EP1432839B1 - Verwendung von austenitischem nichtrostendem stahl - Google Patents

Verwendung von austenitischem nichtrostendem stahl Download PDF

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Publication number
EP1432839B1
EP1432839B1 EP02780214A EP02780214A EP1432839B1 EP 1432839 B1 EP1432839 B1 EP 1432839B1 EP 02780214 A EP02780214 A EP 02780214A EP 02780214 A EP02780214 A EP 02780214A EP 1432839 B1 EP1432839 B1 EP 1432839B1
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EP
European Patent Office
Prior art keywords
wire
weight
alloy
content
manganese
Prior art date
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Expired - Lifetime
Application number
EP02780214A
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English (en)
French (fr)
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EP1432839A1 (de
Inventor
Hakan Silfverlin
Charlotte Ulfvin
Gustaf Zetterholm
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires

Definitions

  • the present invention relates to the use of an austenitic stainless steel alloy with high Cr-, Mo-, Mn-, N- and Ni-contents with a combination of high corrosion resistance and good mechanical properties, such as high tensile strength and good ductility, which is especially suitable for use for applications in the extraction of oil and gas, such as e.g. wire, more specially as reinforcement wire of a diameter of 1.0 mm or thinner in the application wirelines.
  • wirelines or well logging cables of stainless steel i.e. ropes or strands are used within applications for offshore oil- and gasextraction.
  • these are usually designed in such way that they contain a plurality of insulated electric leaders or cables, such as e.g. fiber optical cables, which are in their entirety covered of one or more bearing helical wound steel wire.
  • GB-A-2329722 which hereby is included as reference, gives an overview about the state of the art regarding wellbore logging and forms of execution for well logging cables, without claiming to be complete.
  • the selection of steel grades is primarily determined by the demand on strength, tensile strength, ductility and corrosion properties, especially under the prevailing conditions in an oil- or gas well and by temperatures up to 250°C.
  • the application is to a large extent limited by the load-resistances to fatigue due to repeated use in oil- and gasindustry, especially in applications as slickline or wellbore logging cable and in this application of repeated reeling and transport over a so-called pulley wheel.
  • the corresponding profile of requirements can also be directed to strip- and wiresprings, where high requirements on strength, fatigue- and corrosion properties occur. In all those cases the use is ascending limited by reasons of corrosion or load.
  • the object of the present invention to provide a stainless steel alloy wire with austenitic matrix having the composition given below and simultaneously high strength in combination with high ductility and load-resistance against general corrosion at high temperatures, especially at temperatures up to 250°C.
  • the stainless steel alloy wire has a tensile strength of at least 310 kpsi at wire diameters of 1.0 mm or thinner in applications for oil and gas extraction.
  • an alloy according to the present invention which contains (in weight-%): Cr 24.0-30.0 Ni 25.0-34.0 Mo 3.0-6.0 Mn >2.0-6.0 N 0.2-0.4 C up to 0.05 Si up to 1.0 S up to 0.02 Cu up to 3.0 W 0-6.0
  • N 0.2-0.4 C up to 0.05 Si up to 1.0 S up to 0.02 Cu up to 3.0 W 0-6.0
  • Mg, Ce, Ca, B, La, Pr, Zr, Ti, Nd up to 2.0 and the balance Fe and normally occurring impurities and additions.
  • the alloy wire according to the invention contains therefore, in weight-percent: Cr 24-30 Ni 25-34 Mo 3.0-6.0 Mn >2-6 N 0.2-0.4 C up to 0.05 Si up to 1.0 S up to 0.02 Cu up to 3 W 0-6.0 a or more of the Elements Mg, Ce, Ca, B, La, Pr, Zr, Ti, Nd up to 2.0 and the balance Fe and normally occurring impurities and additions.
  • the importance of the alloying elements for the present alloy is the following:
  • a high content of nickel homogenizes a high alloyed steel by increasing the solubility of Cr and Mo.
  • the austenite stabilizing nickel suppresses the forming of the unwanted phases sigma-, laves- and chi-phase, which to a large extent consists of exactly the alloying elements chromium and molybdenum.
  • a disadvantage is that nickel decreases the solubility in the alloy and detoriates the hot workability, which entails an upper limitation for the nickel quantity in the alloy.
  • the present invention has shown that high contents of nitrogen can be allowed at nickel contents according to the above-mentioned by balance the high nickel content to high chromium- and manganese-contents.
  • the Ni-content of the alloy should therefore be limited to 25.0-32.0 weight-%, preferably to at least 26.0 weight-%, more preferably at least 30.0 weight-% or 31.0 weight-%.
  • the upper limit for the Ni-content is preferably 34.0 weight-%
  • Chromium (Cr) is a very active element in order to improve the resistance to a plurality of corrosion types. Furthermore, a high chromium-content implies that one may a very good N-solubility in the material. It is thus desirable to keep the chromium-content as high as possible in order to improve the corrosion resistance. For very good amounts of the corrosion resistance, the chromium-content should be at least 24.0 weight-%, preferably 27.0 -29.0 weight-%. However, high contents of Cr increase the risk for intermetallic precipitations, for what reason the chromium-content must be limited upwards to max 30.0 weight-%.
  • Molybdenum Molybdenum (Mo) In modern corrosion resistant austenitic steels frequently a high alloying addition of the element molybdenum will be made in order to increase the resistance to corrosion attacks in general.
  • molybdenum elevates the corrosion rate.
  • An explanation is molybdenum's tendency of precipitation, which gives rise to unwanted phases during sensitization. Therefore, a high chromium-content is chosen in favor of a high molybdenum content, even in order to obtain an optimum structural stability of the alloy.
  • both alloying elements increase the tendency of precipitation, but tests show that molybdenum does this more than twice as much as chromium.
  • the molybdenum content should be limited to between 2.0 and up to 6.0 weight-%, preferably to at least 3.7 weight-%, preferably to at least 4.0 weight-%.
  • the upper limit for molybdenum content is 6.0 weight-%, preferably 5.5 weight-%.
  • the precipitation of intermetallic phase is favored by increasing contents of chromium and molybdenum, but can be restrained by addition of N as well as Ni to the alloy.
  • the Ni-content is limited mainly by aspect of costs as well as of that it strongly decreases solubility of N in smelt. Consequently, the N-content is limited of the solubility in smelt and also in the solid phase, where precipitation of Cr-nitrides can occur.
  • the Mn- and Cr-content can be increased and the Ni-content be decreased.
  • Mo is considered giving rise to increased risk for precipitation of intermetallic phase, why it has been considered being necessary to limit this content.
  • higher contents of alloying elements have not been limited with consideration to the structural stability.
  • Tungsten increases the load-resistance to pitting- and crevice corrosion. But alloying with too high contents of tungsten in combination with that the Cr-content as well as Mo-content are high, means that the risk for intermetallic precipitations increases.
  • the content of tungsten should therefore lie within the range of 0 to 6.0 weight-%, preferably 0 to 4.0 weight-%.
  • a manganese-addition implies a decreasing of the hardness during hot working, which one can understand from diagram on Fig. 1, which shows the required stress during hot working for variants of the alloy with high respectively low manganese-content.
  • the good hot workability of the alloy makes alloy excellent suitable for the production of tubes, wire and strip etc.
  • manganese has been found influencing negatively on hot ductility of the alloy, such as described by the formula below. Its strong positive influence as hardness decreasing alloying element during hot working was estimated as more important.
  • the content of manganese of the alloy should be higher than 2.0 weight-%, preferably 3.0 to 6.0 weight-%, more preferably 4.0-6.0 weight-%.
  • Carbon (C) has limited solubility in both ferrite and austenite.
  • the limited solubility implies a risk for precipitation of chromium-carbides and therefore the content should not exceed 0.05 weight-%, preferably not exceed 0.03 weight-%.
  • Si Silicon
  • Si is utilized as desoxidation agent for the steel production and also increases the flowability during production and welding.
  • too high contents of Si lead to precipitation of unwanted intermetallic phase, for what reason the content should be limited to max 1.0 weight-%, preferably max 0.8 weight-%, more preferably to 0.5 weight-%.
  • Sulfur(S) influences the corrosion resistance negatively by forming easily dissolvable sulfides. Furthermore, the hot workability deteriorates for what reason the content of sulfur is limited to max 0.02 weight-%.
  • Nitrogen (N) is like molybdenum a popular alloying element in modern corrosion resistant austenites in order to increase the corrosion resistance, but also the alloys mechanical strength.
  • nitrogen is foremost the increasing of the mechanical strength by nitrogen, which will be exploited.
  • the invention exploits also that nitrogen increases the mechanical strength of the alloy as consequence of interstitial soluted atoms, which cause stresses in the crystal structure.
  • a high strength is of vital importance for the intended applications as sheets, heat exchangers, production tubes, wire- and strip springs, riggwire, wirelines and also slicklines.
  • By using a high tensile material the possibility is given to obtain the same strength, but with less material consumption and thereby less weight. Simultaneously, this increases the requirements on the ductility of the material.
  • springs their susceptibility for absorbing elastic energy is of decisive importance.
  • the nitrogen content should be 0.20-0.40 weight-%, preferably 0.35-0.40 weight-%.
  • Copper(Cu) The influence of copper on corrosion properties of the austenitic steel is disputed. However, it seems to be clear that copper strongly improves the corrosion resistance in sulfuric acid, which is of big importance for range of applications of the alloy. During tests copper has also shown being an element, which is favorable for the production of tubes, for what reason a copper-addition is particularly important for material aimed for tube applications. However, from the experience it is known that a high copper-content in combination with a high manganese-content strongly detoriates the hot ductility, for what reason the upper limit for copper-content is determined to 3.0 weight-%. The copper-content is preferably at the most 1.5 weight-%.
  • At least one of the ductility additions as magnesia (Mg), calcium (Ca), cerium (Ce), boron (B), lanthanum (La), praseodym (Pr), zirconium (Zr), titanium (Ti) and neodymium (Nd) should be added in a content of up to 2.0 weight-% in purpose to improve the hot workability.
  • compositions for the tested alloys according to the invention and for known alloys are specified in comparing purpose.
  • known alloys being used as references are, in those cases where they were used for testing, the interval which defines the composition that was tested and which lies within the standard for the alloy.
  • Table 1 shows some embodiments for the alloy according to the invention.
  • the negative influence of molybdenum on the required tension is demonstrated of variants X and P in Fig 1.
  • the positive influence of manganese on the required tension is demonstrated of variants S and P in Fig 2.
  • the ductility of the material in delivery finish was evaluated with the help of businesstypical torsion- and winding-tests.
  • the torsion-test was executed by twisting a 20-cm long wire until that that the breaking arises, but at least 5 turns.
  • the winding-tests were executed by winding a wire at least 5 turns round its own axis and subsequently wind the wire up without that breaking or cracks arise.
  • the present invention manages the requirements on the ductility also in a high strength supply condition. As described in Figure 4 the alloy of the present invention manages the requirement son the ductility also at amounts of the tensile strength exceeding 310 kpsi.
  • the stress-diagram for a wire in wireline-applications is mainly assembled of three components, which are shown in Table 2: the dead weight of the wire according to equation (1), the carried load according to equation (2) and also of the tension, which is induced of the measurement equipment's support-wheel according to equation (3) and the total tension as the total of the partial stresses according to equation (4).
  • Table 2 the dead weight of the wire according to equation (1), the carried load according to equation (2) and also of the tension, which is induced of the measurement equipment's support-wheel according to equation (3) and the total tension as the total of the partial stresses according to equation (4).
  • Table 2 shows how large the load above the dead weight, wire produced of an alloy according to the invention compared with wire produced of the well-known alloy UNS N08028 can carry as function of the length of the wire.
  • a long wire, as in the intended application slickline can be up to approximately 30.000 foot long and gets a noticeable dead weight, which loads the wire.
  • This dead weight is generally carried up of a wheel of different curvature, which gives further rise to loads for the wire.
  • a smaller wire diameter manages stronger curvatures.
  • Figure 6 shows how large load inclusive dead weight and bending stress a wire, produced of the new alloy compared to wire produced from of the well-known alloy UNS N08028, can carry as function of the diameter of the breaking wheel.
  • the alloy wire according to the invention shows surprisingly a very high corrosion resistance in environments, which are relevant for the application wirelines. Until now the test shows surprising results, but is in moment of writing still not brought to an end. The test was exhibited in an environment according to the following: Saturated NaCl (26 weight-%) + 5 weight-% MgCl 2 + 5% H 2 S at 177°C and 5000 psi (34.5MPa) during 336 hours.
  • the wire was then annealed at 260°C during 24 hours and showed thereafter a tensile strength of 310 kpsi (2135 MPa).
  • the material showed also good results in the torsion- and winding tests as described in example 2.

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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)
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Claims (2)

  1. Verwendung einer austenitischen nichtrostenden Legierung mit der folgenden Zusammensetzung in Gewichtsprozent: Cr 24 - 30 Ni 25-34 Mo 3-6 Mn >2-6 N 0,20 - 0,40 C bis zu 0,05 Si bis zu 1,0 S bis zu 0,02 Cu bis zu 3,0 W 0-6,0
    eines oder mehrere der Elemente Mg, Ce, Ca, B, La, Pr, Zr, Ti, Nd
    bis zu 2,0
    und Rest Eisen und normalerweise auftretende Verunreinigungen,
    welche eine Kombination aus guter Korrosionsbeständigkeit und guten mechanischen Eigenschaften zeigt, insbesondere eine Zugfestigkeit von wenigstens 310 kpsi bei Durchmessern von 1,0 mm und dünner, als Draht mit einem Durchmesser von 1,0 mm oder dünner bei der Öl- und Gasextraktion.
  2. Verwendung einer austenitischen nichtrostenden Legierung nach Anspruch 1 als Verstärkungsdraht bei der Anwendung Drahtleitungen.
EP02780214A 2001-09-25 2002-09-25 Verwendung von austenitischem nichtrostendem stahl Expired - Lifetime EP1432839B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0103234 2001-09-25
SE0103234A SE527177C2 (sv) 2001-09-25 2001-09-25 Användning av ett austenitiskt rostfritt stål
PCT/SE2002/001749 WO2003027344A1 (en) 2001-09-25 2002-09-25 Use of an austenitic stainless steel

Publications (2)

Publication Number Publication Date
EP1432839A1 EP1432839A1 (de) 2004-06-30
EP1432839B1 true EP1432839B1 (de) 2007-06-20

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EP02780214A Expired - Lifetime EP1432839B1 (de) 2001-09-25 2002-09-25 Verwendung von austenitischem nichtrostendem stahl

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US (1) US20050028893A1 (de)
EP (1) EP1432839B1 (de)
AT (1) ATE365236T1 (de)
DE (1) DE60220809T2 (de)
SE (1) SE527177C2 (de)
WO (1) WO2003027344A1 (de)

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Publication number Priority date Publication date Assignee Title
SE531305C2 (sv) * 2005-11-16 2009-02-17 Sandvik Intellectual Property Strängar för musikinstrument
US8862551B2 (en) * 2005-12-29 2014-10-14 Nextlabs, Inc. Detecting behavioral patterns and anomalies using activity data
JP4288528B2 (ja) * 2007-10-03 2009-07-01 住友金属工業株式会社 高強度Ｃｒ−Ｎｉ合金材およびそれを用いた油井用継目無管
DE102014108311B4 (de) * 2013-06-13 2015-01-15 Thyssenkrupp Steel Europe Ag Auswahlverfahren für Stahlgüten
CN108138295B (zh) * 2015-10-19 2021-09-14 山特维克材料技术公司 新型奥氏体不锈合金
CN107326288A (zh) * 2017-05-27 2017-11-07 苏州铭晟通物资有限公司 一种耐腐蚀性金属材料
CN107419194A (zh) * 2017-06-29 2017-12-01 振石集团东方特钢有限公司 一种超级奥氏体不锈钢板卷的加工方法
JP6823221B1 (ja) * 2020-07-31 2021-01-27 日本冶金工業株式会社 高耐食オーステナイト系ステンレス鋼とその製造方法

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Also Published As

Publication number Publication date
EP1432839A1 (de) 2004-06-30
DE60220809D1 (de) 2007-08-02
SE0103234D0 (sv) 2001-09-25
WO2003027344A1 (en) 2003-04-03
DE60220809T2 (de) 2008-03-06
SE527177C2 (sv) 2006-01-17
SE0103234L (sv) 2003-03-26
ATE365236T1 (de) 2007-07-15
US20050028893A1 (en) 2005-02-10
WO2003027344A8 (en) 2004-04-22

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