WO2013151992A1 - Cost-effective ferritic stainless steel - Google Patents

Cost-effective ferritic stainless steel Download PDF

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Publication number
WO2013151992A1
WO2013151992A1 PCT/US2013/034940 US2013034940W WO2013151992A1 WO 2013151992 A1 WO2013151992 A1 WO 2013151992A1 US 2013034940 W US2013034940 W US 2013034940W WO 2013151992 A1 WO2013151992 A1 WO 2013151992A1
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WO
WIPO (PCT)
Prior art keywords
percent
weight
stainless steel
ferritic stainless
titanium
Prior art date
Application number
PCT/US2013/034940
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English (en)
French (fr)
Inventor
Joseph A. DOUTHETT
Shannon K. CRAYCRAFT
Original Assignee
Ak Steel Properties, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to UAA201410374A priority Critical patent/UA111115C2/uk
Priority to KR1020177013474A priority patent/KR101821170B1/ko
Priority to KR1020147030826A priority patent/KR20150003255A/ko
Priority to SI201330592A priority patent/SI2834381T1/sl
Priority to MX2014011875A priority patent/MX358188B/es
Priority to RU2014138182/02A priority patent/RU2598739C2/ru
Priority to RS20170341A priority patent/RS55821B1/sr
Priority to CN201380018563.7A priority patent/CN104245990A/zh
Application filed by Ak Steel Properties, Inc. filed Critical Ak Steel Properties, Inc.
Priority to HRP20170298TT priority patent/HRP20170298T1/hr
Priority to AU2013243635A priority patent/AU2013243635B2/en
Priority to JP2015504675A priority patent/JP6113827B2/ja
Priority to ES13716682.3T priority patent/ES2620428T3/es
Priority to EP13716682.3A priority patent/EP2834381B1/en
Priority to CA2868278A priority patent/CA2868278C/en
Priority to IN8452DEN2014 priority patent/IN2014DN08452A/en
Publication of WO2013151992A1 publication Critical patent/WO2013151992A1/en
Priority to ZA2014/07915A priority patent/ZA201407915B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • 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
    • C22C38/48—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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium

Definitions

  • ASTM Type 304 stainless steel comparable to that of ASTM Type 304 stainless steel but that is substantially nickel-free, dual stabilized with titanium and columbium to provide protection from intergranular corrosion, and contains chromium, copper, and molybdenum to provide pitting resistance without sacrificing stress corrosion cracking resistance.
  • Such a steel is particularly useful for commodity steel sheet commonly found in commercial kitchen applications, architectural components, and automotive applications, including but not limited to commercial and passenger vehicle exhaust and selective catalytic reduction (SCR) components.
  • the inter-relationship of and amount of titanium, columbium, carbon, and nitrogen are controlled to achieve subequilibrium surface quality, substantially equiaxed cast grain structure, and substantially full stabilization against intergranular corrosion.
  • the inter-relationship of chromium, copper, and molybdenum is controlled to optimize corrosion resistance.
  • Subequilibrium melts are typically defined as compositions with titanium and nitrogen levels low enough so that they do not form titanium nitrides in the alloy melt. Such precipitates can form defects, such as surface stringer defects or laminations, during hot or cold rolling. Such defects can diminish formability, corrosion resistance, and appearance.
  • Fig. 1 was derived from an exemplary phase diagram, created using thermodynamic modeling for elements of titanium and nitrogen at the liquidus temperature for an embodiment of the ferritic stainless steel. To be substantially free of titanium nitrides and be considered subequilibrium, the titanium and nitrogen levels in the ferritic stainless steel should fall to the left or lower portion of the solubility curve shown in Fig. 1.
  • the titanium nitride solubility curve, as shown in Fig. 1 can be represented mathematically as follows:
  • Equation 1 Using Equation 1, if the nitrogen level is maintained at or below 0.020% in an embodiment, then the titanium concentration for that embodiment should be maintained at or below 0.25%. Allowing the titanium concentration to exceed 0.25% can lead to the formation of titanium nitride precipitates in the molten alloy. However, Fig. 1 also shows that titanium levels above 0.25% can be tolerated if the nitrogen levels are less than 0.02%.
  • Embodiments of the ferritic stainless steels exhibit an equiaxed cast and rolled and annealed grain structure with no large columnar grains in the slabs or banded grains in the rolled sheet. This refined grain structure can improve formability and toughness.
  • This grain structure there should be sufficient titanium , nitrogen and oxygen levels to seed the solidifying slabs and provide sites for equiaxed grains to initiate.
  • the minimum titanium and nitrogen levels are shown in Fig. 1 , and expressed by the following equation:
  • Equation 2 Using the Equation 2, if the nitrogen level is maintained at or below 0.02% in an embodiment, the minimum titanium concentration is 0.125%).
  • the parabolic curve depicted in Fig. 1 reveals an equiaxed grain structure can be achieved at nitrogen levels above 0.02% nitrogen if the total titanium concentration is reduced.
  • An equiaxed grain structure is expected with titanium and nitrogen levels to the right or above of plotted Equation 2. This relationship between subequilibrium and titanium and nitrogen levels that produced equiaxed grain structure is illustrated in Fig. 1 , in which the minimum titanium equation (Equation 2) is plotted on the liquidus phase diagram of Fig. 1. The area between the two parabolic lines is the range of titanium and nitrogen levels in the embodiments.
  • the titanium level necessary for an equiaxed grain structure and subequilibrium conditions was determined when the maximum nitrogen level was 0.02%.
  • the respective Equations 1 and 2 yielded 0.125% minimum titanium and 0.25% maximum titanium.
  • using a maximum of 0.025%) carbon and applying Equation 3 would require minimum columbium contents of 0.25% and 0.13%, respectively for the minimum and maximum titanium levels.
  • the aim for the concentration of columbium would be 0.25%.
  • the copper level between 0.40-0.80%) in a matrix consisting of about 21% Cr and 0.25%) Mo one can achieve an overall corrosion resistance that is comparable if not improved to that found in commercially available Type 304L.
  • the one exception may be in the presence of a strongly acidic reducing chloride like hydrochloric acid.
  • the copper-added alloys show improved performance in sulfuric acid.
  • the optimal Cr, Mo, and Cu level, in weight percent satisfies the following two equations:
  • Equation 4 20.5 ⁇ Cr + 3.3Mo
  • Equation 5 0.6 ⁇ Cu+Mo ⁇ 1.4 when Cu max ⁇ 0.80
  • Embodiments of the ferritic stainless steel can contain carbon in amounts of about
  • Embodiments of the ferritic stainless steel can contain manganese in amounts of about 0.40 or less percent by weight.
  • Embodiments of the ferritic stainless steel can contain phosphorus in amounts of about 0.030 or less percent by weight.
  • Embodiments of the ferritic stainless steel can contain sulfur in amounts of about
  • Embodiments of the ferritic stainless steel can contain silicon in amounts of about
  • Some embodiments can contain about 0.40% silicon.
  • Embodiments of the ferritic stainless steel can contain chromium in amounts of about 20.0 - 23.0 percent by weight. Some embodiments can contain about 21.5— 22 percent by weight chromium, and some embodiments can contain about 21.75% chromium.
  • Embodiments of the ferritic stainless steel can contain nickel in amounts of about
  • Embodiments of the ferritic stainless steel can contain nitrogen in amounts of about 0.020 or less percent by weight.
  • Embodiments of the ferritic stainless steel can contain copper in amounts of about
  • Some embodiments can contain about 0.45 - 0.75 percent by weight copper and some embodiments can contain about 0.60 % copper.
  • Embodiments of the ferritic stainless steel can contain molybdenum in amounts of about 0.20 - 0.60 percent by weight. Some embodiments can contain about 0.30 - 0.5 percent by weight molybdenum, and some embodiments can contain about 0.40% molybdenum.
  • Embodiments of the ferritic stainless steel can contain titanium in amounts of about 0.10 - 0.25 percent by weight. Some embodiments can contain about 0.17— 0.25 percent by weight titanium, and some embodiments can contain about 0.21 % titanium.
  • Embodiments of the ferritic stainless steel can contain columbium in amounts of about 0.20 - 0.30 percent by weight. Some embodiments can contain about 0.25% columbium.
  • Embodiments of the ferritic stainless steel can contain aluminum in amounts of about 0.010 or less percent by weight.
  • ferritic stainless steels are produced using process conditions known in the art for use in manufacturing ferritic stainless steels, such as the processes described in U.S. Patent Nos. 6,855,213 and 5,868,875.
  • the ferritic stainless steels may also include other elements known in the art of steelmaking that can be made either as deliberate additions or present as residual elements, i.e., impurities from steelmaking process.
  • a ferrous melt for the ferritic stainless steel is provided in a melting furnace such as an electric arc furnace.
  • This ferrous melt may be formed in the melting furnace from solid iron bearing scrap, carbon steel scrap, stainless steel scrap, solid iron containing materials including iron oxides, iron carbide, direct reduced iron, hot briquetted iron, or the melt may be produced upstream of the melting furnace in a blast furnace or any other iron smelting unit capable of providing a ferrous melt.
  • the ferrous melt then will be refined in the melting furnace or transferred to a refining vessel such as an argon-oxygen-decarburization vessel or a vacuum- oxygen-decarburization vessel, followed by a trim station such as a ladle metallurgy furnace or a wire feed station.
  • the steel is cast from a melt containing sufficient titanium and nitrogen but a controlled amount of aluminum for forming small titanium oxide inclusions to provide the necessary nuclei for forming the as-cast equiaxed grain structure so that an annealed sheet produced from this steel also has enhanced ridging characteristics.
  • titanium is added to the melt for deoxidation prior to
  • titanium and nitrogen can be present in the melt prior to casting so that the ratio of the product of titanium and nitrogen divided by residual aluminum is at least about 0.14.
  • required for deoxidation can be added for combining with carbon and nitrogen in the melt but preferably less than that required for saturation with nitrogen, i.e., in a sub-equilibrium amount, thereby avoiding or at least minimizing precipitation of large titanium nitride inclusions before solidification.
  • the cast steel is hot processed into a sheet.
  • sheet is meant to include continuous strip or cut lengths formed from continuous strip and the term “hot processed” means the as-cast steel will be reheated, if necessary, and then reduced to a predetermined thickness such as by hot rolling. If hot rolled, a steel slab is reheated to 2000° to 2350°F (1093°-1288°C), hot rolled using a finishing temperature of 1500 - 1800°F (816 - 982°C) and coiled at a temperature of 1000 - 1400°F (538 - 760°C).
  • the hot rolled sheet is also known as the "hot band.”
  • the hot band may be annealed at a peak metal temperature of 1700 - 2100°F (926 - 1 149°C).
  • the hot band may be descaled and cold reduced at least 40% to a desired final sheet thickness.
  • the hot band may be descaled and cold reduced at least 50% to a desired final sheet thickness. Thereafter, the cold reduced sheet can be final annealed at a peak metal temperature of 1700 - 2100°F (927-1149°C).
  • the ferritic stainless steel can be produced from a hot processed sheet made by a number of methods.
  • the sheet can be produced from slabs formed from ingots or continuous cast slabs of 50-200 mm thickness which are reheated to 2000° to 2350°F (1093°-1288°C) followed by hot rolling to provide a starting hot processed sheet of 1 - 7 mm thickness or the sheet can be hot processed from strip continuously cast into thicknesses of 2 - 26 mm.
  • the present process is applicable to sheet produced by methods wherein continuous cast slabs or slabs produced from ingots are fed directly to a hot rolling mill with or without significant reheating, or ingots hot reduced into slabs of sufficient temperature to be hot rolled in to sheet with or without further reheating.
  • the level of copper in the 21 Cr + residual Mo melt chemistry did appear to have an "optimal" level in that adding 1% Cu resulted in diminished return. This confirms the behavior observed in the ferric chloride pitting test. Additional melt chemistries were submitted for vacuum melting in hopes to create cleaner steel specimens and determine the optimal copper addition in order to achieve the best overall corrosion resistance.
  • the cold reduced material had a final anneal at 1825F (996°C) followed by a final descale.
  • Electrochemical evaluations including corrosion behavior diagrams (CBD) and cyclic polarization studies were performed and compared to the behavior of Type 304L steel.
  • the anodic nose represents the electrochemical dissolution that takes place at the surface of the material prior to reaching a passive state.
  • an addition of at least 0.25% molybdenum and a minimum of approximately 0.40% copper reduce the current density during anodic dissolution to below the measured value for Type 304L steel.
  • the maximum copper addition that allows the anodic current density to remain below that measured for Type 304L steel falls approximately around 0.85%, as shown by the graph of the line identified as Fe21CrXCu.25Mo in Fig. 4.
  • Examples 2 and commercially available Type 304L steel in 3.5% sodium chloride solution show the anodic behavior of the ferritic stainless steel through active anodic dissolution, a region of passivity, a region of transpassive behavior and the breakdown of passivity. Additionally the reverse of these polarization scans identifies the repassivation potential.
  • the breakdown potential exhibited in the above mentioned cyclic polarization scans was documented as shown in Fig. 5 and Fig. 6, and evaluated to measure the effects of copper additions, if any.
  • the breakdown potential was determined to be the potential at which current begins to consistently flow through the broken passive layer and active pit imitation is taking place.
  • Example 2 it showed that a chromium level of 21% and a small molybdenum addition can maximize the repassivation reaction.
  • the relationship of copper to the repassivation potential appeared to become detrimental as the copper level increased, as shown by the graph of the line identified as Fe21CrXCu.25Mo in Fig. 7 and Fig. 8.
  • the investigated chemistries of Examples 2 were able to achieve a repassivation potential that was higher than Type 304L steel, as shown by Fig. 7 and Fig. 8.
  • a ferritic stainless steel of the composition set forth below in Table 4 (ID 92, Example 2) was compared to Type 304L steel with the composition set forth Table 4:
  • Example 2 exhibits more electrochemical resistance, higher breakdown potential, and higher repassivation potential than the comparative Type 304L steel, as shown in Fig. 9 and Fig. 10. It will be understood various modifications may be made to this invention without departing from the spirit and scope of it. Therefore, the limits of this invention should be determined from the appended claims.

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  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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PCT/US2013/034940 2012-04-02 2013-04-02 Cost-effective ferritic stainless steel WO2013151992A1 (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
UAA201410374A UA111115C2 (uk) 2012-04-02 2013-02-04 Рентабельна феритна нержавіюча сталь
HRP20170298TT HRP20170298T1 (hr) 2012-04-02 2013-04-02 Ekonomični feritni nehrđajući čelik
SI201330592A SI2834381T1 (sl) 2012-04-02 2013-04-02 Stroškovno ugodno feritno nerjavno jeklo
MX2014011875A MX358188B (es) 2012-04-02 2013-04-02 Acero inoxidable ferritico rentable.
RU2014138182/02A RU2598739C2 (ru) 2012-04-02 2013-04-02 Экономичная ферритная нержавеющая сталь
RS20170341A RS55821B1 (sr) 2012-04-02 2013-04-02 Isplativ feritni nerđajući čelik
CN201380018563.7A CN104245990A (zh) 2012-04-02 2013-04-02 成本效益的铁素体不锈钢
KR1020177013474A KR101821170B1 (ko) 2012-04-02 2013-04-02 비용-효과적인 페라이트계 스테인리스강
JP2015504675A JP6113827B2 (ja) 2012-04-02 2013-04-02 費用対効果が高いフェライト系ステンレス鋼
KR1020147030826A KR20150003255A (ko) 2012-04-02 2013-04-02 비용-효과적인 페라이트계 스테인리스강
AU2013243635A AU2013243635B2 (en) 2012-04-02 2013-04-02 Cost-effective ferritic stainless steel
ES13716682.3T ES2620428T3 (es) 2012-04-02 2013-04-02 Acero inoxidable ferrítico económico
EP13716682.3A EP2834381B1 (en) 2012-04-02 2013-04-02 Cost-effective ferritic stainless steel
CA2868278A CA2868278C (en) 2012-04-02 2013-04-02 Cost-effective ferritic stainless steel
IN8452DEN2014 IN2014DN08452A (forum.php) 2012-04-02 2013-04-02
ZA2014/07915A ZA201407915B (en) 2012-04-02 2014-10-30 Cost-effective ferritic stainless steel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261619048P 2012-04-02 2012-04-02
US61/619,048 2012-04-02

Publications (1)

Publication Number Publication Date
WO2013151992A1 true WO2013151992A1 (en) 2013-10-10

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PCT/US2013/034940 WO2013151992A1 (en) 2012-04-02 2013-04-02 Cost-effective ferritic stainless steel

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US (1) US9816163B2 (forum.php)
EP (1) EP2834381B1 (forum.php)
JP (1) JP6113827B2 (forum.php)
KR (2) KR101821170B1 (forum.php)
CN (2) CN110144528A (forum.php)
AU (1) AU2013243635B2 (forum.php)
CA (1) CA2868278C (forum.php)
ES (1) ES2620428T3 (forum.php)
HR (1) HRP20170298T1 (forum.php)
HU (1) HUE033762T2 (forum.php)
IN (1) IN2014DN08452A (forum.php)
MX (1) MX358188B (forum.php)
PL (1) PL2834381T3 (forum.php)
RS (1) RS55821B1 (forum.php)
RU (1) RU2598739C2 (forum.php)
SI (1) SI2834381T1 (forum.php)
TW (1) TWI482866B (forum.php)
UA (1) UA111115C2 (forum.php)
WO (1) WO2013151992A1 (forum.php)
ZA (1) ZA201407915B (forum.php)

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Publication number Priority date Publication date Assignee Title
UA111115C2 (uk) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. Рентабельна феритна нержавіюча сталь
ES2717547T3 (es) * 2014-09-02 2019-06-21 Jfe Steel Corp Chapa de acero inoxidable ferrítico para carcasa de SCR de urea
JP6276316B2 (ja) * 2016-03-30 2018-02-07 新日鐵住金ステンレス株式会社 マフラーハンガー
FR3088343B1 (fr) * 2018-11-09 2021-04-16 Fond De Sougland Acier de fonderie refractaire ferritique
JPWO2023042470A1 (forum.php) * 2021-09-16 2023-03-23
JP7700978B1 (ja) * 2024-03-21 2025-07-01 Ｊｆｅスチール株式会社 脱硝装置用フェライト系ステンレス鋼

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