other reasons for the phenomena of oxidation by water vapor which are manifested inside the tubes and which have been more recently studied. Indeed, the scale formed inside the superheater tubes is a thermal insulator between the fumes (heat source) and the water vapor to overheat. And a thick calamine on the steam side (inside the tube) results in a higher temperature of the metal than when the calamine is thin. However, the negative influence of temperature on creep resistance is exponential.
A caractéristique de résistance au fluage identique, un tube en acier résistant à l'oxydation par la vapeur pourra donc surchauffer la vapeur à une plus haute température qu'un tube en acier moins résistant à l'oxydation par la vapeur.A characteristic of identical creep resistance, a steel tube resistant to oxidation by steam can thus superheat steam at a higher temperature than a steel tube less resistant to oxidation by steam.
En outre, en cas de calamine épaisse et/ou peu adhérente, une exfoliation de celle-ci peut avoir pour conséquence :In addition, in case of calamine thick and / or little adherent, exfoliation thereof may result in:
dans le cas des tubes de surchauffeurs une accumulation de la calamine exfoliée dans les épingles des serpentins de surchauffeurs, entravant la circulation de vapeur et pouvant causer des éclatements de tubes surchauffeurs par surchauffe catastrophique, un entraînement de la calamine exfoliée, issue tant des tubes surchauffeurs que des collecteurs de vapeur ou des conduites de vapeur, dans les aubes de la turbine avec un risque d'érosion et/ou abrasion et de destruction de celles-ci. Etat de la techniquein the case of superheater tubes, an accumulation of the exfoliated calamine in the pins of the superheater coils, hindering the circulation of steam and possibly causing bursting of superheater tubes by catastrophic overheating, entrainment of the exfoliated calamine resulting from the superheater tubes steam collectors or steam lines in the blades of the turbine with a risk of erosion and / or abrasion and destruction thereof. State of the art
Pour le moment, les codes de calcul de chaudière ne prennent pas en compte de manière fine les caractéristiques de résistance à l'oxydation à chaud (on utilise des règles empiriques définissant de manière trop pessimiste une surépaisseur pour l'oxydation à chaud tant par les fumées que par la vapeur d'eau).For the time being, the boiler calculation codes do not take into account the characteristics of resistance to hot oxidation (empirical rules are used which define too pessimistically an extra thickness for hot oxidation by both smoked only by water vapor).
Approche de la DemanderesseApplicant's approach
Dans WO 02/081766, la Demanderesse a proposé une composition d'acier pour tubes sans soudure ayant de très bonnes propriétés en termes tant de résistance à la rupture par fluage que de résistance à l'oxydation à chaud.In WO 02/081766, the Applicant has proposed a steel composition for seamless tubes having very good properties in terms of both creep rupture resistance and resistance to hot oxidation.
Cette composition est désignée commercialement VMl 2. Elle a surpris les inventeurs en ce qui concerne la résistance à l'oxydation à chaud par la vapeur à 600°C et 65O0C, qui est très supérieure à celle des aciers à 9 % Cr, égale voire supérieure à celle de l'acier X 20 Cr Mo V 12-1 contenant également 12 % Cr et presque aussi bonne que celle de la nuance austénitique TP 347 FG contenant 18 % Cr.This composition is commercially designated VMI 2. It surprised the inventors with regard to resistance to hot oxidation by steam at 600 ° C. and 65 ° C., which is much higher than that of the 9% Cr steels. equal or superior to that of X 20 Cr Mo V 12-1 steel also containing 12% Cr and almost as good as that of TP 347 FG austenitic grade containing 18% Cr.
Des résultats expérimentaux obtenus à l'Ecole des Mines de Douai ont été présentés à la conférence "High Température Corrosion and Protection of Matériaux 6, les Embiez 2004, et ont été publiés dans Materials Science Forum, Vol 461-464 (2004) p. 1039-1046, sous le titre "Steam Corrosion Résistance of New 12 % Ferrite Boiler Steels".Experimental results obtained at the Ecole des Mines de Douai were presented at the conference "High Temperature Corrosion and Protection of Materials 6, Embiez 2004, and were published in Materials Science Forum, Vol 461-464 (2004) p. 1039-1046, under the title "Steam Corrosion Resistance of New 12% Ferrite Boiler Steels".
Les auteurs (V. Lepingle et al.) ont observé qu'il est difficile de prévoir de manière quantitative la cinétique d'oxydation à chaud, les éléments de la composition chimique de l'acier pouvant avoir une influence non linéaire, voire fonctionner en synergie. Ils ont notamment fait apparaître l'existence de deux types distincts de mécanismes de croissance intervenant dans l'oxydation à chaud, illustrés sur les Figures I et 2.The authors (V. Lepingle et al.) Have observed that it is difficult to predict in a quantitative way the kinetics of hot oxidation, the elements of the chemical composition of steel being able to have a non-linear influence, or even to work with synergy. In particular, they showed the existence of two distinct types of growth mechanisms involved in hot oxidation, illustrated in Figures I and 2.
La figure 1 illustre le mécanisme régissant classiquement l'oxydation à chaud des aciers à 9-12 % Cr. Comme on le voit, l'oxyde germe de manière homogène sur l'ensemble de la surface.Figure 1 illustrates the mechanism conventionally governing the hot oxidation of 9-12% Cr steels. As can be seen, the oxide germs homogeneously over the entire surface.
Le mécanisme de la figure 2 est relatif à la nuance VM 12, à certaines compositions d'acier X20 Cr Mo V 12-1 et à la nuance austénitique TP 347 FG à grains fins: ici, l'oxyde naît sous forme de germes isolés qui doivent se développer en surface avant de constituer une couche et se développer en profondeur. Ce mécanisme conduit à des cinétiques lentes d'oxydation et à des calamines adhérentes.The mechanism of FIG. 2 relates to the grade VM 12, to certain compositions of X20 Cr Mo V 12-1 steel and to the austenitic grade TP 347 FG with fine grains: here, the oxide is born in the form of isolated seeds. which must develop on the surface before forming a layer and develop in depth. This mechanism leads to slow oxidation kinetics and adherent calamines.
D'autres travaux se sont également intéressés à prédire la cinétique d'oxydation à chaud par la vapeur d'eau.Other studies have also focused on predicting the kinetics of hot oxidation by water vapor.
Une communication de Zurek et al. a été également présentée à la conférence Les Embiez et publiée dans "Materials Sciences Forum", Vol 461-464 (2004) pp 791-798. Elle montre qualitativement l'influence de divers éléments chimiques sur la variation de la constante Kp de la loi d'oxydation empiriqueA paper by Zurek et al. was also presented at the conference Les Embiez and published in "Materials Sciences Forum", Vol 461-464 (2004) pp 791-798. It qualitatively shows the influence of various chemical elements on the variation of the constant Kp of the empirical oxidation law
Δm = Kp fΔm = Kp f
dans laquelle Δm est l'accroissement de masse par oxydation et t le temps, tandis que z est généralement pris égal à 1/2. La constante Kp présentant une décroissance brutale au-delà d'une certaine teneur en chrome.where Δm is the oxidation mass increase and t is the time, while z is usually 1/2. The constant Kp exhibiting a sudden decrease beyond a certain chromium content.
Les principales conclusions que l'on peut tirer de Zurek et al. sont les suivantes (voir figure 3) : L'ajout de manganèse déplace vers la droite la zone de forte décroissance de Kp en fonction de la teneur en chrome ; Selon ce travail, l'addition de Mn tend à contrarier l'effet bénéfique du Cr ;The main conclusions that can be drawn from Zurek et al. are as follows (see Figure 3): The addition of manganese shifts to the right the zone of strong decay of Kp as a function of the chromium content; According to this work, the addition of Mn tends to thwart the beneficial effect of Cr;
L'ajout de silicium ou de cobalt déplace au contraire vers la gauche la zone de forte décroissance de Kp en fonction de la teneur en chrome. Selon ce travail, Si et Co ont une influence bénéfique qui étend le domaine d'action du Cr.The addition of silicon or cobalt displaces on the contrary to the left the zone of strong decay of Kp as a function of the chromium content. According to this work, Si and Co have a beneficial influence that extends the field of action of Cr.
On comprend qu'il est difficile d'en tirer des indications précises sur les propriétés de tel ou tel alliage.It is understood that it is difficult to draw precise indications on the properties of any particular alloy.
Osgerby et al. ( S. Osgerby, A. Fry "Assessment of steam oxidation behaviour of high température plant materials" Proceedings from the 4th international EPRI conférence , October 25-28, 2004 - Hilton Head Island, South Carolina - pp 388-401) ont également étudié l'oxydation de divers aciers et alliages de Ni par la vapeur d'eau. Ils ont effectué sur les résultats un traitement à l'aide de réseaux de neurones. Ils ont abouti à des équations qui dans le cas des aciers ferritiques à 9 - 12 % Cr montrent quantitativement une influence positive de Cr, Si, Mn et Mo et une influence négative de W.Osgerby et al. (S. Osgerby, A. Fry "Assessment of Steam Oxidation Behavior of High Temperature Plant Materials" Proceedings from the 4th International EPRI Conference, October 25-28, 2004 - Hilton Head Island, South Carolina - pp. 388-401) also studied the oxidation of various steels and Ni alloys by water vapor. They performed on the results a treatment using neural networks. They resulted in equations which in the case of ferritic steels at 9-12% Cr show quantitatively a positive influence of Cr, Si, Mn and Mo and a negative influence of W.
Globalement, les conclusions de ces travaux sont diverses, et même opposées en ce qui concerne le cas du manganèse dans les aciers ferritiques.Overall, the conclusions of this work are diverse, and even opposite as regards the case of manganese in ferritic steels.
La Demanderesse a cherché à mieux faire, et en particulier à obtenir des éléments quantitatifs permettant d'améliorer les aciers existants, notamment ceux à 9 % Cr dont la résistance à l'oxydation est considérée jusqu'à présent insuffisante et ceux à 2,25 % Cr.The Applicant has sought to do better, and in particular to obtain quantitative elements to improve existing steels, including those with 9% Cr whose resistance to oxidation is considered until now insufficient and those to 2.25 % Cr.
Expérimentations de Ia DemanderesseExperiments of the Applicant
L'Ecole des Mines de Douai a tout d'abord mis au point à l'occasion d'un contrat d'étude avec la Demanderesse une formule de prévision de la perte d'épaisseur de métal (déterminée après décapage de l'oxyde formé sans attaque du métal) sur un an à partir d'une modélisation de l'influence de l'ensemble des éléments de la composition chimique.The Ecole des Mines de Douai first developed, on the occasion of a study contract with the Applicant, a formula for predicting the loss of metal thickness (determined after etching of the oxide formed without metal attack) over one year from a modeling of the influence of all elements of the chemical composition.
Cette formule dite LPL (Lowerest Protective Layer of Scale) n'est pas publique et les termes n'en sont pas connus de la Demanderesse.This so-called LPL (Lower Protective Layer of Scale) is not public and the terms are unknown to the Applicant.
La Demanderesse a simplement pu constater des écarts notables entre les résultats expérimentaux et les résultats obtenus par application de la formule LPL, qui lui ont été communiqués.The Applicant has simply been able to note significant differences between the experimental results and the results obtained by application of the LPL formula, which were communicated to him.
La Demanderesse a donc repris les mesures de la cinétique d'oxydation à chaud par la vapeur d'eau à 6500C présentées à la conférence Les Embiez 2004 (voir ci- dessus) sur 16 échantillons d'aciers à structure ferritique (ferrite + perlite, bainite revenue, martensite revenue) dont la teneur en Cr va de 2,25 % (T22 - T23) à 13 %. La figure 4 est un tableau de composition des aciers testés avec, en dernière colonne, les valeurs des mesures de corrosion correspondant à la perte d'épaisseur de métal sur un an (vitesse de corrosion Vcor) pour ces aciers.The Applicant has therefore resumed measurements of the hot oxidation kinetics by water vapor at 650 ° C. presented at the conference Les Embiez 2004 (see above) on 16 samples of steels with a ferritic structure (ferrite + perlite, bainite revenue, martensite revenue) whose Cr content ranges from 2.25% (T22 - T23) to 13%. FIG. 4 is a composition table of the steels tested with, in the last column, the values of the corrosion measurements corresponding to the loss of metal thickness over one year (Vcor corrosion rate) for these steels.
Le terme « ND » dans le tableau de la figure 4 signifie « non disponible ».The term "ND" in the table of Figure 4 means "not available".
La Demanderesse a réalisé sur ces résultats expérimentaux une analyse statistique rnultidimensionnelle. Elle s'est fondée sur une pluralité de termes traduisant une approche empirique raisonnée de certains mécanismes ou influences, qui déterminent la vitesse de corrosion Vcor.The Applicant has performed on these experimental results a multivariate statistical analysis. It is based on a plurality of terms reflecting a reasoned empirical approach of certain mechanisms or influences, which determine the Vcor corrosion rate.
Après plusieurs essais, la Demanderesse a obtenu la formule [21] annexée, qui exprime la vitesse de corrosion Vcor à 650°C, sur le long terme, c'est-à-dire sur une période de l'ordre d'une année.After several tests, the Applicant has obtained the formula [21] attached, which expresses the corrosion rate Vcor at 650 ° C, in the long term, that is to say over a period of about a year .
La formule [21] donne la perte d'épaisseur moyenne de métal (en mm) sur un an d'exposition à la vapeur d'eau à 650°C. Cette perte d'épaisseur moyenne est elle même déduite d'une perte de poids du métal après décapage sélectif de l'oxyde, en conditions standard. La formule [21] comporte différents termes précisés comme suit :The formula [21] gives the average loss of metal thickness (in mm) over one year of exposure to water vapor at 650 ° C. This average loss of thickness is it even deduced from a weight loss of the metal after selective etching of the oxide, under standard conditions. Formula [21] has various terms as follows:
Les teneurs de la formule [21] sont exprimées en % en poids (ou en masse).The contents of formula [21] are expressed as% by weight (or by weight).
Les coefficients α (alpha), β (béta) et δ (delta) et ceux qui interviennent dans les expressions B et C ont sensiblement les valeurs indiquées en annexe 1, Section 3, expressions [31] à [36].The coefficients α (alpha), β (beta) and δ (delta) and those involved in the expressions B and C have substantially the values indicated in appendix 1, section 3, expressions [31] to [36].
A côté de cela, si l'on examine la formule [21] globalement, il apparaît qu'elle comporte notamment :Besides this, if we examine the formula [21] globally, it appears that it includes in particular:
une fonction de la teneur en chrome qui comprend un terme en 1/Cr2 avec un terme d'allure en 1/Cr (terme 1/A), et un terme correctif en Cr (terme B), une fonction polynomiale (ici du second degré) de la teneur en Manganèsea function of the chromium content which comprises a term in 1 / Cr 2 with a term of appearance in 1 / Cr (term 1 / A), and a corrective term in Cr (term B), a polynomial function (here of second degree) of the Manganese content
(terme C), une contribution conjointe (notée q) de W + Ni (tungstène + nickel) qui est d'une part en l/-q dans le terme A, et d'autre part en q dans le terme C. les autres teneurs n'interviennent qu'une seule fois, d'une manière qui se lit directement sur la formule. Les figures 5 et 6 illustrent comment cette nouvelle formule Vcor en ordonnées (Vcor predicted) se compare aux résultats expérimentaux connus de la Demanderesse en abscisses (Vcor measured). Il en découle :(term C), a joint contribution (noted q) of W + Ni (tungsten + nickel) which is on the one hand in l / -q in the term A, and on the other hand in q in the term C. the other grades occur only once, in a way that reads directly from the formula. FIGS. 5 and 6 illustrate how this new Vcor-ordinate formula (Vcor predicted) compares with the experimental results known to the Applicant on the abscissa (Vcor measured). It follows:
- en figure 5 (partie de droite), que la correspondance est excellente pour des teneurs en Chrome voisines de 2,25 %, en figure 5 (partie de gauche), ainsi qu'en figure 6, qui est un détail de la partie de gauche de la figure 5, que la correspondance est également excellente pour des teneurs en Chrome voisines de 9 % et 12 %.in FIG. 5 (right-hand part), that the correspondence is excellent for chromium contents close to 2.25%, in FIG. 5 (left-hand part), as well as in FIG. 6, which is a detail of the part on the left of FIG. 5, the correspondence is also excellent for chromium contents close to 9% and 12%.
En bref, la modélisation et l'expérience donnent des résultats remarquablement concordants. Bien évidemment, l'invention n'est pas limitée à l'expression de la formule [21], dont on sait écrire des équivalents d'allure différente. On peut également en écrire des équivalents simplifiés, d'usage plus local (en termes de fourchettes de teneurs), compte-tenu des propriétés de variation de chacun des termes, ou de leurs éléments. Enfin, si la formule [21] a été établie à 650°C, elle est naturellement valable pour d'autres températures, inférieures ou supérieures. Par exemple, une nuance d'acier ayant une vitesse de corrosion plutôt élevée à 650 °C pourra être acceptable à des températures inférieures, si elle a des propriétés intéressantes d'un point de vue quelconque, y compris un coût de fabrication moindre.In short, modeling and experience yield remarkably consistent results. Obviously, the invention is not limited to the expression of the formula [21], which is known to write equivalents of different appearance. One can also write simplified equivalents, of more local use (in terms of ranges of contents), taking into account the properties of variation of each of the terms, or their elements. Finally, if the formula [21] was set at 650 ° C, it is naturally valid for other temperatures, lower or higher. For example, a steel grade having a rather high corrosion rate at 650 ° C may be acceptable at lower temperatures, if it has interesting properties from any point of view, including a lower manufacturing cost.
Plus finement, la Demanderesse a constaté une forte influence néfaste de la teneur en Mn au-dessus d'environ 0,25 %, conformément aux indications de la formule [21] (fourchette de teneurs étudiée : 0,2 - 0,53%). Elle a également constaté que la teneur en Si joue peu lorsque Si est supérieur ou égal à 0,20 % (fourchette de teneurs étudiée : 0,09 - 0,47%). Elle a également noté l'absence d'influence significative de la teneur en carbone dans les limites étudiées (0,1 -0,2%).More finely, the Applicant has found a strong detrimental influence of the Mn content above about 0.25%, according to the indications of the formula [21] (grade range studied: 0.2 - 0.53% ). It also found that the Si content plays little when Si is greater than or equal to 0.20% (grade range studied: 0.09-0.47%). It also noted the absence of significant influence of the carbon content within the limits studied (0.1-0.2%).
La Demanderesse s'est alors intéressée à rechercher parmi les nuances performantes ferritiques des spécifications ASTM, A213 et A335 pour usage en chaudières (T91, P91, T92, P92, T23, P23, T24, P24) des domaines particuliers de composition chimique qui conduisent à des calamines minces et très adhérentes permettant de faire mieux travailler les tubes à des températures de vapeur de l'ordre de 600°, voire 650° C et des pressions de vapeur de l'ordre de 300 bars.The Applicant was then interested in searching among the ferritic performance grades of the specifications ASTM, A213 and A335 for use in boilers (T91, P91, T92, P92, T23, P23, T24, P24) particular areas of chemical composition that lead with thin and very adherent calamines to make the tubes work better at steam temperatures of the order of 600 ° or 650 ° C and vapor pressures of the order of 300 bar.
En général, les fabricants de tubes commandent jusqu'à présent leur acier dans le bas des fourchettes de teneur en chrome, compte tenu du coût de cet élément et de son caractère alphagène de cet élément. Par exemple, pour une fourchette théorique de 8,00 à 9,50 % pour le grade T91 de I1ASTM A213, les fabricants de tubes commandent un acier contenant autour de 8,5% Cr, ce qui minimise le risque de présence de ferrite delta sur produit.In general, pipe manufacturers have so far ordered their steel at the lower chromium range, given the cost of this element and its alphagenic nature of this element. For example, for a theoretical range of 8.00 to 9.50% for T91 grade of I 1 ASTM A213, tube manufacturers control a steel containing around 8.5% Cr, which minimizes the risk of ferrite delta on product.
Quant au manganèse, on sait qu'il permet de fixer le soufre de l'acier, et que cette fixation évite des problèmes de forgeabilité (brûlure de l'acier). Ainsi, alors que la fourchette de l'ASTM A213 est de 0,30 - 0, 60% pour le grade T91, il est habituel d'élaborer les aciers pour usage à haute température avec des teneurs en manganèse voisines de 0,50 %, donc dans le haut de cette fourchette.As for the manganese, it is known that it makes it possible to fix the sulfur of the steel, and that this fixation avoids problems of forgeability (burning of the steel). Thus, while the range of ASTM A213 is 0.30-0.60% for T91 grade, it is usual to develop steels for high temperature use with manganese contents close to 0.50%. , so at the top of this range.
En général, les nuances d'acier proposées ici pour des tubes sans soudure destinés à véhiculer de la vapeur d'eau sous pression et température élevées comprennent (en poids) 1,8 à 13 % de chrome (Cr), moins de 1 % de silicium (Si) et entre 0,10 et 0,45 % de manganèse (Mn). En option, l'acier comprend une addition d'au moins 1 élément choisi parmi le molybdène (Mo), le tungstène (W), le cobalt (Co), le vanadium (V), le niobium (Nb), le titane (Ti), le bore (B) et l'azote (N).In general, the steel grades proposed here for seamless tubes for conveying water vapor under high pressure and temperature include (by weight) 1.8 to 13% chromium (Cr), less than 1% silicon (Si) and between 0.10 and 0.45% manganese (Mn). As an option, the steel comprises an addition of at least 1 element chosen from molybdenum (Mo), tungsten (W), cobalt (Co), vanadium (V), niobium (Nb), titanium ( Ti), boron (B) and nitrogen (N).
Au vu de l'expérience acquise, la Demanderesse s'est focalisée sur deux groupes de nuances performantes en fluage car alliées au Mo ou au W et microalliées (Nb, V, N et éventuellement B et Ti) et améliorables du point de vue oxydation à chaud. Ce sont :In view of the experience acquired, the Applicant has focused on two groups of performance shades in creep because alloyed with Mo or W and microalliés (Nb, V, N and possibly B and Ti) and oxidation improvable hot. Those are :
- premier groupe les aciers à 2,25 % Cr : grades T/P22, T/P23, T/P24 - second groupe les aciers à 9 %. Cr : grades T/P91, T/P92 II en a découlé l'identification de nuances d'aciers spéciaux particulièrement avantageuses en termes de vitesse de corrosion, comme on va le voir maintenant.- first group steels at 2.25% Cr: grades T / P22, T / P23, T / P24 - second group steels at 9%. Cr: T / P91, T / P92 grades This has led to the identification of special grades of steels particularly advantageous in terms of corrosion rate, as will be seen now.
Mode de réalisation ElO : aciers T22 et P22ElO embodiment: T22 and P22 steels
Les normes ASTM A213 et A335 définissent respectivement les grades T22 et P22 comme contenant :ASTM standards A213 and A335 define grades T22 and P22 respectively as containing:
- 0,30 à 0,60 % Mn - au plus 0,50 % Si- 0.30 to 0.60% Mn - at most 0.50% Si
- 1,90 à 2,60 % Cr- 1.90 to 2.60% Cr
- 0,87 à 1,13 % Mo0.87 to 1.13% Mo
- 0,05 à 0,15 % C- 0.05 to 0.15% C
- au plus 0,025 % S - au plus 0,025 % P- not more than 0,025% S - not more than 0,025% P
S 'agissant de grades anciens, ils ne contiennent pas de microadditions de Ti,With respect to old grades, they do not contain microadditions of Ti,
Nb, V et B.Nb, V and B.
Dans le tableau TlO ci-après, les colonnes 2 à 7 précisent les compositions pour un acier de référence du domaine, et pour trois autres aciers proposés (désignés en colonne 1). Dans la colonne Vcor mesurée, « ND » signifie non disponible. On comprendra que les essais requis pour déterminer une vitesse de corrosion fiable et précise à haute température sur un an sont particulièrement longs, délicats et dispendieux.In Table TlO below, columns 2 to 7 specify the compositions for a domain reference steel, and for three other proposed steels (designated in column 1). In the measured Vcor column, "ND" means unavailable. It will be understood that the tests required to determine a reliable and accurate corrosion rate at high temperature over one year are particularly long, delicate and expensive.
Pour l'acier de référence (RIO), on voit que la valeur mesurée et la valeur prédite par la formule [21] se correspondent presque exactement. La formule [21] étant ainsi vérifiée, on en tire des indications sur d'autres nuances d'acier de ce mode de réalisation ElO. Ces autres nuances sont représentées par trois exemples, notésFor the reference steel (RIO), it can be seen that the measured value and the value predicted by the formula [21] correspond almost exactly. Since the formula [21] is thus verified, it gives indications on other steel grades of this embodiment ElO. These other nuances are represented by three examples, noted
ElO-max, ElO-med, et ElO-min, d'après la vitesse de corrosion obtenue. Tableau TlOElO-max, ElO-med, and ElO-min, according to the corrosion rate obtained. Table TlO
La sélection des nuances ElO permet un gain compris entre 18 % (pour ElO-ax) et 42 % (pour ElO-min), par rapport à la vitesse de corrosion de la composition « référence » RIO.The selection of ElO grades allows a gain of between 18% (for ElO-ax) and 42% (for ElO-min), compared to the corrosion rate of the composition "reference" RIO.
Dans ce mode ElO, l'acier comporte entre 2,3 et 2,6 % Cr.In this ElO mode, the steel has between 2.3 and 2.6% Cr.
Préférentiellement, l'acier du mode ElO comporte une teneur en Si comprise entre 0,20 et 0,50 % et très préférentiellement entre 0,30 et 0,50 %. Préférentiellement, l'acier comprend une teneur en Mn comprise entre 0,30 et 0,45 %.Preferably, the steel of the ElO mode comprises an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%. Preferably, the steel comprises an Mn content of between 0.30 and 0.45%.
L'acier selon ce mode ElO comporte préférentiellement entre 0,87 et 1% Mo. Il ne comporte pas d'addition volontaire de W, le tungstène étant un résiduel de l'acier et sa teneur de l'ordre de 0,01%.Steel according to this mode ElO preferably comprises between 0.87 and 1% Mo. It does not include a voluntary addition of W, tungsten being a residual steel and its content of about 0.01% .
Très préférentiellement, l'acier selon le mode ElO possède des teneurs en Cr, Mn, Si, Mo, W, Ni, Co dont la valeur Vcor calculée selon l'équation [21] est au plus égale à environ 0,9 mm/an, de préférence 0,85 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,7 mm/an.Very preferably, the steel according to the mode ElO has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.9 mm / year, preferably 0.85 mm / year. Better results are obtained for Vcor at most equal to about 0.7 mm / year.
Mode de réalisation EIl : aciers T23 et P23Embodiment EIl: T23 and P23 steels
Les normes ASTM A213 et A335 définissent respectivement les grades T23 et P23 comme contenant : - 0,10 à 0,60 % MnASTM standards A213 and A335 define grades T23 and P23 respectively as containing: - 0.10 to 0.60% Mn
- au plus 0,50 % Si- not more than 0.50% Si
- 1,90 à 2,60 % Cr- 1.90 to 2.60% Cr
- 0,05 à 0,30 % Mo - 1,45 à 1,75 % W- 0.05 to 0.30% Mo - 1.45 to 1.75% W
- 0,04 à 0,10 % C- 0.04 to 0.10% C
- au plus 0,030 % P- not more than 0,030% P
- auplus 0,010 % S- more than 0.010% S
- 0,20 à 0,30 % V - 0,02 à 0,08 % Nb- 0.20 to 0.30% V - 0.02 to 0.08% Nb
- 0,0005 à 0,006 % B- 0.0005 to 0.006% B
- au plus 0,030 % de N- not more than 0,030% of N
- au plus 0,030 % d'Al- not more than 0,030% of Al
Le remplacement d'une grosse partie du molybdène par le tungstène et les microadditions donnent à ces grades des caractéristiques de résistance au fluage très améliorées par rapport aux grades T/P22. Une telle amélioration ne permet par contre pas d'augmenter la limite supérieure de tenue en température vis à vis de l'oxydation à chaud.The replacement of a large proportion of molybdenum by tungsten and microadditions gives these grades very improved creep characteristics compared to T / P22 grades. Such an improvement does not, on the other hand, make it possible to increase the upper temperature resistance limit with respect to hot oxidation.
Dans le tableau TIl ci-après, les colonnes 2 à 7 précisent les compositions pour un acier de référence du domaine, et pour trois autres aciers proposés (désignés en colonne 1). Pour l'acier de référence, on voit que la valeur mesurée et la valeur prédite par la formule [21] se correspondent exactement. La formule [21] étant ainsi vérifiée, on en tire des indications sur les trois autres nuances d'acier de ce mode de réalisation El 1, notées El 1-max, El 1-med, et El 1-min, d'après la vitesse de corrosion obtenue. Tableau TIlIn Table TIl below, columns 2 to 7 specify the compositions for a domain reference steel, and for three other proposed steels (designated in column 1). For the reference steel, we see that the measured value and the value predicted by the formula [21] correspond exactly. The formula [21] being thus verified, it gives indications on the other three steel grades of this embodiment El 1, denoted El 1-max, El 1-med, and El 1-min, according to the corrosion rate obtained. TIl Table
La sélection des nuances EIl permet un gain compris entre 12 % (pour El 1- max) et 51 % (pour EI l -min), par rapport à la vitesse de corrosion de la composition « référence ».The selection of the shades EIl allows a gain of between 12% (for El 1- max) and 51% (for EI l -min), with respect to the corrosion rate of the "reference" composition.
Dans ce mode EIl, l'acier comporte entre 2,3 et 2,6 % Cr.In this mode, the steel has between 2.3 and 2.6% Cr.
Préférentiellement, l'acier du mode EI l comporte une teneur en Si comprise entre 0,20 et 0,50 % et très préférentiellement entre 0,30 et 0,50 %. Préférentiellement, l'acier comprend une teneur en Mn comprise entre 0,25 et 0,45 %.Preferably, the steel of mode EI 1 has an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%. Preferably, the steel comprises an Mn content of between 0.25 and 0.45%.
L'acier selon ce mode El 1 comporte préférentiellement entre 1,45 % et 1,60 % W et entre 0,05 et 0,20 % Mo.The steel according to this mode El 1 preferably comprises between 1.45% and 1.60% W and between 0.05 and 0.20% Mo.
Très préférentiellement, l'acier selon le mode El 1 possède des teneurs en Cr, Mn, Si, Mo, W, Ni, Co dont la valeur Vcor calculée selon l'équation [21] est inférieure à environ 1,4 mm/an, de préférence au plus égale à environ 1,25 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,9 mm/an.Very preferably, the steel according to the mode El 1 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is less than about 1.4 mm / year. preferably at most equal to about 1.25 mm / year. Better results are obtained for Vcor at most equal to about 0.9 mm / year.
Mode de réalisation E 12 : aciers T24/P24Embodiment E 12: T24 / P24 steels
Ces aciers contiennent selon la norme ASTM A213 0,30 à 0,70 % Mn 0,15 à 0,45 % Si 2,20 à 2,60 % Cr 0,70 à 1,10 % Mo 0,04 à 0,10 % C au plus 0,020 % P auplus 0,010 % S 0,20 à 0,30 % V 0,06 à 0,10 % Ti 0,0015 à 0,0020 % B au plus 0,012 % N au plus 0,020 % AlThese steels contain according to ASTM A213 0.30 to 0.70% Mn 0.15 to 0.45% Si 2.20 to 2.60% Cr 0.70 to 1.10% Mo 0.04 to 0.10% C at most 0.020% P at most 0.010% S 0.20 to 0.30% V 0.06 to 0 , 10% Ti 0.0015 to 0.0020% B at most 0.012% N at most 0.020% Al
Le tableau Tl 2 ci-après est construit de manière semblables aux tableaux TlO et TI l.Table Tl 2 below is constructed similarly to Tables T10 and TI1.
Tableau T12Table T12
Le gain est plus limité sur la sélection selon l'invention : de 9 % (E12-max) à 30 % (E12-min). Il est estimé que cela tient essentiellement au fait que la marge sur la teneur en Cr est plus faible que pour les modes de réalisation El 0 ou El 1.The gain is more limited on the selection according to the invention: from 9% (E12-max) to 30% (E12-min). It is believed that this is mainly because the margin on the Cr content is lower than for the embodiments El 0 or El 1.
Selon ce mode E12, l'acier comporte entre 2,4 et 2,6 % Cr. Préférentiellement, l'acier comporte une teneur en Si comprise entre 0,20 et 0,45 % et très préférentiellement entre 0,30 et 0,45 %. Préférentiellement, l'acier comprend une teneur en Mn comprise entre 0,30 et 0,45 %. L'acier selon ce mode E12 ne comporte pas d'addition de W (teneur en tungstène résiduelle de l'ordre de 0,01%) ; sa teneur en Mo est de préférence comprise entre 0,70 et 0,9 %.According to this mode E12, the steel comprises between 2.4 and 2.6% Cr. Preferably, the steel has an Si content of between 0.20 and 0.45% and very preferably between 0.30 and 0.45%. Preferably, the steel comprises an Mn content of between 0.30 and 0.45%. The steel according to this mode E12 does not include any addition of W (residual tungsten content of the order of 0.01%); its Mo content is preferably between 0.70 and 0.9%.
Très préférentiellement, l'acier selon ce mode El 2 possède des teneurs en Cr,Very preferably, the steel according to this mode El 2 has contents of Cr,
Mn, Si, Mo, W, Ni, Co dont la valeur Vcor calculée selon l'équation [21] est au plus égale à environ 0,8 mm/an et de préférence au plus égale à environ 0,75 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,7 mm/an.Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.8 mm / year and preferably at most equal to about 0.75 mm / year. Better results are obtained for Vcor at most equal to about 0.7 mm / year.
On observera que les modes ElO, EIl et E12 (globalement notés El) sont assez proches, en termes de teneur en Chrome, Manganèse et Silicium. Ainsi, d'autres teneurs en Cr, Mn et/ou Si de l'un de ces modes El peuvent être appliquées au moins partiellement à un autre mode El .It will be observed that the modes ElO, EIl and E12 (generally rated El) are quite similar in terms of chromium, manganese and silicon content. Thus, other contents Cr, Mn and / or Si of one of these modes El can be applied at least partially to another mode El.
Mode réalisation E20 ; aciers T9 et P9Embodiment mode E20; T9 and P9 steels
Les normes ASTM A213 et A335 définissent respectivement les grades T9 et P9 comme contenant :ASTM standards A213 and A335 define grades T9 and P9, respectively, as containing:
- 0,30 à 0,60 % Mn - 0,25 à 1,00 % Si- 0.30 to 0.60% Mn - 0.25 to 1.00% Si
- 8,00 à 10,00 % Cr- 8.00 to 10.00% Cr
- 0,90 à 1,10 % Mo- 0.90 to 1.10% MB
- au plus 0,15 % C- not more than 0,15% C
- au plus 0,025 % P - au plus 0,025 % S- not more than 0,025% P - not more than 0,025% S
Par rapport aux modes de réalisation E21 et E22 exposés plus loin dans le texte, les aciers selon le mode de réalisation E20 ne contiennent pas de microadditions de V, Nb, N ou B.With respect to the embodiments E21 and E22 discussed later in the text, the steels according to embodiment E20 do not contain microadditions of V, Nb, N or B.
Dans le tableau T20 ci-après, les colonnes 2 à 7 précisent les compositions pour un acier de référence du domaine, et pour trois autres aciers proposés (désignés en colonne 1). Dans la colonne Vcor mesurée, « ND » signifie non disponible. On comprendra que les essais requis pour déterminer une vitesse de corrosion fiable et précise à haute température sur un an sont particulièrement longs, délicats et dispendieux.In Table T20 below, columns 2 to 7 specify the compositions for a reference steel of the domain, and for three other proposed steels (designated in column 1). In the measured Vcor column, "ND" means unavailable. It will be understood that the tests required to determine a reliable corrosion rate and Precise at high temperatures over a year are particularly long, delicate and expensive.
On a tiré de la formule [21] des indications sur différentes nuances d'acier de ce mode de réalisation E20. Ces nuances sont représentées par trois exemples, notés E20-max, E20-med, et E20-min, d'après la vitesse de corrosion obtenue.Formula [21] has been derived from the indications for different grades of steel of this embodiment E20. These grades are represented by three examples, denoted E20-max, E20-med, and E20-min, according to the corrosion rate obtained.
Tableau T20Table T20
La sélection des nuances E20 permet un gain compris entre 16 % (pour E20- max) et 89 % (pour E20-min), par rapport à la vitesse de corrosion de la composition « référence » R20.The selection of the grades E20 allows a gain of between 16% (for E20-max) and 89% (for E20-min), relative to the corrosion rate of the "reference" composition R20.
Dans ce mode E20, l'acier comporte entre 9.2 et 10.00 % Cr.In this mode E20, the steel has between 9.2 and 10.00% Cr.
Préférentiellement, l'acier du mode E20 comporte une teneur en Si comprise entre 0,25 et 0,50 % et très préférentiellement entre 0,30 et 0,40 %. Préférentiellement, l'acier comprend une teneur en Mn comprise entre 0,30 et 0,45 %.Preferably, the steel of the mode E20 has an Si content of between 0.25 and 0.50% and very preferably between 0.30 and 0.40%. Preferably, the steel comprises an Mn content of between 0.30 and 0.45%.
L'acier selon ce mode E20 comporte préférentiellement entre 0,90 et 1,00% Mo. Il ne comporte pas d'addition volontaire de W, le tungstène étant un résiduel de l'acier et sa teneur de l'ordre de 0,01%. Très préférentiellement, l'acier selon le mode E20 possède des teneurs en Cr, Mn, Si, Mo, W, Ni, Co dont la valeur Vcor calculée selon l'équation [21] est au plus égale à environ 0,09 mm/an, de préférence 0,06 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,04 mm/an.The steel according to this mode E20 preferably comprises between 0.90 and 1.00% Mo. It does not include a voluntary addition of W, the tungsten being a residual of the steel and its content of the order of 0, 01%. Very preferably, the steel according to the mode E20 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.09 mm / year, preferably 0.06 mm / year. Better results are obtained for Vcor at most equal to about 0.04 mm / year.
Mode de réalisation E21 : aciers T91/P91Embodiment E21: T91 / P91 steels
Ces aciers contiennent selon les normes ASTM A213 et A335 : - 0,30 à 0,60 % MnThese steels contain according to ASTM standards A213 and A335: - 0.30 to 0.60% Mn
- 0,20 à 0,50 % Si- 0.20 to 0.50% Si
- 8,00 à 9,50 % Cr- 8.00 to 9.50% Cr
- 0,85 à 1,05 % Mo- 0.85 to 1.05% MB
- au plus 0,40 % Ni - 0,08 à 0,12 % C- not more than 0.40% Ni - 0.08 to 0.12% C
- au plus 0,020 % P- not more than 0,020% P
- au plus 0,010 % S- not more than 0,010% S
- 0,18 à 0,25 % V- 0.18 to 0.25% V
- 0,06 à 0,1 % Nb - 0,030 à 0,070 % N- 0.06 to 0.1% Nb - 0.030 to 0.070% N
- au plus 0,040 % Al- not more than 0,040% Al
Le tableau T21 ci-après est construit de manière semblable au tableau TlO.Table T21 below is constructed similarly to Table T10.
Tableau T21Table T21
Le gain sur la sélection de ces modes de réalisations E21 va de 10 % (E21-max) à 80 % (E21-min). Il est remarquable que, pour E21-min, la valeur obtenue est cinq fois plus faible que la valeur de référence. The gain on the selection of these embodiments E21 ranges from 10% (E21-max) to 80% (E21-min). It is remarkable that for E21-min, the value obtained is five times lower than the reference value.
Selon ce mode E21, l'acier comporte entre 8,9 et 9,5 % Cr.According to this mode E21, the steel comprises between 8.9 and 9.5% Cr.
Préférentiellement, l'acier comporte une teneur en Si comprise entre 0,20 et 0,50 % et très préférentiellement entre 0,30 et 0,50 %.Preferably, the steel comprises an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%.
Préférentiellement, l'acier comprend une teneur en Mn comprise entre 0,30 etPreferably, the steel comprises a Mn content of between 0.30 and
0,45 %. Il comporte préférentiellement entre 0,85 % et 0,95 % Mo.0.45%. It preferably comprises between 0.85% and 0.95% Mo.
Préférentiellement, l'acier selon le mode de réalisation E21 comprend au plus 0,2 % Ni (et très préférentiellement au plus 0,1%), et pratiquement pas de tungstène (résiduel de l'ordre de 0,01%).Preferably, the steel according to embodiment E21 comprises at most 0.2% Ni (and very preferably at most 0.1%), and practically no tungsten (residual of the order of 0.01%).
Très préférentiellement l'acier selon le mode E21 possède des teneurs en Cr, Mn, Si, Mo, W, Ni, Co dont la valeur Vcor calculée selon l'équation [21] est inférieure à environ 0,1 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,07 mm/an.Very preferably, the steel according to the mode E21 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is less than about 0.1 mm / year. Better results are obtained for Vcor at most equal to about 0.07 mm / year.
Mode de réalisation E22 : aciers T92/P92Embodiment E22: T92 / P92 steels
Ces aciers contiennent selon les normes ASTM A213 et A335 : - au plus 0,30 à 0,60 % MnThese steels contain according to ASTM A213 and A335: - at most 0.30 to 0.60% Mn
- au plus 0,50 % Si- not more than 0.50% Si
- 8,50 à 9,50 % Cr- 8.50 to 9.50% Cr
- 0,30 à 0,60 % Mo- 0.30 to 0.60% Mo
- 1,50 à 2,00 % W - au plus 0,40 % Ni- 1.50 to 2.00% W - at most 0.40% Ni
- 0,07 à 0,13 % C- 0.07 to 0.13% C
- au plus 0,020 % P au plus 0,010 % S 0,15 à 0,25 % V 0,04 à 0,09 % Nb 0,001 à 0,006 % B 0,030 à 0,070 % N au plus 0,040 % Al- not more than 0,020% P not more than 0.010% S 0.15 to 0.25% V 0.04 to 0.09% Nb 0.001 to 0.006% B 0.030 to 0.070% N not more than 0.040% Al
Le tableau T22 ci-après est construit de manière semblable au tableau TlO.Table T22 below is constructed similarly to Table T10.
Tableau T22Table T22
Ici, le gain sur la sélection de ces modes de réalisations E22 va de 2 % (E22- max) à 52 % (E22-min).Here, the gain on the selection of these embodiments E22 ranges from 2% (E22- max) to 52% (E22-min).
Selon ce mode de réalisation E22, l'acier comporte entre 8,9 et 9,5 % Cr.According to this embodiment E22, the steel comprises between 8.9 and 9.5% Cr.
Préférentiellement, l'acier du mode E22 comporte une teneur en Si comprise entre 0,20 et 0,50 % et très préférentiellement entre 0,30 et 0,50 %.Preferably, the steel of mode E22 has an Si content of between 0.20 and 0.50% and very preferably between 0.30 and 0.50%.
Préférentiellement, l'acier du mode E22 comprend une teneur en Mn comprise entre 0,30 et 0,45 % et plus préférentiellement entre 0,30 et 0,40%.Preferably, the steel of mode E22 comprises an Mn content of between 0.30 and 0.45% and more preferably between 0.30 and 0.40%.
L'acier selon le mode E22 comporte préférentiellement entre 0,30 % et 0,45 % Mo. Il comporte entre 1 ,50 et 1 ,75 % W. Préférentiellement, l'acier selon le mode E22 comprend au plus 0,2 % Ni et très préférentiellement au plus 0,1%.The steel according to the mode E22 preferably comprises between 0.30% and 0.45% Mo. It comprises between 1.50 and 1.75% W. Preferably, the steel according to the mode E22 comprises at most 0.2% Ni and very preferably at most 0.1%.
Très préférentiellement l'acier selon le mode E22 possède des teneurs en Cr, Mn, Si, Mo, W, Ni, Co qui, selon l'équation [21], donnent une valeur Vcor au plus égale à environ 0,11 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,08 mm/an.Very preferably, the steel according to the mode E22 has contents of Cr, Mn, Si, Mo, W, Ni, Co which, according to the equation [21], give a value Vcor at most equal to about 0.11 mm / year. Better results are obtained for Vcor at most equal to about 0.08 mm / year.
On observera que les modes E21 et E22 (globalement notés E2) sont assez proches, en termes de teneur en Chrome, Manganèse et Silicium. Ainsi, les autres teneurs en Cr, Mn et/ou Si de l'un de ces modes E2 peuvent être appliquées au moins partiellement à l'autre.It will be observed that the modes E21 and E22 (generally noted E2) are quite similar in terms of chromium, manganese and silicon content. Thus, the other contents of Cr, Mn and / or Si of one of these modes E2 can be applied at least partially to the other.
On considérera maintenant une situation intermédiaire.We will now consider an intermediate situation.
Mode de réalisation E30 ; aciers T5 et P5Embodiment E30; T5 and P5 steels
Les normes ASTM A213 et A335 définissent respectivement les grades T5 et P5 comme contenant : - 0,30 à 0,60 % MnASTM A213 and A335 define T5 and P5, respectively, as containing: - 0.30 to 0.60% Mn
- au plus 0,50 % Si- not more than 0.50% Si
- 4,00 à 6,00 % Cr- 4.00 to 6.00% Cr
- 0,45 à 0,65 % Mo- 0.45 to 0.65% MB
- au plus 0,15 % C - au plus 0,025 % P- not more than 0,15% C - not more than 0,025% P
- au plus 0,025 % S- not more than 0,025% S
Dans le tableau T30 ci-après, les colonnes 2 à 7 précisent les compositions pour un acier de référence du domaine, et pour trois autres aciers proposés (désignés en colonne 1). Dans la colonne Vcor mesurée, « ND » signifie non disponible. On comprendra que les essais requis pour déterminer une vitesse de corrosion fiable et précise à haute température sur un an sont particulièrement longs, délicats et dispendieux.In Table T30 below, columns 2 to 7 specify the compositions for a reference steel of the domain, and for three other proposed steels (designated in column 1). In the measured Vcor column, "ND" means unavailable. It will be understood that the tests required to determine a reliable corrosion rate and Precise at high temperatures over a year are particularly long, delicate and expensive.
On a tiré de la formule [21] des indications sur différentes nuances d'acier de ce mode de réalisation E30. Ces nuances sont représentées par trois exemples, notés E30-max, E30-med, et E30-min, d'après la vitesse de corrosion obtenue.Formula [21] has been derived from the indications for different grades of steel of this embodiment E30. These grades are represented by three examples, noted E30-max, E30-med, and E30-min, according to the corrosion rate obtained.
Tableau T30Table T30
La sélection des nuances E30 permet un gain compris entre 15 % (pour E30- max) et 55 % (pour E30-min), par rapport à la vitesse de corrosion de la composition « référence » R30.The selection of grades E30 allows a gain of between 15% (for E30-max) and 55% (for E30-min), compared to the corrosion rate of the composition "reference" R30.
Dans ce mode E30, l'acier comporte entre 5.2 et 6.00 % Cr.In this mode E30, the steel has between 5.2 and 6.00% Cr.
Préférentiellement, l'acier du mode E30 comporte une teneur en Si comprise entre 0,25 et 0,50 % et très préférentiellement entre 0,30 et 0,45 %. Préférentiellement, l'acier comprend une teneur en Mn comprise entre 0,30 et 0,45 %.Preferably, the steel of the E30 mode comprises an Si content of between 0.25 and 0.50% and very preferably between 0.30 and 0.45%. Preferably, the steel comprises an Mn content of between 0.30 and 0.45%.
L'acier selon ce mode E30 comporte préférentiellement entre 0,45 et 0.60%The steel according to this mode E30 preferably comprises between 0.45 and 0.60%
Mo. Il ne comporte pas d'addition volontaire de W, le tungstène étant un résiduel de l'acier et sa teneur de l'ordre de 0,01%.Mo. It does not include a voluntary addition of W, tungsten being a residual steel and its content of the order of 0.01%.
Très préférentiellement, l'acier selon le mode E30 possède des teneurs en Cr, Mn, Si, Mo, W, Ni, Co dont la valeur Vcor calculée selon l'équation [21] est au plus égale à environ 0,23 mm/an, de préférence 0,20 mm/an. De meilleurs résultats sont obtenus pour Vcor au plus égale à environ 0,17 mm/an.Very preferably, the steel according to the mode E30 has contents of Cr, Mn, Si, Mo, W, Ni, Co whose Vcor value calculated according to the equation [21] is at most equal to about 0.23 mm / year, preferably 0.20 mm / year. Better results are obtained for Vcor at most equal to about 0.17 mm / year.
Le modèle utilisé conduit à augmenter la teneur en certains éléments alphagènes tels que Cr, Si et à réduire la teneur en certains éléments gammagènes tels que Mn et Ni5 ce qui peut favoriser l'apparition de ferrite delta.The model used leads to increase the content of some alphagenic elements such as Cr, Si and to reduce the content of some gammagenic elements such as Mn and Ni 5 which can promote the appearance of delta ferrite.
Si la réduction de teneur en Mo et/ou W (éléments alphagènes) est insuffisante pour compenser l'augmentation de teneur en Cr, Si et la réduction de celle en Mn et Ni du point de vue de l'apparition de ferrite delta, il y aura lieu d'ajuster la teneur en éléments gammagènes comme N et C qui n'interviennent pas dans le présent modèle. On utilisera à cet égard des formules connues de prévision de ferrite delta en fonction des teneurs en chrome équivalent et nickel équivalent.If the reduction in Mo and / or W content (alphagenic elements) is insufficient to compensate for the increase in Cr, Si content and the reduction of that in Mn and Ni from the point of view of the appearance of delta ferrite, it It will be necessary to adjust the content of gamma-like elements such as N and C that are not involved in the present model. In this respect, it will be possible to use known formulas for prediction of delta ferrite as a function of the contents of equivalent chromium and equivalent nickel.
La technique proposée pour optimiser des aciers spéciaux comprend les éléments suivants. On part d'une nuance ou grade d'acier connu ayant des propriétés connues autres que la corrosion à chaud, que l'on cherche à optimiser du point de vue corrosion à chaud. On calcule une propriété de corrosion à long terme selon un modèle tel que celui de la formule [21] sur une composition de référence. On cherche au voisinage de l'acier connu une fourchette particulière de composition de la nuance d'acier conduisant à une meilleure valeur de la propriété de corrosion selon le même modèle.The proposed technique for optimizing special steels includes the following elements. It starts from a known steel grade or grade with known properties other than hot corrosion, which we want to optimize from the point of view of hot corrosion. A long-term corrosion property is calculated according to a model such as that of formula [21] on a reference composition. In the vicinity of the known steel, a particular range of composition of the steel grade is sought, leading to a better value of the corrosion property according to the same model.
Dès lors que le modèle est de grande fiabilité, cette technique a de nombreux avantages, dont :Since the model is highly reliable, this technique has many advantages, including:
éviter de fabriquer des aciers inhabituels seulement pour des tests de corrosion, éviter les délicats et coûteux tests de corrosion à long terme et haute température.avoid making unusual steels only for corrosion tests, avoid delicate and expensive long-term and high temperature corrosion tests.
Cette technique permet surtout d'utiliser des données ciblées et non outrageusement pessimistes pour la conception de chaudières ou de tuyauteries de vapeur et par là de minimiser la surépaisseur de corrosion prise en compte dans les calculs de conception.This technique makes it possible especially to use targeted and not outrageously pessimistic data for the design of boilers or piping systems. steam and thereby minimize the extra thickness of corrosion taken into account in the design calculations.
Elle permet en outre d'augmenter la température de vapeur à température de métal donné et d'éviter des exfoliations de calamine en favorisant la germination hétérogène et discontinue de l'oxyde en surface de l'acier du côté vapeur.It also makes it possible to increase the vapor temperature at a given metal temperature and to avoid calamine exfoliations by promoting the heterogeneous and discontinuous germination of the oxide on the surface of the steel on the vapor side.
L'acier selon l'invention peut également être utilisé sans que la liste soit exhaustive comme tôle pour fabriquer des tubes soudés, des raccords, des réacteurs, des pièces de chaudronnerie, comme pièce moulée pour fabriquer des corps de turbine ou des corps de vannes de sécurité, comme pièce forgée pour fabriquer des arbres et des rotors de turbine, des raccords, comme poudre métalliques pour réaliser des composants divers en métallurgie des poudres, comme métal d'apport de soudure et d'autres applications similaires. The steel according to the invention can also be used without the list being exhaustive as sheet to manufacture welded tubes, fittings, reactors, boiler parts, as molded part for manufacturing turbine bodies or valve bodies as forging for making turbine shafts and rotors, fittings, as metal powder for making various components in powder metallurgy, as solder metal and other similar applications.
Annexe 1Annex 1
Section 1Section 1
Section 2 Section 2
Section 3Section 3
Alpha = 2.828 (31)Alpha = 2.828 (31)
Beta = 0.237 (32)Beta = 0.237 (32)
A = Cr - (Mo + W + Ni + Co) (33)A = Cr - (Mo + W + Ni + Co) (33)
Delta = 0.091 (34)Delta = 0.091 (34)
B = 1.40 - 0.12 * Cr + 0.007 / Si (35)B = 1.40 - 0.12 * Cr + 0.007 / Si (35)
C = 1.2 * Mn * Mn - 0.53 * Mn + 0.02 * (W + Ni) - 0.012 (36) C = 1.2 * Mn * Mn - 0.53 * Mn + 0.02 * (W + Ni) - 0.012 (36)

Claims

Revendications claims
1. Composition d'acier pour applications spéciales, caractérisée en ce qu'elle comprend, en poids, environ 1,8 à 11 % de Chrome, moins de 1 % de Silicium, et entre 0,20 et 0,45 % de Manganèse, les teneurs de la composition d'acier étant ajustées selon un modèle prédéterminé, choisi pour obtenir des caractéristiques de tenue à l'oxydation à chaud sensiblement optimales dans des conditions données de performances à haute température.1. Steel composition for special applications, characterized in that it comprises, by weight, about 1.8 to 11% of chromium, less than 1% of silicon, and between 0.20 and 0.45% of manganese , the contents of the steel composition being adjusted according to a predetermined model, selected to obtain substantially optimal hot oxidation resistance characteristics under given high temperature performance conditions.
2. Composition d'acier selon la revendication 1, caractérisée en ce qu'elle comprend comme addition ou comme résiduel au moins un élément choisi parmi le molybdène, le tungstène, le cobalt, et le nickel.2. A steel composition according to claim 1, characterized in that it comprises as addition or as residual at least one element selected from molybdenum, tungsten, cobalt, and nickel.
3. Composition d'acier selon l'une des revendications 1 et 2, caractérisée en ce qu'elle comporte une teneur de silicium en poids comprise entre environ 0,20 et 0,50 %, de préférence entre environ 0,30 et 0,50%.3. Steel composition according to one of claims 1 and 2, characterized in that it comprises a silicon content by weight of between about 0.20 and 0.50%, preferably between about 0.30 and 0 , 50%.
4. Composition d'acier selon l'une des revendications 1 à 3, caractérisée en ce qu'elle comporte une teneur de manganèse en poids comprise entre 0,25 et 0,45 % environ.4. A steel composition according to one of claims 1 to 3, characterized in that it comprises a manganese content by weight of between 0.25 and 0.45%.
5. Composition d'acier selon l'une des revendications 1 à 4, caractérisée en ce que ledit modèle comporte au moins un terme de contribution du chrome, et un terme de contribution du manganèse seul.5. A steel composition according to one of claims 1 to 4, characterized in that said model comprises at least one chromium contribution term, and a contribution term of manganese alone.
6. Composition d'acier selon la revendication 5, caractérisée en ce que ledit terme de contribution du manganèse seul comprend une fonction polynomiale du second degré de la teneur en manganèse.Steel composition according to claim 5, characterized in that said manganese contribution term alone comprises a polynomial function of the second degree of the manganese content.
7. Composition d'acier selon l'une des revendications 5 et 6, caractérisée en ce que ledit terme de contribution du chrome comprend un terme quadratique en inverse de la teneur en chrome, et un terme en inverse d'une quantité contenant la teneur en chrome.7. Steel composition according to one of claims 5 and 6, characterized in that said chromium contribution term comprises a quadratic term in inverse of the chromium content, and a reverse term of a quantity containing the chromium content.
8. Composition d'acier selon l'une des revendications précédentes, caractérisée en ce qu'elle comporte entre 2,3 et 2,6 % en poids de Chrome, environ.8. A steel composition according to one of the preceding claims, characterized in that it comprises between 2.3 and 2.6% by weight of chromium, approximately.
9. Composition d'acier selon la revendication 8, caractérisée en ce qu'elle comporte, en poids, entre 1,45 % et 1,60 % de tungstène et entre 0,05 et 0,20 % de molybdène (El 1).9. A steel composition according to claim 8, characterized in that it comprises, by weight, between 1.45% and 1.60% of tungsten and between 0.05 and 0.20% of molybdenum (El 1). .
10. Composition d'acier selon la revendication 9, caractérisée par des teneurs en poids de Cr, Mn5 Si5 Mo, W, Ni, Co telles que la valeur de corrosion Vcor selon la relation [21] est inférieure à environ 1,4, de préférence au plus égale à environ 1,25 (EI l).10. The composition of steel according to claim 9, characterized by contents by weight of Cr, Mn 5 Si 5 Mo, W, Ni, Co such that the corrosion value Vcor according to the equation [21] is less than about 1, 4, preferably at most equal to about 1.25 (EI 1).
11. Composition d'acier selon la revendication 8, caractérisée en ce qu'elle comporte, en poids, entre 0,87 et 1 % de molybdène et très peu de tungstène (ElO).11. A steel composition according to claim 8, characterized in that it comprises, by weight, between 0.87 and 1% molybdenum and very little tungsten (ElO).
12. Composition d'acier selon la revendication 11, caractérisée par des teneurs en poids de Cr, Mn5 Si, Mo, W5 Ni, Co telles que la valeur de corrosion Vcor selon la relation [21] est au plus égale à environ 0,9, de préférence est au plus égale à environ 0,85 (ElO).12. The composition of steel according to claim 11, characterized by contents by weight of Cr, Mn 5 Si, Mo, W 5 Ni, Co such that the corrosion value Vcor according to the equation [21] is at most equal to about 0.9, preferably is at most about 0.85 (EO).
13. Composition d'acier selon la revendication 8, caractérisée en ce qu'elle comporte, en poids, entre 2,4 et 2,6 % de chrome, entre 0,70 et 0,90 % de molybdène et pratiquement pas de tungstène (E 12).13. A steel composition according to claim 8, characterized in that it comprises, by weight, between 2.4 and 2.6% chromium, between 0.70 and 0.90% molybdenum and substantially no tungsten (E 12).
14. Composition d'acier selon la revendication 11, caractérisée par des teneurs en poids de Cr, Mn, Si, Mo, W, Ni, Co telles que la valeur de corrosion Vcor selon la relation [21] au plus égale à environ 0,8, de préférence au plus égale à environ 0,75 (E12). 14. A steel composition according to claim 11, characterized by the weight contents of Cr, Mn, Si, Mo, W, Ni, Co such that the Vcor corrosion value according to the relationship [21] at most equal to about 0 , 8, preferably at most equal to about 0.75 (E12).
15. Composition d'acier selon l'une des revendications 1 à 7, caractérisée en ce qu'elle comporte entre 8,9 et 9,5 % en poids de Chrome, environ.15. A steel composition according to one of claims 1 to 7, characterized in that it comprises between 8.9 and 9.5% by weight of chromium, approximately.
16. Composition d'acier selon la revendication 15, caractérisée en ce qu'elle comporte entre 0,85 % et 0,95 % de molybdène (E21).16. A steel composition according to claim 15, characterized in that it comprises between 0.85% and 0.95% molybdenum (E21).
17. Composition d'acier selon la revendication 16, caractérisée par une teneur en Mo comprise entre 0,85 et 0,95 % Mo et sensiblement une absence de W, et dont la valeur de corrosion Vcor selon la relation [21] est inférieure à environ 0,1, de préférence au plus égale à environ 0,07 (E21 ).17. A steel composition according to claim 16, characterized by a Mo content between 0.85 and 0.95% Mo and substantially an absence of W, and whose corrosion value Vcor according to the relationship [21] is less at about 0.1, preferably at most about 0.07 (E21).
18. Composition d'acier selon la revendication 15, caractérisée en ce qu'elle comporte entre 1,50 et 1,75 % de tungstène et entre 0,30 et 0,45% de molybdène (E22).18. A steel composition according to claim 15, characterized in that it comprises between 1.50 and 1.75% of tungsten and between 0.30 and 0.45% of molybdenum (E22).
19. Composition d'acier selon la revendication 18, caractérisée par des teneurs en poids de Cr, Mn, Si, Mo, W, Ni, Co, dont la valeur de corrosion Vcor selon la relation [21] est au plus égale à environ 0,11, de préférence 0,08 (E22).19. A steel composition according to claim 18, characterized by the weight contents of Cr, Mn, Si, Mo, W, Ni, Co, whose corrosion value Vcor according to the relationship [21] is at most equal to about 0.11, preferably 0.08 (E22).
20. Composition d'acier selon l'une des revendications 15 à 19, caractérisée en ce qu'elle comporte moins de 0,2 % de nickel.20. Steel composition according to one of claims 15 to 19, characterized in that it comprises less than 0.2% nickel.
21. Tube sans soudure ou accessoire, essentiellement constitué d'une composition d'acier selon l'une des revendications précédentes.21. Seamless tube or accessory, essentially consisting of a steel composition according to one of the preceding claims.
22. Application de la composition d'acier à des tubes sans soudure et accessoires, destinés à générer, à véhiculer ou à conditionner de la vapeur d'eau sous pression et température élevées. 22. Application of the steel composition to seamless tubes and accessories for generating, conveying or conditioning high pressure water vapor and temperature.
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CN101466859A (en) 2009-06-24
MX2008015740A (en) 2009-03-02
EP2027300B8 (en) 2012-11-14
FR2902111A1 (en) 2007-12-14
AU2007255279A1 (en) 2007-12-13
EA200870608A1 (en) 2009-04-28
ES2371534T3 (en) 2012-01-04
UA97368C2 (en) 2012-02-10
US20100307430A1 (en) 2010-12-09
KR20090023475A (en) 2009-03-04
JP2009540118A (en) 2009-11-19
EA015633B1 (en) 2011-10-31
EP2027300B1 (en) 2011-08-17
CA2654521A1 (en) 2007-12-13
CN101466859B (en) 2012-08-22
PL2027300T3 (en) 2012-01-31
AU2007255279B2 (en) 2011-10-13
CA2654521C (en) 2014-10-14
US9005520B2 (en) 2015-04-14
BRPI0712148B1 (en) 2018-09-11
HRP20110850T1 (en) 2011-12-31
ATE520796T1 (en) 2011-09-15
WO2007141427A2 (en) 2007-12-13
BRPI0712148A2 (en) 2012-02-22
WO2007141427A3 (en) 2008-07-31

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