US20100272594A1 - Ferritic stainless steel with excellent brazeability - Google Patents

Ferritic stainless steel with excellent brazeability Download PDF

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US20100272594A1
US20100272594A1 US12/735,156 US73515608A US2010272594A1 US 20100272594 A1 US20100272594 A1 US 20100272594A1 US 73515608 A US73515608 A US 73515608A US 2010272594 A1 US2010272594 A1 US 2010272594A1
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stainless steel
ferritic stainless
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Nobuhiko Hiraide
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Nippon Steel Stainless Steel Corp
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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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to ferritic stainless steel which is used as members that are assembled by braze joining.
  • members include EGR (Exhaust Gas Recirculation) coolers, oil coolers, heat exchange equipments used in automobiles and various types of plants, aqueous urea solution tanks used in automotive urea SCR (Selective Catalytic Reduction) systems, automotive fuel delivery system components, and the like.
  • EGR exhaust Gas Recirculation
  • oil coolers oil coolers
  • heat exchange equipments used in automobiles and various types of plants
  • aqueous urea solution tanks used in automotive urea SCR (Selective Catalytic Reduction) systems
  • automotive fuel delivery system components and the like.
  • These members are generally complex in shape, and many of them are precision parts.
  • As the brazing method the case of interest is where braze joining is conducted at high temperatures under low oxygen partial pressures, such as Ni braze and Cu braze.
  • EGR coolers the objective of EGR coolers is to lower combustion temperature and reduce NO x which is a harmful gas by cooling engine exhaust gas and subsequently returning it to the intake side for recombustion.
  • thermal efficiency is required in the heat exchanger portion of the EGR cooler, and satisfactory thermal conductivity is desirable.
  • austenitic stainless steel such as SUS 304 and SUS 316 is used, and assembly is generally conducted by braze joining.
  • stainless steel for brazing there are, for example, the following types of steel sheet.
  • Patent Document 1 discloses a precoated braze-covered metal sheet fabricated by conducting suspension of Ni brazing material with organic binders, and conducting spray application onto the surface of a stainless steel sheet, after which heating is conducted.
  • Patent Document 2 discloses a method for manufacturing a nickel braze-covered stainless steel sheet with excellent self-brazing properties, wherein a stainless steel sheet having regulated surface roughness is coated with Ni brazing material by plasma spraying.
  • stainless steel which is covered in Examples is austenitic stainless steel, and ferritic stainless steel is not particularly disclosed.
  • Patent Document 3 discloses a ferritic stainless steel for an ammonia-water absorption cycle heat exchanger which has excellent brazeability and which includes 0.08% or less of C, 0.01 to 2.0% of Si, 0.05 to 1.5% of Mn, 0.05% or less of P, 0.01% or less of S, 13 to 32% of Cr, 3.0% or less of Mo, 0.005 to 0.1% of Al, 1.0% or less of Ni, 1.0% or less of Cu, and 0.05% or less of Ti.
  • Ti is limited to 0.05% or less, because carbides or nitrides of Ti form a film that inhibits brazing.
  • Table 1 records 18 types of ferritic stainless steel, and the C contents are in a range of 0.031 to 0.032% which are higher values than the C content range of the high-purity ferritic stainless steel that is now generally manufactured.
  • Patent Document 1 Japanese Unexamined Patent Application, First Publication No. H1-249294
  • Patent Document 2 Japanese Unexamined Patent Application, First Publication No. 2001-26855
  • Patent Document 3 Japanese Unexamined Patent Application, First Publication No. H11-236654
  • the present invention aims to provide a ferritic stainless steel having excellent brazeability in the case where brazing is conducted at high temperatures under low oxygen partial pressures, as with Ni braze and Cu braze.
  • Ni brazing and Cu brazing are usually conducted at 1000 to 1100° C. in a hydrogen atmosphere or a vacuum on the order of 10 ⁇ 3 to 10 ⁇ 4 torr.
  • brazing is conducted at 800 to 900° C. in a vacuum atmosphere on the order of 10 ⁇ 4 to 10 ⁇ 5 torr.
  • these conditions are often for cases of ideal conditions such as small-scale experiments, while in the case of using large-scale, mass-production facilities, it is thought that the atmosphere would be inferior in a degree of vacuum or that the atmosphere would have a high dew point due to limitations imposed by the structure of the facilities and requirements of the manufacturing process.
  • FIG. 1 shows the results of evaluation of the wettability of braze under the same test steels and test conditions as the below-mentioned examples. As shown in FIG. 1 , it was found that the wettability of braze is satisfactory within a region where, in terms of the mass % of elements, Ti—3N ⁇ 0.03 and Al ⁇ 0.5 are satisfied, and 10(Ti—3N)+Al ⁇ 0.5 is further satisfied (here, the atomic symbols in the above formulae indicate the content (mass %) of the respective element, and the numerical values that precede the atomic symbols are constants).
  • austenitic stainless steels such as SUS 304 and SUS 316 are used in EGR coolers, but diffusion of elements is quicker in ferrite than in austenite, and oxide film formation is also concomitantly quicker. Therefore, a satisfactory compositional range is limited to a narrower range in ferritic stainless steel.
  • the present invention is a ferritic stainless steel with excellent brazeability that was made based on the aforementioned findings, and a summary thereof is as follows.
  • the ferritic stainless steel with excellent brazeability of the present invention contains, in terms of mass percent, 0.03% or less of C, 0.05% or less of N, 0.015% or more of C+N, 0.02 to 1.5% of Si, 0.02 to 2% of Mn, 10 to 22% of Cr, 0.03 to 1% of Nb, and 0.5% or less of Al, and further contains Ti in a content that satisfies the following formulae (1) and (2), with the remainder composed of Fe and unavoidable impurities.
  • Ti, N, and Al indicate the contents of the respective elements expressed in mass %.
  • one or more selected from the group consisting of, in terms of mass %, 3% or less of Mo; 3% or less of Ni; 3% or less of Cu; 3% or less of V; and 5% or less of W may further be included.
  • One or more selected from the group consisting of, in terms of mass %, 0.002% or less of Ca; 0.002% or less of Mg; and 0.005% or less of B may further be included.
  • a ferritic stainless steel with excellent brazeability which is suitable for members that are fabricated by braze joining such as parts of complex shape and precision parts of small size in EGR coolers, oil coolers, heat exchange equipment used in automobiles and various types of plants, aqueous urea tanks used in automotive urea SCR systems, automotive fuel delivery system components, and the like.
  • FIG. 1 is a drawing which shows the relation of the wettability of braze to the Ti content and the Al content.
  • the present invention was made based on the aforementioned findings concerning Ti and Al, in particular, as well as Nb and C+N.
  • the chemical composition of steel prescribed by the present invention is explained below in further detail. It should be noted that % signifies mass %.
  • C As it lowers intergranular corrosion resistance and workability, it is necessary to suppress its content to a low level. Consequently, it is set to be within a range of 0.03% or less. However, in the case where the C content is excessively lowered, crystal grain coarsening is promoted during brazing, and the cost of refinement is increased. Therefore, it is preferable to set the C content to be within a range of 0.002% or higher, and the C content is more preferably within a range of 0.005 to 0.02%.
  • N This is a useful element for pitting corrosion resistance, but it is necessary to lower its content to a low level, because it degrades intergranular corrosion resistance and workability. Consequently, it is set to be within a range of 0.05% or less. However, in the case where the N content is excessively lowered, crystal grain coarsening is promoted during brazing, and the cost of refinement is increased. Therefore, it is preferable to set the N content to be within a range of 0.002% or higher, and the N content is more preferably within a range of 0.005 to 0.03%.
  • C+N Given that carbonitrides of Nb inhibits crystal grain coarsening during heating in brazing and strength reduction of the member is inhibited, 0.015% or higher of C+N is required, and 0.02% or higher is preferable. In the case where C and N are excessively added, intergranular corrosion resistance and workability are degraded. Therefore, it is preferable to set the upper limit to be within a range of 0.04% or less.
  • Si This is useful as a deoxidizing element, and is also an element that is effective in corrosion resistance, but as it lowers workability, its content is set to be within a range of 0.02 to 1.5%, and the Si content is more preferably within a range of 0.1 to 1%.
  • Mn This is useful as a deoxidizing element, but in the case where Mn is excessively included, corrosion resistance is degraded, it is set to be within a range of 0.02 to 2%, and the Mn content is preferably within a range of 0.1 to 1%.
  • Examples of assumed corrosive environments include open air environments, cooling water environments, exhaust gas-condensate environments, and the like, and from the standpoint of ensuring corrosion resistance in such environments, at least 10% or more of Cr is required. Corrosion resistance improves as its content increases, but workability and manufacturability decline. Therefore, the upper limit is set to be within a range of 22% or less, and the Cr content is preferably within a range of 15 to 21%.
  • Ti is often added with the objective of fixing C and N, and enhancing intergranular corrosion resistance of welded parts, workability, and the like.
  • Ti is an element which inhibits brazeability, and it is necessary to strictly limit its content including its content as an impurity. Consequently, the Ti content is set to be within a range where the value of Ti—3N satisfies 0.03% or less, and it is preferable that the value of Ti—3N be within a range of 0.02% or less.
  • workability is degraded when the Ti content is too low, it is preferable to set the Ti content to be within a range where the value of Ti—3N satisifies ⁇ 0.08% or more. In cases where there are no particular requirements for workability and the like, it is also acceptable to omit Ti.
  • Nb It is an important element from the standpoint that carbonitrides of Nb inhibits crystal grain coarsening during heating in brazing, and strength reduction of the member is inhibited. Moreover, it is useful in enhancing high-temperature strength and enhancing intergranular corrosion properties of welded parts, and it is necessary to include Nb at a content of 0.03% or more. However, in the case where Nb is excessively added, workability and manufacturability are degraded. Therefore, its upper limit is set to be within a range of 1% or less. The Nb content is preferably within a range of 0.2 to 0.8%, and more preferably within a range of 0.3 to 0.6%.
  • the value of Nb/(C+N) be set to be within a range of 8 or more (the atomic symbols in the aforementioned formula indicate the content (mass %) of the respective element).
  • Al This is a useful element in terms of refinement for its deoxidizing effects and the like, and it is also effective in enhancing formability. No particular lower limit is set, but in order to stably obtain these effects, the Al content is preferably within a range of 0.002% or more. However, in the case where the Al content is more than 0.5%, it inhibits brazeability which is the most important property of the present invention. Therefore, the Al content is set to be within a range of 0.5% or less. The Al content is preferably within a range of 0.003 to 0.1%. In the case where deoxidation is accomplished by an element other than Al such as Si, it is acceptable to omit Al.
  • Mo For purposes of enhancing corrosion resistance, it may be included at a content within a range of 3% or less. Stable effects are obtainable when the content is within a range of 0.3% or higher. In the case where Mo is excessively added, workability is degraded, and cost is increased due to its expensiveness. Accordingly, it is preferable that its content be within a range of 0.3 to 3%.
  • Ni For purposes of enhancing corrosion resistance, it may be included at a content within a range of 3% or less. Stable effects are obtainable when the content is within a range of 0.2% or higher. In the case where Ni is excessively added, workability is degraded, and cost is increased due to its expensiveness. Accordingly, it is preferable that its content be within a range of 0.2 to 3%.
  • Cu For purposes of enhancing corrosion resistance, it may be included at a content within a range of 3% or less. Stable effects are obtainable when the content is within a range of 0.2% or higher. In the case where Cu is excessively added, workability is degraded, and cost is increased due to its expensiveness. Accordingly, it is preferable that its content be within a range of 0.2 to 3%.
  • V For purposes of enhancing corrosion resistance, it may be included at a content within a range of 3% or less. Stable effects are obtainable when the content is within a range of 0.2% or higher. In the case where V is excessively added, workability is degraded, and cost is increased due to its expensiveness. Accordingly, it is preferable that its content be within a range of 0.2 to 3%.
  • W For purposes of enhancing corrosion resistance, it may be included at a content within a range of 5% or less. Stable effects are obtainable when the content is within a range of 0.5% or higher. In the case where W is excessively added, workability is degraded, and cost is increased due to its expensiveness. Accordingly, it is preferable that its content be within a range of 0.5 to 5%.
  • the total content of two or more selected from the group consisting of Mo, Ni, Cu, V, and W be within a range of 6% or less.
  • Ca This is a useful element in terms of refinement for its deoxidation effects and the like, and Ca may be included at a content within a range of 0.002% or less. In the case where it is included, it is preferable that the content be within a range of 0.0002% or higher because stable effects are obtainable.
  • Mg This is a useful element in terms of refinement for its deoxidation effects and the like, and is also useful in structural refinement, and enhancing workability and toughness. Mg may be included at a content within a range of 0.002% or less. In the case where it is included, it is preferable that the content be within a range of 0.0002% or higher because stable effects are obtainable.
  • B This is a useful element in enhancing secondary workability, and B may be included at a content within a range of 0.005% or less. In the case where it is included, it is preferable that the content be within a range of 0.0002% or higher because stable effects are obtainable.
  • the content of P which is an unavoidable impurity is within a range of 0.04% or less.
  • S content is preferable to be within a range of 0.01% or less.
  • the general process for manufacturing ferritic stainless steel is acceptable.
  • a molten steel is produced in a converter furnace or electric furnace, the molten steel is refined in an AOD furnace or VOD furnace or the like, and the refined molten steel is made into a slab by the continuous casting method or the ingot-making method.
  • stainless steel is manufactured via the processes of hot rolling, annealing of hot-rolled steel sheet, acid pickling, cold rolling, finish annealing, and acid pickling.
  • it is also acceptable to omit annealing of hot-rolled steel sheet and it is also acceptable to repeatedly conduct cold rolling, finish annealing, and acid pickling.
  • Formula (1) is Ti—3N
  • Formula (2) is 10(Ti—3N)+Al
  • the underlined parts in Table 1 and Table 2 indicate values outside the range of the present invention.
  • the ferritic stainless steel with excellent brazing of the present invention is suitable for members that are fabricated by braze joining as with parts of complex shape and precision parts of compact size such as EGR coolers, oil coolers, heat exchange equipment used in automobiles and various types of plants, aqueous urea tanks in automotive urea SCR systems, automotive fuel delivery system components, and the like.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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US12/735,156 2007-12-28 2008-12-24 Ferritic stainless steel with excellent brazeability Abandoned US20100272594A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2007339732 2007-12-28
JP2007339732 2007-12-28
JP2008307534A JP5390175B2 (ja) 2007-12-28 2008-12-02 ろう付け性に優れたフェライト系ステンレス鋼
JP2008307534 2008-12-02
PCT/JP2008/073394 WO2009084526A1 (ja) 2007-12-28 2008-12-24 ろう付け性に優れたフェライト系ステンレス鋼

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US (1) US20100272594A1 (ja)
EP (1) EP2224030B1 (ja)
JP (1) JP5390175B2 (ja)
KR (1) KR20100087236A (ja)
CN (2) CN101903548A (ja)
CA (1) CA2707518C (ja)
WO (1) WO2009084526A1 (ja)

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US20100051145A1 (en) * 2008-08-26 2010-03-04 Hyundai Motor Company Egr cooler for vehicles and method of manufacturing the same
US20100150770A1 (en) * 2006-05-09 2010-06-17 Nobuhiko Hiraide Stainless Steel Excellent in Corrosion Resistance, Ferritic Stainless Steel Excellent in Resistance to Crevice Corrosion and Formability, and Ferritic Stainless Stee Excellent in Resistance to Crevice Corrosion
US20110110812A1 (en) * 2008-07-23 2011-05-12 Nobulhiko Hiraide Ferrite stainless steel for use in producing urea water tank
US20110176953A1 (en) * 2008-10-24 2011-07-21 Nobuhiko Hiraide Ferritic stainless steel sheet for egr coolers
US20130272912A1 (en) * 2010-11-11 2013-10-17 Jfe Steel Corporation Ferritic stainless steel excellent in oxidation resistance
US20140069619A1 (en) * 2011-03-29 2014-03-13 Nippon Steel & Sumikin Stainless Steel Corporation Ferritic stainless steel for biofuel supply system part, biofuel supply system part, ferritic stainless steel for exhaust heat recovery unit, and exhaust heat recovery unit
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US10450625B2 (en) 2014-07-31 2019-10-22 Jfe Steel Corporation Ferritic stainless steel and method for producing same
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US10752973B2 (en) 2014-10-31 2020-08-25 Nippon Steel & Sumikin Stainless Steel Corporation Ferrite-based stainless steel with high resistance to corrosiveness caused by exhaust gas and condensation and high brazing properties and method for manufacturing same
US11634801B2 (en) * 2016-09-28 2023-04-25 Posco Co., Ltd Ferritic stainless steel having reduced carbon sludge adsorption for exhaust system heat exchanger and method of manufacturing same

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UA111115C2 (uk) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. Рентабельна феритна нержавіюча сталь
WO2014157104A1 (ja) 2013-03-29 2014-10-02 新日鐵住金ステンレス株式会社 ろう付け性に優れたフェライト系ステンレス鋼板、熱交換器、熱交換器用フェライト系ステンレス鋼板、フェライト系ステンレス鋼、燃料供給系部材用フェライト系ステンレス鋼、及び燃料供給系部品
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JP6150830B2 (ja) * 2015-03-06 2017-06-21 日新製鋼株式会社 Ｃｕろう付け時の耐Ｃｕ粒界浸透性に優れたフェライト系ステンレス鋼およびろう継手
EP3112492A1 (en) 2015-06-29 2017-01-04 Vallourec Oil And Gas France Corrosion resistant steel, method for producing said steel and its use thereof
KR102337567B1 (ko) * 2017-05-26 2021-12-08 제이에프이 스틸 가부시키가이샤 페라이트계 스테인리스강
CN111057947A (zh) * 2019-12-09 2020-04-24 宁波宝新不锈钢有限公司 一种具有良好高温强度的铁素体不锈钢及其制备方法
JP2023088240A (ja) * 2021-12-14 2023-06-26 本田技研工業株式会社 ろう付方法

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EP2224030A4 (en) 2010-12-22

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