US20040109784A1 - Steel and steel tube for high- temperature use - Google Patents

Steel and steel tube for high- temperature use Download PDF

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US20040109784A1
US20040109784A1 US10/472,758 US47275803A US2004109784A1 US 20040109784 A1 US20040109784 A1 US 20040109784A1 US 47275803 A US47275803 A US 47275803A US 2004109784 A1 US2004109784 A1 US 2004109784A1
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steel
content
less
ferrite
steel according
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Alireza Arbab
Bruno Lefebvre
Jean-Claude Vaillant
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Vallourec Tubes France SAS
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Assigned to V & M FRANCE reassignment V & M FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEFEBVRE, BRUNO, VAILLANT, JEAN-CLAUDE, ARBAB, ALIREZA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to steels for use under stress at high temperatures of about 600° C. to 650° C., more particularly steels known as ferritic steels with a high chromium content with a tempered martensitic structure both at ambient temperature and at service temperatures.
  • the invention is applicable to tubular metal products such as superheater tubes, reheater tubes, headers or pipings for superheated or reheated steam for boilers, or tubes for furnaces for chemistry or petrochemistry.
  • Such products are usually seamless tubes obtained after a severe hot plastic deformation operation carried out on solid bars of highly specialized steel.
  • Such steels are highly resistant to corrosion by steam because of their chromium content and have high creep rupture strengths of up to 700° C. due to their austenitic structure.
  • tubes of ASTM A213 T91 steel (generally used for small superheater tubes) or ASTM A335 P91 (generally used for the largest pipes for header or superheated steam piping) are known. These grades contain 0.1% C, 9% Cr, 1% Mo, 0.2% V, 0.08% Nb and 0.05% N and have a creep rupture strength at 10 5 hrs at 600° C. ( ⁇ R10 5 h600° C. ) of 98 MPa.
  • ASTM A213 T92 steel (or ASTM A335 P92 steel) has a chemical composition close to T91/P91 except that the Mo content is greatly reduced and it contains 1.8% W and a tiny amount of boron; the creep rupture strength at 10 5 hrs at 600° C. ( ⁇ R10 5 h600° C. ) for that steel is of the order of 120 MPa.
  • Said steels T91, P91, T92, P92 contain 9% Cr and some of their users believe that such a Cr content is insufficient to resist hot oxidation and/or corrosion by steam beyond 600° C., in particular at 650° C. because of the metal temperature envisaged for the tubes of the superheaters in future power stations.
  • flaking of said layer when it is too large may lead to accumulation of debris in the bends in the superheaters, impeding the movement of steam with a supplemental risk of overheating the tubes. Flaking can also result in debris being entrained into the turbine and can thus damage its blades.
  • German DIN 17175 X20CrMoV12-1 (abbreviated to X20) steel is also known, containing 0.20% C, 11% to 12% Cr, 1% Mo and 0.2% V.
  • That steel is claimed to be more resistant to hot oxidation than T91 or T92 because of its Cr content, but it is far less resistant to creep rupture than T91/P91 and it is difficult to weld, in particular when very thick.
  • a C content of 0.20% or more appears to be not much desirable as regards weldability. Adding a large amount of Ni, though, has the disadvantage of greatly reducing the Ac1 point and thus limiting the maximum tempering temperature of the tubes; it also appears to be deleterious to the creep rupture strength.
  • U.S. Pat. No. 5,069,870 discloses the addition of Cu (austenite forming element) in amounts of 0.4% to 3% to a 12% Cr steel to compensate for the increase in Cr content.
  • adding Cu causes problems as regards forgeability when fabricating tubes for superheaters by hot rolling.
  • a grade with 11% Cr, 1.8% W, 1% Cu and micro-alloyed with V, Nb and N with the same disadvantages is defined in ASTM A213 and A335 and termed T122, P122.
  • Japanese patent application JP-A-4 371 551 discloses adding between 1% and 5% (and generally more than 2%) of Co (also austenite forming) to a steel containing 0.1% C, 8% to 13% Cr, 1% to 4% W, 0.5% to 1.5% Mo, less than 0.20% Si (and in fact less than 0.11% Si) and micro-alloyed with V, Nb, N and B to obtain a creep rupture resistance that is very high and a Charpy V-notch impact test strength that is sufficient after ageing.
  • Co also austenite forming
  • European patent application EP-A-0 892 079 also proposes adding Co in amounts of 0.2% to 5% but in a steel containing less than 10% Cr, which does not solve the problem described above.
  • Japanese patent application JP-A-11 061 342 and European patent application EP-A-0 867 523 also propose adding Co, but jointly with the addition of Cu for the first document and at least 1% Ni for the second document.
  • European patent application EP-A-0 758 025 also proposes adding Co, generally in very large amounts; for that reason, to prevent the formation of intermetallic precipitates based on Cr, Mo, Co, W, C and Fe, that document jointly proposes adding (Ti or Zr) and alkaline-earths (Ca, Mg, Ba) or rare earths (Y, Ce, La).
  • JP-A-8 187 592 also proposes adding Co with a particular relationship between the (Mo+W) and (Ni+Co+Cu) contents, but said additions and relationships are proposed for optimizing the composition of the added materials for welding, and are not proposed to tolerate forming such as that carried out when fabricating seamless tubes (forgeability properties).
  • JP-A-8 225 833 also proposes adding Co, but concerns a heat treatment to reduce the amount of residual austenite and not a chemical composition; the chemical composition ranges are thus broad and a teaching for the envisaged use cannot be deduced therefrom.
  • the present invention proposes the production of a steel:
  • the steel under consideration contains, by weight: C 0.06% to 0.20% Si 0.10% to 1.00% Mn 0.10% to 1.00% S 0.010% or less Cr 10.00% to 13.00% Ni 1.00% or less W 1.00% to 1.80% Mo such that (W/2 + Mo) is 1.50% or less Co 0.50% to 2.00% V 0.15% to 0.35% Nb 0.030% to 0.150% N 0.030% to 0.120% B 0.0010% to 0.0100%
  • the remainder of the chemical composition of said steel is constituted by iron and impurities or residual elements resulting from or necessary to steelmaking and casting.
  • the amounts of the constituents of the chemical composition are linked so that after normalization heat treatment between 1050° C. and 1080° C. and tempering, the steel has a tempered martensitic structure that is free of or almost free of ⁇ ferrite.
  • the carbon is in the form of carbides or carbonitrides the initial distribution and the change in said distribution of which with time act on the mechanical characteristics at ambient temperature and at the service temperature.
  • a C content of less than 0.06% would render obtaining a structure free of ⁇ ferrite and the production of the desired creep characteristics difficult.
  • a C content of more than 0.20% is deleterious to the weldability of the steel.
  • a content range of 0.10-0.15% is preferred.
  • This element is an element that deoxidizes liquid steel and also limits the kinetics of hot oxidation by air or steam in particular, according to the inventors, acting in synergy with the chromium content.
  • a content of less than 0.10% of Si is insufficient for producing said effects.
  • Si is a ferrite forming element which has to be limited to avoid the formation of ⁇ ferrite and it also tends to encourage precipitation of embrittling phases in service. For this reason, its content is limited to 1.00%.
  • a content range of 0.20% to 0.60% is preferred.
  • This element encourages deoxidation and fixes the sulphur. It also reduces the formation of ⁇ ferrite.
  • a content range of 0.15% to 0.50% is preferred.
  • This element essentially forms sulphides which reduce the impact properties in the transverse direction and forgeability.
  • An S content limited to 0.010% prevents the formation of defects when hot piercing billets during the fabrication of seamless tubes.
  • This element is found both dissolved in the steel matrix and precipitated in the form of carbides.
  • a minimum Cr content of 10% and preferably 11% is necessary for the hot oxidation behaviour.
  • the maximum Ni content is limited to 0.50%.
  • This element which is both dissolved and precipitated in the form of carbides and intermetallic phases, is findamental to the creep behaviour at 600° C. and above, hence the minimum content of 1.00%.
  • this element is expensive, highly segretative and ferrite forming, and tends to form embrittling intermetallic phases.
  • This element has an effect similar to tungsten even though it appears to be less effective as regards creep strength.
  • the molybdenum content is preferably 0.50% or less.
  • This element stabilizes austenite and thus enables more than 10% Cr to be tolerated; it also improves the creep strength properties; a minimum content of 0.50% is thus desirable.
  • this element contributes to forming embrittling intermetallic compounds that can precipitate at the service temperature; further, it is very expensive.
  • the inventors of the present invention have surprisingly established that a range of cobalt contents of 0.50% to 2.00% and preferably 1.00% to 1.50% can satisfy the aims for said steel and in particular provide an optimum compromise between the various, possibly contradictory characteristics (for example oxidation resistance, creep strength and forgeability), using a relatively simple metallurgy and a limited manufacturing cost for metal products.
  • This element forms nitrides and carbonitrides that are very fine and stable and thus very important for the creep rupture strength.
  • a content of less than 0.15% is insufficient for producing the desired result.
  • a content of more than 0.35% is deleterious as regards the risk of the appearance of ⁇ ferrite.
  • a preferred range is from 0.20% to 0.30%.
  • this element forms stable carbonitrides and its addition reinforces the stability of vanadium compounds.
  • a Nb content of less than 0.030% is insufficient.
  • a Nb content of more than 0.15% is not favorable as the Nb carbonitrides may become too large and reduce the creep resistance.
  • a preferred range is from 0.050% to 0.100%.
  • This austenite forming element can reduce the appearance of ⁇ ferrite.
  • a nitrogen content of more than 0.120% results in blow holes in ingots, billets or slabs in the steels under consideration and as a result to defects in the metal products. The same risk exists on welding when processing said products.
  • a nitrogen content range of 0.040% to 0.100% is preferred.
  • This element contributes to stabilizing carbides when added in an amount in excess of 0.0010%.
  • a content of more than 0.0100% can, however, substantially reduces the burning temperature of products, in particular of as cast products, and thus is detrimental.
  • This element is also ferrite forming and scavenges nitrogen; thus, Al contents of more than 0.050% are discouraged.
  • aluminium can be added to obtain a final content of up to 0.050%.
  • a Ca or Mg content of less than 0.0010% results from exchanges between liquid steel and slag containing lime or magnesia in a highly deoxidized medium: they are thus inevitable steelmaking residuals.
  • calcium can optionally be added in amounts of a little over 0.0010% to improve castability and/or control the form of oxides and sulphides.
  • a Ca content of more than 0.0100% denotes an oxygen-rich and therefore dirty steel and is thus discouraged.
  • the steel of the invention Apart from iron, which is the base constituent of steel, and the elements indicated above, the steel of the invention only contains other elements as impurities; examples are phosphorus and oxygen, and residuals deriving mainly from the iron added to the furnace to produce the steel or from exchange with the slag or refractories or necessary to the steelmaking and casting processes.
  • the copper content (resulting from furnaced scrap and not from deliberate addition) remains less than 0.25% and optionally less than 0.10%. Contents of more than said contents may proscribe certain hot rolling processes for seamless tube rolling and require the use of more expensive glass extrusion processes.
  • Structure almost free of ⁇ ferrite means a structure containing no more than 2% of ⁇ ferrite and preferably no more than 1% of ⁇ ferrite (measured with an absolute precision of ⁇ 1%).
  • FIG. 1 shows a diagram of ⁇ ferrite content against equivalent chromium content for different specimens of heat treated steels containing 8% to 13% of Cr.
  • FIG. 2 shows a diagram of the results of forgeability tests on steel F in accordance with the invention compared with other steels.
  • FIG. 3 shows, for the same steel F compared with other steels, a diagram of hot tensile tests, FIG. 3 a ) relating to the yield point and FIG. 3 b ) to the tensile strength.
  • FIG. 4 shows, for the same steel F compared with other steels, a transition curve for the Charpy V-notch impact strength test.
  • FIG. 5 shows, for the same steel F compared with other steels, a graph of results of creep rupture strength tests under a constant unit load.
  • FIG. 6 shows, for the same steel F compared with other steels, a master curve for the results of creep rupture strength tests under different unit loads as a function of the Larson-Miller parameter.
  • a 100 kg laboratory heat formed from the steel of the invention was produced under vacuum (F).
  • FIG. 1 shows the relationship between an equivalent chromium parameter (Cr equ ) derived from the chemical composition and the ⁇ ferrite content:
  • FIG. 1 we show the ⁇ ferrite content measured by image analysis in the optical microscope for a certain number of heats of T91, P91, T92 and X20 as a function of the parameter Cr equ .
  • FIG. 1 provides analytical evidence that the amounts of elements in heat F lie within the ranges given in the chemical composition defined in claim 1 .
  • Table 1 shows the chemical composition of this heat F and the mean chemical composition of known prior art grades (weight %) as well as the corresponding value of the parameter Cr equ .
  • Said heat F contains no added Ca and its Al content is less than 0.010% (Al and Ca as residuals).
  • FIG. 2 shows the reduction in area results.
  • the ⁇ ferrite content was less than 15% up to 1250° C. and less than 20% up to 1280° C.
  • the burning temperature was over 1320° C.
  • Table 3 shows the results obtained compared with typical results for known steels.
  • Temperature Ac1 of 830° C. for steel F is comparable with that of P91 and P92 and much higher than that of P122 containing copper which does not allow a tempering temperature of more than 780° C. In contrast, a tempering temperature of 800° C. is entirely possible with steel F of the invention.
  • microstructure and hardness were measured after a normalizing heat treatment of 20 minutes at 1060° C. (treatment N1) or 1080° C. (treatment N2); the results are shown in Table 4. TABLE 4 Results after normalizing heat treatment microstructure HV10 hardness present invention treatment N1 martensite ( ⁇ 0.5% ⁇ 420 (F) ferrite) treatment N2 martensite (0.5% ⁇ 410 ferrite) comparative steel P92 martensite ( ⁇ 0.5% ⁇ 425 ferrite)
  • FIG. 5 The results of the stress rupture test at 120 MPa are shown in FIG. 5 as a function of the parameter 1000/T (in ° K ⁇ 1 ), as is conventional for this type of grade.
  • the temperatures were selected so that the maximum duration of the test was close to 4000 h.
  • FIG. 5 allows the temperature corresponding to a test duration of 10 5 h to be extrapolated for a unit load. It can be seen that for steel F, this temperature at least equals if not exceeds that of steel P92.
  • LMP Larson-Miller parameter
  • FIG. 6 shows that the tests are favourable compared with the mean master curve (solid line) and the lower scatter band (dotted line) for steels T92 and P92 defined by ASME.
  • TP347H (austenitic grade, 18% Cr-10% Ni—Nb).
  • the steel of the invention allows thus to produce boilers with a steam temperature of more than 600° C. completely from ferritic steel, including the hottest parts of the boiler.
  • TABLE 8 Corrosion rate corrosion rate (mm/year) steel type grade 600° C. 650° C. present invention F 0.008 0.013 comparative steels T22 0.175 1 T23 0.216 1.43 T91 0.055 0.09 T92 0.070 0.10 T122 0.074 0.114 X20 0.076 0.116 TP347H 0.026 0.077 TP347GF(*) 0.001 0.020
  • grade F of the invention perfectly fits in with sulphur contents of 0.005% or less or even 0.003% or less, and does not necessitate the addition of rare earths and/or alkaline-earths which are difficult to implement.
  • Ingots were forged into solid bars with a diameter of 180 mm, which were then transformed into seamless tubes with an outer diameter of 60.3 mm and a thickness of 8.8 mm using continuous rolling over a retained mandrel with diameter reduction on a stretch reducing-mill.
  • Table 10 shows the results of tensile tests at ambient temperature on tubes treated by normalization at 1060° C. and tempering for 2 h at 780° C.
  • Table 11 shows the results of Charpy V-notch impact strength tests on tubes that underwent the same heat treatment as that for the tensile tests.
  • TABLE 10 Results of ambient temperature tensile tests on steel tubes of the invention R p0.2 (MPa) R m (MPa) A5.65 ⁇ square root ⁇ s (%) tube, 60.3 ⁇ 8.8 mm 564 781 26 tube, 406.4 ⁇ 35 mm 587 784 23

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
US10/472,758 2001-04-04 2002-04-03 Steel and steel tube for high- temperature use Abandoned US20040109784A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0104551 2001-04-04
FR0104551A FR2823226B1 (fr) 2001-04-04 2001-04-04 Acier et tube en acier pour usage a haute temperature
PCT/FR2002/001151 WO2002081766A1 (fr) 2001-04-04 2002-04-03 Acier et tube en acier pour usage a haute temperature

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US (1) US20040109784A1 (cs)
EP (1) EP1373589B1 (cs)
JP (1) JP2004526058A (cs)
KR (1) KR20040007489A (cs)
CN (1) CN1317415C (cs)
AT (1) ATE280843T1 (cs)
AU (1) AU2002302671B8 (cs)
BR (1) BR0208629B1 (cs)
CA (1) CA2442299C (cs)
CZ (1) CZ299079B6 (cs)
DE (1) DE60201741T2 (cs)
ES (1) ES2231694T3 (cs)
FR (1) FR2823226B1 (cs)
MX (1) MXPA03008934A (cs)
PL (1) PL196693B1 (cs)
RU (1) RU2293786C2 (cs)
WO (1) WO2002081766A1 (cs)

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CN112981057A (zh) * 2021-02-05 2021-06-18 大唐锅炉压力容器检验中心有限公司 一种低硬度p91钢试块的制备方法
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DE602008003811D1 (de) * 2007-07-10 2011-01-13 Aubert & Duval Sa Gehärteter martensitischer stahl mit geringem oder ohne kobaltanteil, verfahren zur herstellung eines teils aus diesem stahl und in diesem verfahren hergestelltes teil
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DE102008010749A1 (de) * 2008-02-20 2009-09-24 V & M Deutschland Gmbh Stahllegierung für einen niedrig legierten Stahl zur Herstellung hochfester nahtloser Stahlrohre
FR2942808B1 (fr) * 2009-03-03 2011-02-18 Vallourec Mannesmann Oil & Gas Acier faiblement allie a limite d'elasticite elevee et haute resistance a la fissuration sous contrainte par les sulfures.
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