US20030133823A1 - Use of a duplex stainless steel alloy - Google Patents

Use of a duplex stainless steel alloy Download PDF

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US20030133823A1
US20030133823A1 US10/232,727 US23272702A US2003133823A1 US 20030133823 A1 US20030133823 A1 US 20030133823A1 US 23272702 A US23272702 A US 23272702A US 2003133823 A1 US2003133823 A1 US 2003133823A1
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ferrite
content
weight
austenite
heats
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Ann Sundstrom
Pasi Kangas
Anna-Lena Nystrom
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SANKVIK AB
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
    • C22C38/18—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite

Definitions

  • the present invention relates to stainless steel alloys, and more particularly to a duplex stainless steel alloy with ferritic-austenitic matrix with high resistance to corrosion in combination with good structural stability and a combination of mechanical properties which make it suitable for use in applications in environments where a high corrosion resistance is required, such as in chloride-containing environments, such as oil refining processes and hydro-metallurgical processes.
  • Previously used metallic materials are titanium-alloyed and super duplex alloys.
  • the superduplex steel Zeron 100 shows problems at welds, mainly caused by an unbalanced microstructure as a result of precipitation of sigma phase.
  • the material according to the present invention although having a high alloying content exhibits extraordinarily workability, particularly hot workability and shall be well-suited for production as bars, tubes, such as welded and seamless tubes, plate, strip, wire, welding wire, constructive parts, such as e.g. flanges and couplings.
  • duplex stainless steel alloys which contain (in weight %) up to 0.03% C, up to 0.5% Si, 24.0-30.0% Cr, 4.9-10.0% Ni, 3.0-5.0% Mo, 0.28-0.5% N, 0-3.0% Mn, 0-0.0030% B, up to 0.010% S, 0-0.03% Al, 0-0.010% Ca, 0-3.0% W, 0-2.0% Cu, 0-3.5% Co, 0-0.3% Ru, balance Fe and inevitable impurities and which shows a content of ferrite in the range of 40 to 65 volume % and a PRE number of at least between 46 and 50 in both the austenite and ferrite phases and with an optimum relationship between PRE austenite and PRE ferrite in the range of 0.90 to 1.15; preferably between 0.9 and 1.05.
  • FIG. 1 shows CPT values from tests of the test heats in the modified ASTM G48C test in “Green Death” solution compared with the duplex steels SAF2507, SAF 2906 as well as that high alloyed austenitic steel 654SMO.
  • FIG. 2 shows CPT values attained with the assistance of the modified ASTM G48C test in “Green Death” solution for the test heats compared with the duplex steel SAF2507 as well as the austenitic steel 654SMO.
  • FIG. 3 shows average amount for avfillerningen in mm/year in 2% HCl at a temperature of 75° C.
  • FIG. 4 shows scores from hot ductility testing for most of the heats.
  • the alloy according to the invention contains (in weight %): C Max 0.03% Si Max 0.5% Mn 0-3.0% Cr 24.0-30.0% Ni 4.9-10.0% Mo >3.0-5.0% N 0.28-0.5% B 0-0.0030% S max 0.010% Co 0-3.5% W 0-3.0% Cu 0-2.0% Ru 0-0.3% Al 0-0.03% Ca 0-0.010%
  • Carbon (C) has limited solubility in both ferrite and austenite.
  • the limited solubility implies a risk of precipitation of chromium carbides and the content should therefore not exceed 0.03 weight %, preferably not exceed 0.02 weight %.
  • Si is utilized as desoxidation agent in the steel production and increases flowability during production and welding.
  • excessive contents of Si lead to precipitation of unwanted intermetallic phases, thus the content is limited to max 0.5 weight %, preferably max 0.3 weight %.
  • Mn Manganese
  • Mn is added in order to increase the N solubility in the material.
  • Mn only has a limited influence on the N solubility in the type of alloy in question. Instead there are other elements found to have with higher influence on the solubility.
  • Mn in combination with high contents of sulfur can give rise to formation of manganese sulfides, which act as initiation points for pitting corrosion.
  • the content of Mn should therefore be limited to between 0-3.0 weight %, preferably 0.5-1.2 weight %.
  • Chromium (Cr) is an active element in order to improve the resistance to a majority of corrosion types. Furthermore, a high content of chromium implies that one gets a very good N solubility in the material. Thus, it is desirable to keep the Cr content as high as possible in order to improve the corrosion resistance. For very good amounts of corrosion resistance the content of chromium 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 content of chromium must be limited up to max 30.0 weight %.
  • Nickel (Ni) is used as austenite stabilizing element and is added in suitable amounts in order to obtain the desired content of ferrite.
  • Molybdenum (Mo) is an active element, which improves the resistance to corrosion in chloride environments as well as preferably in reducing acids. Too high of a Mo content in combination with high Cr contents implies that the risk for intermetallic precipitations increases.
  • the Mo content in the present invention should lie in the range of 3.0-5.0 weight %, preferably 3.6-4.7 weight %, in particular 4.0-4.3 weight %.
  • Nitrogen (N) is a very active element, which increases the corrosion resistance, the structural stability as well as the strength of the material. Further, a high N content improves recovery of the austenite after welding, which gives good properties within the welded joint. In order to obtain a good effect of N, at least 0.28 weight % N should be added. At high contents of N, the risk for precipitation of chromium nitrides increases, especially when the chromium content is also high. Further, a high N content implies that the risk for porosity increases because of the exceeded solubility of N in the melt. For these reasons the N content should be limited to max 0.5 weight %, preferably >0.35 - 0.45 weight % N is added.
  • Boron (B) is added in order to increase the hot workability of the material. At an excessive content of boron the weldability as well as the corrosion resistance could deteriorate. Therefore, the content of boron should be limited to 0.0030 weight %.
  • S Sulfur influences the corrosion resistance negatively by forming soluble sulfides. Further, the hot workability detonates, for this reason the content of sulfur is limited to max 0.010 weight %.
  • Co Co
  • Co is added primarily in order to improve the structural stability as well as the corrosion resistance.
  • Co is an austenite-stabilizing element.
  • the Co content should at least 0.5 weight %, preferably at least 1.5 weight %. Because cobalt is a relatively expensive element, the addition of cobalt is therefor limited to max 3.5 weight %.
  • Tungsten increases the resistance to pitting and crevice corrosion. But the addition of too much tungsten in combination with high Cr contents as well as high Mo contents, means that the risk for intermetallic precipitations increases.
  • the W content in the present invention should be 0-3.0 weight %, preferably 0.5 to 1.8 weight %.
  • Copper is added in order to improve the general corrosion resistance in acid environments such as sulfuric acid. At the same time Cu influences structural stability. However, high contents of Cu imply that the solid solubility will be exceeded. Therefor the Cu content should be limited to max 2.0 weight %, preferably 0.5 to 1.5 weight %.
  • Ruthenium is added in order to increase the corrosion resistance. Because ruthenium is a very expensive element, the content should be limited to max 0.3 weight %, preferably more than 0 and up to 0.1 weight %.
  • Aluminum (Al) and Calcium (Ca) are used as desoxidation agents at the steel production.
  • the content of Al should be limited to max 0.03 weight % in order to limit the forming of nitrides.
  • Ca has a favorable effect on the hotductility.
  • the Ca content should be limited to 0.010 weight % in order to avoid an unwanted amount of slag.
  • the content of ferrite is important in order to obtain good mechanical properties and corrosion properties as well as good weldability. From a corrosion resistance point of view and a point of view of weldability, a content of ferrite of 40-65% is desirable in order to obtain good properties. Further, high contents of ferrite imply that the impact strength at low temperatures as well as the resistance to hydrogen-induced brittleness suffers.
  • the content of ferrite is therefore 40-65 volume %, preferably 42-60 volume %, more preferably 45-55 volume %.
  • test heats according to this example were produced by casting of 170 kg ingots in the laboratory, which were hot forged to round bars. Those were hot extruded to bars (round bars as well as flat bars), where test material was taken out from the round bars. Further, the flat bars were annealed before cold rolling took place, whereafter further test material was taken out. From a materials engineering point of view, the process can be considered being representative for production on a bigger scale, for example for the production of seamless tubes by the extrusion method, followed by cold rolling. Table 1 shows the composition of the first batch of test heats. TABLE 1 Composition of test heats, weight %.
  • T max sigma was calculated with Thermo-Calc (TC version N thermodynamic database for steel TCFE99) based on characteristic amounts for all specified elements in the different variations.
  • T max sigma is the dissolving temperature for the sigma phase, where high dissolving temperatures indicate lower structural stability.
  • CPT Critical Pitting Temperature
  • the test heat 605183, alloyed with cobalt shows good structural stability at a controlled cooling rate of ( ⁇ 140° C./min) in spite of the fact that it contains high contents of chromium as well as of molybdenum, shows better results than SAF2507 and SAF2906. It appears from this investigation that a high PRE does not solely explain the CPT values.
  • the relationship or ratio of PRE austenite/PRE ferrite is of extreme importance for the properties of the higher alloyed duplex steels, and a very narrow and exact balance between the alloying elements is required in order to obtain this optimum ratio, which lies between 0.9-1.15; preferably 0.9-1.05 and simultaneously obtain PRE values of above 46.
  • the ratio PRE austenite/PRE ferrite against CPT in the modified ASTM G48C test for the test heats is given in Table 3.
  • Tensile test specimen (DR-5C50) were manufactured from extruded bars, ⁇ 20 mm, which were heat treated at temperatures according to Table 2 for 20 minutes followed by cooling down in air, or water (605195, 605197, 605184). The results of the tests are presented in Table 4 and 5. The results of the tensile test show that the contents of chromium, nitrogen and tungsten strongly influence the impact strength of the material. Besides 605153, all heats fulfill the requirement of a 25% elongation at tensile testing at room temperature (RT).
  • Table 6 shows the results from the Tungsten-Inert-Gas remelting test (henceforth-abbreviated TIG), where the heats 605193, 605183, 605184 as well as 605253 show a good structure in the heat affected zone (Heat Affected Zone, henceforth-abbreviated HAZ).
  • the Ti-containing heats show Tin in HAZ.
  • An excessive chromium and nitrogen content results in precipitation of Cr 2 N, which shall be avoided because it detonates the properties of the material.
  • test heats were produced by casting of 270 kg ingots, which were hot forged to round bars. Those were extruded to bars, wherefrom test samples were taken. Afterwards the bar was annealed before cold rolling to flat bars was executed, after that further test material was taken out. Table 7 shows the composition for these test heats.
  • Thermo-Calc-values according to Table 8 are based on characteristic amounts for all specified elements in the different variations.
  • the PRE number for the ferrite and austenite is based on their equilibrium composition at 1100° C.
  • T max sigma is the dissolving temperature for the sigma phase, where high dissolving temperatures indicate lower structural stability.
  • heats lie within the identified range of 0.9-1.15; preferably 0.9-1.05 applicable for the ratio PRE austenite/PRE ferrite at the same time as PRE in both austenite and ferrite is in excess of 44 and for most of the heats even considerably in excess of 44. Some of the heats attain a total PRE of 50. It is very interesting to note that heat 605251, alloyed with 1.5 weight % cobalt, performs almost equivalent with heat 605250, alloyed with 0.6 weight % cobalt, in “Green Death” solution in spite of the lower chromium content in heat 605251. It is particularly surprising and interesting because heat 605251 has a PRE number of ca. 48, which is in excess of some of today's commercial superduplex alloys simultaneously as the T max sigma-value below 1010° C. indicates a good structural stability based on the values in Table 2 in Example 1.
  • Control of the structure shows that the heats 605249, 605251, 605252, 605253, 605254, 605255, 605259, 605260, 605266 as well as 605267 are free from unwanted sigma phase.
  • heat 605249, alloyed with 1.5 weight % cobalt is free from sigma phase
  • heat 605250, alloyed with 0.6 weight % cobalt contains a very small amount of sigma phase. Both heats are alloyed with high contents of chromium, approximately 29.0 weight % and the molybdenum content of approximately 4.25 weight %.
  • heats 605262 and 605263 with addition of 1.0 weight % tungsten show a structure with much sigma phase, while it is interesting to note that heat 605269, also with 1.0 weight % tungsten but with higher content of nitrogen than 605262 and 605263 shows a considerable smaller amount of sigma phase. Consequently, a very good balance between the different alloying elements at these high alloying contents is required of for example chromium and molybdenum in order to obtain good structural properties.
  • Table 11 shows the results from the light optical examination after annealing at 1080° C., 20 min followed by water quenching.
  • the amount of sigma phase is specified with values from 1 to 5, where 1 represents that no sigma phase was detected in the examination, while 5 represents that a very high content of sigma phase was detected in the examination.
  • FIG. 4 shows the results from the hot ductility testing of the most of the heats.
  • a good workability is of course of vital importance in order to be able to produce the material into products in forms such as bars, tubes (such as welded and scarmess tubes), plate, strin. wire welding wire, constructive elements (such as flanges and couplings).
  • the heats 605249,605250, 605251, 605252, 605255, 605266 as well as 605267 show somewhat improved hot ductility values.
  • the material should one or move, if not all of the following:
  • PRE number in ferrite should exceed 45, but preferably be at least 47;
  • PRE number in austenite should exceed 45, but preferably be at least 47;
  • PRE number for the entire alloy should preferably be at least 46;
  • Relationship PRE austenite/PRE ferrite should be 0.9-1.15; preferably 0.9-1.05;
  • the content of ferrite should lie in the range preferably 45-55 volume %;
  • T max sigma should not exceed 1010° C.
  • the content of nitrogen should 0.28-0.5 weight %, preferably 0.35-0.48 weight %, more preferably 0.38-0.40 weight %;
  • the content of cobalt should lie in the range 0-3,5 weight %, preferably 1.0-2.0 weight %, but preferably 1.3-1.7 weight %.
  • the alloy In order to ensure the high nitrogen solubility, i.e. if the content of nitrogen is in the range 0.38-0.40 weight %, should the alloy have at least 29 weight % Cr, as well as at least 3.0 weight % Mo, thus the total content of the elements Cr, Mo and N fulfills the requirements of the PRE number.
  • the oil refining process is very complex and consists of a lot of steps, where non-hydrocarbons such as inorganic chlorides can cause extensive corrosion problems.
  • Crude oil contains different kinds of salts, such as Na, Mg and Ca chlorides.
  • the inorganic MgCl 2 and CaCl 2 are the most critical, because hydrolysis during heating generates hydrochloric acid (HCl).
  • HCl hydrochloric acid
  • the hydrochloric acid can condense on the materials used in the overhead condensers in the refining plant.
  • the forming of HCl could cause serious corrosion problems, especially in combination with the occurrence of solid salts on the surfaces of the materials, which also appear frequently.
  • the corrosion problems in the overhead condensers in the refining plant are in addition to general corrosion, pitting corrosion to crevice corrosion.
  • cooling water rather than the process fluid that cause corrosion problems.
  • the chloride content of the cooling water can vary from zero in de-ionized water up to approximately 1.5% in seawater.
  • EDC ethylene dichloride
  • VMC vinyl chloride monomer
  • Hydro metallurgy means production of metals from aqueous solution by leaching, solution reclaiming process, precipitation of metals and refining. Also in these processes, a high resistance to local corrosion from chlorides in combination with oxidizing metal ions, which are included in the slurry (mixture of the crushed oxide and processing water), and also the resistance to general corrosion from acids occurring in leaching processes and erosion corrosion.
  • Examples for such processes are leaching of nickel and cobalt from laterit ore at high temperatures and high pressure, especially under the preheating step before autoclaves where the acid leaching takes place.

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US10/232,727 2001-09-02 2002-09-03 Use of a duplex stainless steel alloy Abandoned US20030133823A1 (en)

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SE0102932-1 2001-09-02
SE0102932A SE524951C2 (sv) 2001-09-02 2001-09-02 Användning av en duplex rostfri stållegering

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KR (1) KR20040029141A (sv)
CN (1) CN100540713C (sv)
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Cited By (9)

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US20030086808A1 (en) * 2001-09-02 2003-05-08 Ann Sundstrom Duplex stainless steel alloy
US20060191605A1 (en) * 2003-06-30 2006-08-31 Kazuhiro Ogawa Duplex stainless steel
US20060196582A1 (en) * 2003-03-02 2006-09-07 Anders Lindh Duplex stainless steel alloy and use thereof
US20070089810A1 (en) * 2003-03-02 2007-04-26 Sandvik Intellectual Property Ab Duplex stainless steel alloy for use in seawater applications
US20090032246A1 (en) * 2007-03-26 2009-02-05 Hideki Takabe Oil country tubular good for expansion in well and duplex stainless steel used for oil country tubular good for expansion
US20100084121A1 (en) * 2006-12-14 2010-04-08 Sandvik Intellectual Property Ab Plate
EP2215421A1 (en) * 2007-10-26 2010-08-11 Sandvik Intellectual Property Ab Use of a duplex stainless steel in a phosphoric acid production system
CN104822487A (zh) * 2012-11-28 2015-08-05 山特维克知识产权股份有限公司 用于焊覆的焊接材料
EP4310214A4 (en) * 2021-03-15 2024-09-04 Nippon Steel Stainless Steel Corp DUPLEX STAINLESS STEEL

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SE528782C2 (sv) * 2004-11-04 2007-02-13 Sandvik Intellectual Property Duplext rostfritt stål med hög sträckgräns, artiklar och användning av stålet
US7807028B2 (en) 2005-03-09 2010-10-05 Xstrata Queensland Limited Stainless steel electrolytic plates
SE530711C2 (sv) * 2006-10-30 2008-08-19 Sandvik Intellectual Property Duplex rostfri stållegering samt användning av denna legering
JP2008179844A (ja) * 2007-01-23 2008-08-07 Yamaha Marine Co Ltd 二相ステンレス鋼及び二相ステンレス鋼製鋳造品
CN101684541B (zh) * 2008-09-24 2012-08-08 张家港市飞浪泵阀有限公司 用在泵阀产品上的双相不锈钢
CN102011067A (zh) * 2010-12-14 2011-04-13 江苏大学 一种耐空泡腐蚀双相不锈钢
CA2828195C (en) 2011-03-10 2016-10-11 Nippon Steel & Sumitomo Metal Corporation Duplex stainless steel
FI125854B (sv) * 2011-11-04 2016-03-15 Outokumpu Oy Duplex rostfritt stål
US9783876B2 (en) * 2012-03-26 2017-10-10 Nippon Steel & Sumitomo Metal Corporation Stainless steel for oil wells and stainless steel pipe for oil wells
CN104919072B (zh) * 2013-01-15 2017-07-14 株式会社神户制钢所 双相不锈钢钢材和双相不锈钢钢管
US10793930B2 (en) 2016-02-17 2020-10-06 Nippon Steel & Sumikin Stainless Steel Corporation Ferritic-austenitic two-phase stainless steel material and method for manufacturing same
CN106591735B (zh) * 2016-12-05 2019-04-12 四川六合锻造股份有限公司 一种超级双相不锈钢及其制备方法
EP3559295B1 (en) * 2016-12-21 2021-04-28 Sandvik Intellectual Property AB An object comprising a duplex stainless steel and the use thereof

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ATE336605T1 (de) 2006-09-15

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