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US20100316522A1 - Duplex stainless steel alloy and use of this alloy - Google Patents

Duplex stainless steel alloy and use of this alloy Download PDF

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Publication number
US20100316522A1
US20100316522A1 US12/447,689 US44768907A US2010316522A1 US 20100316522 A1 US20100316522 A1 US 20100316522A1 US 44768907 A US44768907 A US 44768907A US 2010316522 A1 US2010316522 A1 US 2010316522A1
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weight
content
alloy according
alloy
ferrite
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Kenneth Göransson
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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
    • C22C38/18—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

Definitions

  • the present invention relates to a duplex stainless steel alloy, which is a steel alloy having a ferritic-austenitic matrix and especially high resistance to corrosion in combination with good structural stability and hotworkability.
  • the ferrite content is 30-70 volume-% and such steel alloys have a well balanced composition, which imparts the material corrosion properties, which make it suitable for use in for instance chloride-containing environments, such as in the sea.
  • the elements Cu and W have shown to be efficient alloying additions for further optimization of the steel's corrosion properties in chloride environments.
  • the element W has by then been used as substitute for a portion of Mo, as for example in the commercial alloy DP3W (UNS S39274) or Zeron100, which contain 2.0% respectively 0.7% W.
  • the latter contains even 0.7% Cu with the purpose to increase the corrosion resistance of the alloy in acid environments.
  • the above-described steel grades have a PRE/PREW-number, irrespective method of calculation, which lies above 40.
  • EP 0 683 241 discloses a duplex stainless steel alloy having a composition resulting in improved properties with respect to resistance to both stress corrosion cracking and pitting in chlorideion-containing environments than most other duplex stainless steel alloys known.
  • this alloy as well as the alloys discussed above is highly susceptible to intermetallic precipitation, especially sigma phase precipitation, which makes the material hard and brittle. Accordingly, the production of a material with good ductility by use of the duplex stainless steel alloy according to EP 0 683 241 is made very difficult.
  • the object of the present invention is to provide a duplex stainless steel alloy of the type defined above and especially in the European patent 0 683 241, which has improved properties, especially ductility and toughness, with respect to such an alloy already known while maintaining at least similar levels of corrosion resistance as such an alloy.
  • the alloy should have a good hotworkability.
  • This object is according to the invention obtained by providing a duplex stainless steel alloy, which contains in weight-%: C max 0.03%, Si ⁇ 0.30%, Mn 0-3.0%, P max 0.030%, S max 0.050%, Cr 25-29%, Ni 5-9%, Mo 4.5-8%, W 0-3%, Cu 0-2%, Co 0-3%, Ti 0-2%, Al 0-0.05%, B 0-0.01%, Ca 0-0.01%, and N 0.35-0.60%, balance Fe and normal occurring impurities, wherein the ferrite content is 30-70 volume-%, and wherein each weight-% of Mo above may optionally be replaced by two (2) weight-% W.
  • a duplex stainless steel alloy with this composition has especially an increased ductility and toughness with respect to the alloy according to EP 0 683 241, and it has also an increased corrosion resistance.
  • Si content By reducing the Si content to be below 0.30 weight-% a significant reduction in sigma phase precipitation is achieved, which is the key to the increased ductility and toughness of the steel alloy according to the invention.
  • Mo when using a comparatively high content of Mo it is highly efficient to reduce the content of Si for reducing the risk for intermetallic precipitations.
  • the content of Si is max 0.25 weight-%, which makes the steel alloy even less prone to sigma-formation for increasing the ductility and toughness of the material. It is expected that the same would be valid if Molybdenum would be partly or entirely replaced by Tungsten.
  • the content of Si is max 0.23 weight-%.
  • the content of Mo is a weight-% and the content of W is b weight-%, wherein a+b/2>5.0.
  • a high content of Mo and/or W results in excellent resistance to corrosion, especially pitting- and crevice corrosion, but the increased risk for intermetallic precipitations with such high contents of these elements is efficiently counteracted by the combination thereof with the low content of Si.
  • a>5.0 It is pointed out that claim 1 is to be interpreted as when starting from the content intervals of Mo (4.5-8%) and W (0-3%) it is possible to replace each % of Mo by 2% of W or conversely, so that the content of Mo may for example be 3% when the content of W is at least 3%.
  • a+b/28 i.e. the total content of Mo and W does not exceed 8%, for keeping the costs thereof at a reasonable level.
  • b 0, i.e. the alloy contains only Mo.
  • the content of Co is 0-0.010 weight.-%.
  • Co is an expensive material, and it has been found that the structure's ability as well as the corrosion resistance improvement influence thereof is not an essential factor in a steel alloy with a composition according to the present invention.
  • the content of ferrite is 40-60 volume-%.
  • the PRE- or PREW-value for both the ferrite and austenite phase may be higher than 47, preferably higher than 48.5, and said average PRE- or PREW-value may be higher than 48, preferably higher than 49. It has turned out that the pitting and crevice corrosion resistance in the steel alloy according to the invention is especially increased by increasing the PRE- or PREW-value of the phase with the lowest such value. It has been found that the steel alloy according to the invention will still have a good hotworkability with a PRE- or PREW-value higher than 49.
  • the ratio between PRE(W)-value for the austenite phase and PRE(W)-value for the ferrite phase lies between 0.90 and 1.15, preferably between 0.95 and 1.05.
  • An alloy according to the present invention is suitable to be used in chloride-containing environments in product forms such as bars, tubes, such as welded and seamless tubes, plate, strip, wire, welding wire, constructive parts, such as for example pump, valves, flanges and couplings.
  • FIG. 1 shows a calculated phase content of a duplex stainless steel alloy according to an embodiment of the invention as a function of temperature
  • FIG. 2 is a graph similar to FIG. 1 for a reference steel alloy according to EP 0 683 241, and
  • FIG. 3 is a micrograph of continuously cooled samples of the alloys according to FIG. 1 and FIG. 2 according to three different cooling speeds.
  • the alloy according to the invention contains (in weight-%):
  • 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 it increases the flowability during production and welding.
  • too high contents of Si lead to precipitation of unwanted intermetallic phase, wherefore the content is limited to below 0.30 weight-%, preferably max 0.25 weight-%, more preferably max 0.23 weight-%.
  • 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 found other elements 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-%.
  • Phosphorus (P) is a common impurity element. If present in amounts greater than approximately 0.05%, it can result in adverse effects on e.g. hot ductility, weldability and corrosion resistance. The amount of P in the alloy should therefore not exceed 0.05%.
  • S Sulfur influences the corrosion resistance negatively by forming soluble sulfides. Furthermore, the hotworkability deteriorates, for what reason the content of sulfur is limited to max 0.030 weight-%, preferably less than 0.010 weight-%.
  • Chromium (Cr) is a much 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 25 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 29 weight-%, preferably 25.5-28 weight-%.
  • Nickel is used as austenite stabilizing element and is added in suitable contents in order to obtain the desired content of ferrite.
  • an addition of 5-9 weight-% nickel is required, and it is preferably 6-8 weight-%.
  • Molybdenum (Mo) is an active element which improves the resistance to corrosion in chloride environments as well as preferably in reducing acids. A too high 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 4.5-8 weight-%, preferably above 5.0 weight-%, in which each weight-% of Mo may optionally be replaced by 2 weight-% W.
  • Tungsten increases the resistance to pitting- and crevice corrosion. But the addition of too high contents of tungsten in combination with that the Cr-contents as well as Mo-contents are high, means that the risk for intermetallic precipitations increases.
  • the W-content in the present invention should lie in the range of 0-3.0 weight-%.
  • Copper (Cu) may be added in order to improve the general corrosion resistance in acid environments such as sulfuric acid. At the same time Cu influences the structural stability. However, thigh contents of Cu imply that the solid solubility will be exceeded. Therefore the Cu-content should be limited to max 2.0 weight-%, preferably between 0 and 1.5 weight-%, more preferred 0.1-0.5 weight-%.
  • Co Co has properties that are intermediate between those of iron and nickel. Therefore, a minor replacement of these elements with Co, or the use of Co-containing raw materials (Ni scrap metal usually contains some Co, in some cases in quantities greater than 10%) will not result in any major change in properties.
  • Co can be used to replace some Ni as an austenite-stabilizing element.
  • Co is a relatively expensive element, so the addition of Co is limited to be within the range of 0-3 weight-%.
  • Titanium (Ti) has a high affinity for N. It can therefore be used e.g. to increase the solubility of N in the melt and to avoid the formation of nitrogen bubbles during casting.
  • excessive amounts of Ti in the material causes precipitation of nitrides during casting, which can disrupt the casting process and the formed nitrides can act as defects causing reduction in corrosion resistance, toughness and ductility. Therefore, the addition of Ti is limited to 2 weight-%.
  • Aluminium (AI) and Calcium (Ca) are used as desoxidation agents at the steel production.
  • the content of Al should be limited to max 0.05 weight-%, preferably max 0.03%, in order to limit the forming of nitrides.
  • Ca has a favourable effect on the hotductility.
  • the Ca-content should be limited to max 0.010 weight-% in order to avoid an unwanted amount of slag.
  • Boron (B) may be added in order to increase the hotworkability of the material. At a too high content of Boron the weldability as well as the corrosion resistance could deteriorate. Therefore, the content of boron should be limited to max 0.01 weight-%.
  • N Nitrogen
  • N is a very active element, which increases the corrosion resistance, the structural stability as well as the strength of the material. Furthermore, a high N-content improves the recovering of the austenite after welding, which gives good properties within the welded joint. In order to obtain a good effect of N, at least 0.35 weight-% N should be added. At high contents of N the risk for precipitation of chromium nitrides increases, especially when simultaneously the chromium content is high. Furthermore, a high N-content implies that the risk for porosity increases because of the exceeded solubility of N in the smelt. For these reasons the N-content should be limited to max 0.60 weight-%, preferably >0.35-0.45 weight-% N is added.
  • the content of ferrite is important in order to obtain good mechanical properties and corrosion properties as well as good weldability. From a corrosion point of view and a point of view of weldability a content of ferrite between 30-70% is desirable in order to obtain good properties. Furthermore, high contents of ferrite imply that the impact strength at low temperatures as well as the resistance to hydrogen-induced brittleness risks deteriorating. The content of ferrite is therefore 30-70 volume-%, preferably 40-60 volume-%.
  • Table 1 shows the content of the two alloys No. 1 and No. 2, in which No. 1 is a duplex stainless steel alloy according to an embodiment of the present invention and alloy No. 2 is such an alloy according to EP 0683241.
  • FIGS. 1 and 2 show the calculated phase contents of alloy No. 1 and alloy No. 2, respectively, as a function of the temperature.
  • CCTSS database TCFE3 with improved models for e.g. duplex alloy compositions.
  • Table 2 above shows the total PRE of the two alloys and the predicted PRE for each phase when quenched from 1100° C., as well as the ratio between PRE in the austenite and in the ferrite. It also shows the predicted ferrite content after a quench from 1100° C. and finally the predicted dissolution temperatures for Cr 2 N and sigma ( ⁇ ) phase, and the predicted presence of any precipitates at 1100° C. Since the precipitation of Cr 2 N is more rapid than that of a phase, two T max , Cr 2 N are presented, one for the case for slow cooling when equilibrium amounts of ⁇ are allowed to precipitate (“with ⁇ ”) and another for rapid cooling when a does not precipitate (“without s”). It is clear that both alloys fulfil the requirements on ferrite content, total PRE as well as PRE balance and minimum PRE in each phase as stated in our WO 03020994.
  • the alloys were produced by melting, casting of ingots and finally press forging.
  • Table 3 shows the results of the forging.
  • the forging was interrupted when severe surface defects began to form, and the total reduction of cross-sectional area during the forging process can thus be used as an estimate of the forgeability of the two alloys.
  • the forged bars were annealed at 1100° C., followed by quenching in water before any further processing was begun.
  • the prematerial used for samples was annealed once more, after sectioning into smaller pieces, at 1100° C. for 1 h, followed by water quench. After this treatment, the different samples were machined.
  • Impact testing was performed on 10 ⁇ 10 mm Charpy v-notch samples (55 mm long) in four different materials conditions: asannealed (i.e. 1100° C./water quench) and with an additional anneal of the impact samples at a lower temperature. Table 4 shows the different materials conditions as well as the resulting impact toughness values. Two samples were tested for each composition and annealing condition.
  • Alloy 1 with a high Mo content and low Si and Co contents has a good impact toughness provided a sufficiently high annealing temperature is used.
  • This Table illustrates a weakness of the alloy 2 according to EP 0 683 241, namely that a Si content higher than 0.5% together with a high Mo content gives a potentially brittle material. Just reducing the Si content (as in the alloy 1 according to the present invention) gives a large improvement in toughness.
  • alloy 1 is slightly less prone to a precipitation than alloy 2. It is pointed out that a “note” of 2, preferably 1, is necessary for making it possible to properly manufacture the material in question.
  • FIG. 3 shows micrographs of the continuously cooled samples heated to 1100° C. Light colour is austenite, brown is ferrite and blackish is ⁇ -phase. It is shown that the formation of ⁇ -phase (blackish) is remarkably weaker for alloy No. 1 according to the present invention than for alloy No. 2 according to EP 0 683 241, which is obviously due to the lower content of Si.
  • Table 6 shows results from tensile testing. Alloy No. 2 is apparently less ductile than alloy No. 1 according to the invention.
  • Critical crevice temperature (CCT) according to MTI-2 and critical pitting temperature (CPT) in “Green Death” solution (1% FeCl 3 +1% CuCl 2 +11% H 2 SO 4 +1.2% HCl) is shown in Table 7.
  • CCT Critical crevice temperature
  • CPT critical pitting temperature
  • the alloy (No. 2) corresponding to EP 0 683 241 is highly susceptible to sigma phase precipitation, which makes the production of a material with good ductility very difficult. This problem is solved by lowering the Si content and a good balance between the PRE-values of the two phases. Furthermore, the alloy No. 2 has a low forgeability. By reducing the Si content of an alloy of the type defined in EP 0 683 241, i.e. by using a composition of alloy No. 1, not only will the ductility and toughness increase, the corrosion resistance is increased as well, which in fact is an effect that was quite unexpected.

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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)
US12/447,689 2006-10-30 2007-10-02 Duplex stainless steel alloy and use of this alloy Abandoned US20100316522A1 (en)

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Application Number Priority Date Filing Date Title
SE0602287A SE530711C2 (sv) 2006-10-30 2006-10-30 Duplex rostfri stållegering samt användning av denna legering
SE0602287-5 2006-10-30
PCT/SE2007/050694 WO2008054300A1 (en) 2006-10-30 2007-10-02 Duplex stainless steel alloy and use of this alloy

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US (1) US20100316522A1 (es)
EP (1) EP2082073A4 (es)
JP (1) JP2010508439A (es)
KR (1) KR20090078813A (es)
CN (1) CN101558180A (es)
BR (1) BRPI0717944A2 (es)
CA (1) CA2667436A1 (es)
EA (1) EA014812B1 (es)
MX (1) MX2009004535A (es)
SE (1) SE530711C2 (es)
UA (1) UA93587C2 (es)
WO (1) WO2008054300A1 (es)

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CN109898015A (zh) * 2019-02-01 2019-06-18 上海加宁新材料科技有限公司 舰船用耐海水腐蚀hdr双相不锈钢的制造方法
US20190300980A1 (en) * 2016-02-17 2019-10-03 Nippon Steel & Sumikin Stainless Steel Corporation Ferritic-austenitic two-phase stainless steel material and method for manufacturing same
EP3712289A4 (en) * 2017-11-15 2021-03-10 Nippon Steel Corporation TWO-PHASE STAINLESS STEEL AND METHOD FOR MANUFACTURING TWO-PHASE STAINLESS STEEL
EP4310214A4 (en) * 2021-03-15 2024-09-04 NIPPON STEEL Stainless Steel Corporation DUPLEX STAINLESS STEEL

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US20110160838A1 (en) * 2009-12-31 2011-06-30 Blanzy Jeffrey S Endoprosthesis containing multi-phase ferrous steel
SE534779C2 (sv) 2010-03-03 2011-12-20 Sandvik Intellectual Property Metod för att tillverka en trådprodukt av rostfritt stål
CN104357763B (zh) * 2014-11-15 2016-07-06 柳州市潮林机械有限公司 一种双相不锈钢管材
CN104451455A (zh) * 2014-11-15 2015-03-25 柳州市潮林机械有限公司 一种双相不锈钢管材
CN104357765B (zh) * 2014-11-15 2016-07-06 柳州市潮林机械有限公司 一种双相不锈钢管材
CN104357764B (zh) * 2014-11-15 2016-06-08 柳州市潮林机械有限公司 一种双相不锈钢管材
CN104357762B (zh) * 2014-11-15 2016-06-08 柳州市潮林机械有限公司 一种双相不锈钢管材
KR101641796B1 (ko) * 2014-12-26 2016-07-22 주식회사 포스코 드로잉성이 우수한 린 듀플렉스 스테인리스강 및 그 제조방법
CN106011689B (zh) * 2015-03-30 2019-05-03 新日铁住金不锈钢株式会社 含臭氧水用双相不锈钢
US20190376156A1 (en) * 2016-12-21 2019-12-12 Sandvik Intellectual Property Ab Use of a duplex stainless steel object
JP6791012B2 (ja) * 2017-05-24 2020-11-25 Ｊｆｅスチール株式会社 耐食性及び耐水素脆性に優れた二相ステンレス鋼
CN108048755B (zh) * 2017-11-10 2019-06-28 洛阳双瑞特种装备有限公司 一种用于流体输送的高硬度耐蚀铸造不锈钢
KR102885372B1 (ko) * 2023-09-14 2025-11-11 부산대학교 산학협력단 페라이트상의 분율이 70 % 이상인 슈퍼 듀플렉스 스테인리스강 및 이의 제조 방법, 니켈 도금된 슈퍼 듀플렉스 스테인리스강 및 이의 제조 방법

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US6048413A (en) * 1994-05-21 2000-04-11 Park; Yong Soo Duplex stainless steel with high corrosion resistance
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190300980A1 (en) * 2016-02-17 2019-10-03 Nippon Steel & Sumikin Stainless Steel Corporation Ferritic-austenitic two-phase stainless steel material and method for manufacturing same
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
EP3712289A4 (en) * 2017-11-15 2021-03-10 Nippon Steel Corporation TWO-PHASE STAINLESS STEEL AND METHOD FOR MANUFACTURING TWO-PHASE STAINLESS STEEL
CN109898015A (zh) * 2019-02-01 2019-06-18 上海加宁新材料科技有限公司 舰船用耐海水腐蚀hdr双相不锈钢的制造方法
EP4310214A4 (en) * 2021-03-15 2024-09-04 NIPPON STEEL Stainless Steel Corporation DUPLEX STAINLESS STEEL

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CA2667436A1 (en) 2008-05-08
EA014812B1 (ru) 2011-02-28
JP2010508439A (ja) 2010-03-18
WO2008054300A9 (en) 2009-06-11
MX2009004535A (es) 2009-05-20
SE0602287L (sv) 2008-05-01
UA93587C2 (ru) 2011-02-25
EP2082073A4 (en) 2011-06-29
EA200970433A1 (ru) 2009-10-30
CN101558180A (zh) 2009-10-14
KR20090078813A (ko) 2009-07-20
BRPI0717944A2 (pt) 2013-12-03
EP2082073A1 (en) 2009-07-29
WO2008054300A1 (en) 2008-05-08
SE530711C2 (sv) 2008-08-19

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