EP3269831B1 - High chromium martensitic heat-resistant seamless steel tube or pipe with combined high creep rupture strength and oxidation resistance - Google Patents

High chromium martensitic heat-resistant seamless steel tube or pipe with combined high creep rupture strength and oxidation resistance Download PDF

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EP3269831B1
EP3269831B1 EP16179114.0A EP16179114A EP3269831B1 EP 3269831 B1 EP3269831 B1 EP 3269831B1 EP 16179114 A EP16179114 A EP 16179114A EP 3269831 B1 EP3269831 B1 EP 3269831B1
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Prior art keywords
steel
seamless tube
pipe according
anyone
pipe
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German (de)
English (en)
French (fr)
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EP3269831A1 (en
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Arno FUCHSMANN
Bernhard Koschlig
Marko SUBANOVIC
Walter Bendick
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Vallourec Deutschland GmbH
Vallourec Tubes France SAS
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Vallourec Deutschland GmbH
Vallourec Tubes France SAS
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Priority to ES16179114T priority Critical patent/ES2846875T3/es
Application filed by Vallourec Deutschland GmbH, Vallourec Tubes France SAS filed Critical Vallourec Deutschland GmbH
Priority to EP16179114.0A priority patent/EP3269831B1/en
Priority to PL16179114T priority patent/PL3269831T3/pl
Priority to PCT/EP2017/067613 priority patent/WO2018011301A1/en
Priority to KR1020197004185A priority patent/KR102475025B1/ko
Priority to MX2019000517A priority patent/MX2019000517A/es
Priority to CN201780039089.4A priority patent/CN109689901A/zh
Priority to US16/314,205 priority patent/US20190203313A1/en
Priority to CA3025133A priority patent/CA3025133A1/en
Priority to BR112019000376-2A priority patent/BR112019000376B1/pt
Priority to EP17743278.8A priority patent/EP3485046B1/en
Priority to JP2019500645A priority patent/JP7016343B2/ja
Priority to EA201990013A priority patent/EA036004B1/ru
Priority to UAA201900275A priority patent/UA124766C2/uk
Priority to AU2017297766A priority patent/AU2017297766B2/en
Publication of EP3269831A1 publication Critical patent/EP3269831A1/en
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
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    • C21D2211/00—Microstructure comprising significant phases
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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Definitions

  • the invention relates to martensitic high chromium heat-resistant seamless steel tubes or pipes for components operating at elevated temperatures i.e. between 550 and 750°C and high stresses.
  • the steel tubes or pipes according to the invention can be used in power generation, chemical and petrochemical industry.
  • the ferritic/martensitic high Cr steel materials are widely used in the modern power plants as reheater/superheater tubes and as steam pipes. Further improvement of the net efficiency of thermal power plants will require an increase of the steam parameters pressure and temperature. Therefore, the realization of more efficient power plant cycles will require stronger materials with improved steam-side oxidation resistance.
  • the known efforts to develop new martensitic high chromium steel that combines excellent creep properties and superior oxidations resistance have failed so far due to the formation of the so called Z-phase.
  • Z-phase is a complex nitride that coarsens quickly thereby consuming the surrounding strengthening MX precipitates, M being: Nb, V and X being: C, N.
  • Elevated Cr contents i.e. containing more than 9wt.-% of Cr, which are essential for good steam oxidation resistance, however, increase the driving force for Z-phase formation and also enhance the coarsening rate of chromium carbide precipitates. Both, the loss of the microstructure stabilizing effect of MX and chromium carbide precipitates are responsible for the drop in the long-term creep rupture strength of martensitic high Cr heat-resistant steel grades. Hence, the major challenge for future steel developments is to resolve the apparent contradiction between the creep rupture strength and oxidation resistance.
  • ASTM Grades 91 and 92 are widely used, both containing 9 wt.-%Cr with creep rupture strengths after 10 5 h at 600°C at 90 and 114MPa respectively.
  • the main difference between the two steels is that Grade 92 contains W in the range of 1.8 wt.-% and reduced Mo of 0.4 wt.-% compared to 1 wt.-% in case of Grade 91.
  • Grade 92 contains small amounts of B below 0.005 wt.-%.
  • Both steels suffer from insufficient oxidation resistance in steam atmospheres at temperatures above 600°C, which is limiting the application temperature range significantly.
  • the oxide scale acts as thermal insulator thereby increasing the metal temperature and consequently reducing lifetime of corresponding components.
  • the oxide scales if spalled off during operation, will cause erosion damage on the following steam carrying components or after entering the steam turbine on turbine blades and guiding vanes. Spalled oxide scales may cause tube blockage especially in the region of bends, impeding the steam flow often resulting in local overheating and catastrophic failure.
  • X20CrMoV11-1 is a well established high Cr ferritic/martensitic steel for high temperature applications containing 0.20wt.-% C, 10.5-12 wt.-percent Cr, 1 wt.-% Mo and 0.2wt.-% V.
  • This steel exhibits oxidation properties which are better than that of ASTM steel grades 91 and 92 due to higher Cr contents, but poor creep rupture strength (creep rupture strength after 10 5 h at 600°C being around 59MPa). Additionally the hot-workability and weldability are deteriorated due to high C content of 0.20 wt.-%.
  • ASTM Grade 122 contains 10-12%Cr, 1.8%W, 1%Cu and also V, Nb and N additions to induce the precipitation of MX strengthening particles.
  • the creep rupture strength is significantly below that of ASTM Grade 92 that presents a creep rupture strength of 98MPa after 10 5 h at 600°C.
  • Another steel with 11 to 12 wt.-% of Cr exists. it is mainly used as thin-walled tube, and is called VM12-SHCsteels that combines good steam-side oxidation resistance and the creep rupture strength at the level of ASTM Grade 91.Such steel concept is known from patent application WO02081766 disclosing a steel for high temperature use containing by weight : 0.06 to 0.20% of C, 0.10 to 1.00% of Si, 0.10 to 1.00% of Mn, not more than 0.010% of S, 10.00 to 13.00% of Cr, not more than 1.00% of Ni, 1.00 to 1.80% of W, Mo such that (W/2+Mo) is not more than 1.50%, 0.50 to 2.00% of Co, 0.15 to 0.35% of V, 0.040 to 0.150% of Nb, 0.030 to 0.12% of N, 0.0010 to 0.0100% of B and optionally up to 0.0100% of Ca, the rest of the chemical composition consisting of iron and impurities or residues resulting
  • the chemical constituent contents preferably verify a relationship such that the steel after normalizing heat treatment between 1050 and 1080 °C and tempering has a tempered martensite structure free or practically free of delta ferrite. Compared to this steel, creep rupture strength can still be improved while keeping the other properties such as corrosion resistance and mechanical properties unaffected.
  • the object of the present invention is therefore to provide a martensitic heat-resistant seamless steel tube or pipe with substantially better creep rupture strength than ASTM Grade 92 steel for pipes and tubes, and with hot corrosion and steam oxidation behavior comparable or better than X20CrMoV11-1 and VM12-SHC steels, described in the state of the art.
  • a further object of the invention is to obtain a steel exhibiting martensitic microstructure with a limitation of the delta ferrite, also known as ⁇ -ferrite, content to 5 vol.-% in average.
  • Another object of the invention was to provide a steel that allows the fabrication of small or large diameter seamless and welded tubes and pipes, forgings and plates using the known and established manufacturing processes.
  • the steel is suited as a production material for whole variety of components operating under stress at elevated temperatures, particularly as seamless and welded tubes/pipes, forgings and plates in power generation, chemical and petrochemical industry.
  • the steel according to the invention is temper resistant, after long tempering times up to 30 hours at 800°C, the yield strength is above or equal 440 MPa, the tensile stress above or equal 620 MPa and toughness at 20°C is above or equal 40 J when tested in longitudinal direction and 27 J when tested in transverse direction.
  • the object can be achieved by a seamless steel tube or pipe for high-temperature applications having the following chemical composition in weight percent:
  • the ratio of boron and nitrogen is such that: B / N ⁇ 1.5 to achieve hot workability.
  • the carbon content is between 0.13 and 0.16%.
  • the Mo content is between 0.30 and 0.60%.
  • B content is between 0.0095 and 0.013%.
  • the microstructure comprises in average at least 95 % of tempered martensite, the balance being delta ferrite.
  • the microstructure comprises in average at least 98 % of tempered martensite, the balance being delta ferrite.
  • the microstructure is martensitic and free of delta ferrite.
  • the invention also relates to a method of production comprising the following steps:
  • the cooling step is done using air cooling or water cooling.
  • the invention also concerns the production of a seamless tube or pipe using the steel according to the invention or the process according to the invention.
  • Figure 1 shows the schematic of mass gain due to oxidation plotted versus chromium content.
  • a martensitic high chromium heat-resistant steel having the following chemical composition:
  • C needs to be added to at least 0.10 % to obtain sufficient carbide precipitation. Additionally C is also an austenite stabilizing element. C contents below 0.10% would imply more ⁇ -ferrite in the microstructure. The upper limit for carbon is 0.16% because excess C addition limits the toughness and weldability properties.
  • Si is used for deoxidation during the steel making process. Additionally, it is one of key elements, which determines the oxidation behavior in steels. In order to achieve the full oxidation improving effect of Si additions an amount of at least 0.20 % is necessary.
  • the upper Si level shall preferably be limited to 0.60 %, because the excess Si addition accelerates the coarsening of precipitates and decreases toughness.
  • Mn is an effective deoxidation element. It ties up sulphur and reduces the ⁇ -ferrite formation. At least 0.30% Mn may be added. The upper limit shall be 0.8%, since excessive additions reduce the strength of steels at elevated temperatures.
  • P is a grain-boundary active element, which reduces the toughness properties of steels.
  • the content has to be limited to 0.020% in order to avoid the negative impact of P on toughness properties.
  • S forms sulfides and reduces the toughness and hot-workability properties of steels.
  • a limitation of upper S content to 0.010 prevents the defect formation during hot-working operation and the negative impact on toughness.
  • Al is a potent deoxidation element used during the steel making process. Excess Al addition above 0.02% can induce AIN formation, thereby reducing the amount of strengthening MX (M being: Nb, V and X being: C, N) nitride precipitates in steel and consequently the creep strength properties.
  • MX being: Nb, V and X being: C, N
  • Cr forms carbides that form at boundaries of the martensitic microstructure. Chromium carbides are essential for stabilization of the martensitic microstructure during exposure at elevated temperatures. Cr improves the high temperature oxidation behavior of steels. Contents of at least 10.5% are necessary to unfold the full oxidation improving effect of Cr additions. Cr contents above 12% result in increased ⁇ -ferrite formation.
  • Mo is an important element for improvement of creep rupture strength that is also responsible for solid solution strengthening. This element is incorporated in carbides and intermetallic phases as well. Mo content of 0.10 % may be added. The Mo additions above 0.60 % will deteriorate toughness and induce increase of ⁇ -ferrite content. Note that M and W contents shall satisfy the relationship (in weight %) 1 ⁇ Mo+0.5 x W ⁇ 1.5, in order to ensure the sufficient precipitation of carbides and intermetallic phases.
  • V combines with N to form coherent MX nitrides (M being : Nb, V and X being : C, N), which contribute to enhancement of long-term creep properties. Contents below 0.15% are not sufficient to achieve this long-term creep improving property effect while contents above 0.30% decrease the toughness and increase the danger for ⁇ -ferrite contents above 5% in average volume.
  • Ni is an important toughness improving element. Therefore, a minimum content of 0.10 % is necessary. However, it reduces A c1 temperature and tends to reduce the creep rupture strength, if added in contents above 0.40 %.
  • B is a decisive element responsible for stabilization of M 23 C 6 carbides and delay of recovery of the martensitic microstructure. It strengthens the grain boundaries and improves the long-term stability of creep rupture strength. In addition, B is responsible for remarkable improvement of creep rupture ductility. For achievement of maximum strengthening effect additions of at least 0.008% are necessary. Contents above 0.015%, however, reduce substantially the maximum processing temperature of steels and are regarded as detrimental. B and N additions shall satisfy the relationship B/N ⁇ 1.5 to enable transformation using known hot-working processes. Indeed, this B/N relationship allows the fabrication of small or large diameter seamless and welded tubes, pipes and plates using manufacturing process according to the invention. Preferably, the B content should be between 0.0095 and 0.0130 (wt %).
  • Nitrogen is necessary for formation of MX (M being: Nb, V and X being: C, N) nitrides and carbonitrides responsible for achievement of creep rupture strength. At least 0.002% may be added. Excessive N additions i.e. above 0.020%, however, result in enhanced BN formation, thereby reducing the strengthening effect of B additions.
  • B and N contents (in weight %) shall satisfy the following relationship: B ⁇ 11 14 N ⁇ 10 ⁇ 1 / 2.45 ⁇ logB + 6.81 ⁇ 14 48 ⁇ Ti ⁇ 0.007
  • Co is a very effective austenite forming element and useful in limiting ⁇ -ferrite formation. Moreover, it has only a weak effect on A c1 temperature. Additionally, it is an element that improves creep strength properties by reducing the size of initial precipitates after heat treatment. Therefore, a minimum content of 1.50% shall be added. However, Co in excessive additions may induce embrittlement due to enhanced precipitaton of intermetallic phases during high temperature operation. At the same time Co is very expensive. Hence, a limitation of additions to 3.00%, preferably to 2.50%, is necessary.
  • Ni, Co, Mn, C and N contents are in accordance with the following equation: 2.6 ⁇ 4 ⁇ ( Ni + Co + 0.5 ⁇ Mn ) - 20 ⁇ ( C + N ) ⁇ 11.2.
  • W is known as an effective solution strengthener. At the same time it is incorporated in carbides and forms C14 Laves phase, which may contribute to creep strength enhancement as well. Therefore, a minimum content of 1.50% is needed. However, this element is expensive, strongly segregating during steel making and casting process and it forms intermetallic phases that lead to significant embrittlement. Hence, the upper limit for W additions may be set to 2.50%. Note that Mo and W contents (in weight %) shall satisfy the relationship 1.00 ⁇ Mo+0.5W ⁇ 1.50 in order to ensure the sufficient precipitation of carbides and intermetallic phases.(15) Nb: 0.02 to 0.07%.
  • Nb forms stable MX carbonitrides important not only for creep properties but also austenite grain size control.
  • a minimum content of 0.02% may be added.
  • Nb contents above 0.07% result in formation of coarse Nb carbides that may reduce the creep strength properties. Therefore the upper limit is set to 0.07%.
  • Ti is a strong nitride forming element. It is helpful to protect free B by forming nitrides. Minimum content of 0.001% is needed for this purpose. Excessive Ti content above 0.020%, however, can reduce toughness properties due to formation of large blocky TiN precipitates.
  • the balance of the steel comprises iron and ordinary residual elements coming from steel making and casting process.
  • impurities we mean elements such as tantalum, zirconium and any other elements that can't be avoided. It is to be mentioned that Tantalum and zirconium are not intentionally added to the steel, however may be present in less than 50 ppm overall as unavoidable impurities.
  • the unavoidable impurities may comprise one or more of copper (Cu), Arsenic (As), tin (Sn), antimony (Sb) and lead (Pb).
  • Cu may be present in a content equal or less than 0.20 %.
  • Element As may be present in a content equal or less than 150 ppm; Sn may be present in a content equal or less than 150 ppm; Sb may be present in a content equal or less than 50 ppm; Pb may be present in a content equal or less than 50 ppm and the total content As + Sn + Sb + Pb is equal or less than 0.04 % in mass.
  • the steel is normalized for a period of about 10 to about 120 minutes in the temperature range between 1050 °C and 1170°C and cooled down in air or water to room temperature, and then tempered for at least one hour in the temperature range between 750°C and 820°C.
  • the resulting steel possesses remarkable and absolutely excellent elevated temperature strength and superior steam-oxidation resistance. Moreover, it was found that by Cr eq. /Ni eq. ratio being less than 2.3, the average ⁇ -ferrite content can be limited to less than 5 vol.% to avoid toughness issues, wherein Cr eq. and Ni eq . are defined as Cr+6Si+4Mo+1.5W+11V+5Nb+8Ti and 40C+30N+2Mn+4Ni+2Co+Cu, respectively. Surprisingly, it was found that the B/N ratio equal or less than 1.5 has to be kept in order to enable the hot-working operation with known transformation processes.
  • the delta ferrite content shall not exceed 5 vol.-% since contents above 5vol.-% will impair the toughness properties.
  • hot forming processes it is meant: hot rolling, pilgering, hot drawing, forging, plug mill, push-bench process where the mandrel rod pushes the elongated hollow through several in-line roll stands to produce a hollow, continuous rolling, and other rolling processes known.
  • Steels in accordance with the present invention (Steel 1, Steel 2) and also comparative example steels (Steel 3, Steel 4), having the chemical composition indicated in Table 1, have been cast to 100 kg ingots using vacuum induction melting furnace, then hot-rolled to plates (13-25mm thickness) and subsequently normalized and tempered.
  • the normalizing heat-treatment was performed in the temperature range of 1060°C to 1100°C for 30 minutes, followed by air cooling to room temperature.
  • the tempering was done at 780°C for 120 minutes, again followed by cooling in air.
  • Comparative example steels 3 and 4 have B contents below 0.008 and are therefore not in accordance with the invention.
  • Ni, Co, Mn, C and N additions do not comply with equation 2.6 ⁇ 4 ⁇ Ni + Co + 0.5 ⁇ Mn ⁇ 20 ⁇ C + N ⁇ 11.2 in wt . ⁇ % .
  • the steel 4 does not fulfill the following formula: B ⁇ 11 14 N ⁇ 10 ⁇ 1 / 2.45 ⁇ logB + 6.81 ⁇ 14 48 ⁇ Ti ⁇ in wt . % either .
  • Creep tests performed in accordance to ISO DIN EN 204, on the specimens of the two example steels showed furthermore a remarkable improvement of the creep rupture strength. This is reflected in rupture times being at least three times more than that of state-of-the-art steels like P91, P91, VM12-SHC, P122 and X20CrMoV11-1 during long-term creep testing at 130MPa and 100MPa. The results are displayed in Table 3. Also the comparative example steels does not reach the creep rupture strength of the steels according to the invention.
  • Figure 1 shows the schematic of mass gain due to oxidation in water vapor atmosphere at elevated temperatures plotted versus chromium content.
  • the basis for the construction of the schematic is the oxidation tests in water vapor atmosphere performed according to ISO 21608:2012.

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EP16179114.0A 2016-07-12 2016-07-12 High chromium martensitic heat-resistant seamless steel tube or pipe with combined high creep rupture strength and oxidation resistance Active EP3269831B1 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
EP16179114.0A EP3269831B1 (en) 2016-07-12 2016-07-12 High chromium martensitic heat-resistant seamless steel tube or pipe with combined high creep rupture strength and oxidation resistance
PL16179114T PL3269831T3 (pl) 2016-07-12 2016-07-12 Bezszwowa rura lub przewód rurowy z martenzytycznej wysoko-chromowej żaroodpornej stali z połączoną wysoką wytrzymałością na zerwanie w wyniku pełzania oraz odpornością na utlenianie
ES16179114T ES2846875T3 (es) 2016-07-12 2016-07-12 Tubo o tubería de acero sin costura martensítico con alto contenido de cromo resistente al calor con una combinación de alta resistencia a la rotura por fluencia y resistencia a la oxidación
EA201990013A EA036004B1 (ru) 2016-07-12 2017-07-12 Высокохромистая мартенситная жаропрочная сталь, характеризующаяся высокой длительной прочностью и сопротивлением окислению
MX2019000517A MX2019000517A (es) 2016-07-12 2017-07-12 Acero martensitico de alto contenido de cromo resistente al calor con alta resistencia a la ruptura por fluencia y resistencia a la oxidacion combinadas.
CN201780039089.4A CN109689901A (zh) 2016-07-12 2017-07-12 具有联合的高蠕变断裂强度和抗氧化性的高铬马氏体耐热钢
US16/314,205 US20190203313A1 (en) 2016-07-12 2017-07-12 High chromium martensitic heat-resistant steel with combined high creep rupture strength and oxidation resistance
CA3025133A CA3025133A1 (en) 2016-07-12 2017-07-12 High chromium martensitic heat-resistant steel with combined high creep rupture strength and oxidation resistance
PCT/EP2017/067613 WO2018011301A1 (en) 2016-07-12 2017-07-12 High chromium martensitic heat-resistant steel with combined high creep rupture strength and oxidation resistance
EP17743278.8A EP3485046B1 (en) 2016-07-12 2017-07-12 High chromium martensitic heat-resistant steel with combined high creep rupture strength and oxidation resistance
JP2019500645A JP7016343B2 (ja) 2016-07-12 2017-07-12 高クリープ破断強度と耐酸化性とを併せ持つ高クロムマルテンサイト系耐熱鋼
KR1020197004185A KR102475025B1 (ko) 2016-07-12 2017-07-12 조합된 고 크리프 파단 강도 및 내산화성을 지닌 마르텐사이트계 고 크롬 내열강
UAA201900275A UA124766C2 (uk) 2016-07-12 2017-07-12 Високохромиста мартенситна жаростійка сталь, що характеризується високою тривалою міцністю та опором до окиснення
AU2017297766A AU2017297766B2 (en) 2016-07-12 2017-07-12 High chromium martensitic heat-resistant steel with combined high creep rupture strength and oxidation resistance
BR112019000376-2A BR112019000376B1 (pt) 2016-07-12 2017-07-12 Tubo sem costura para aplicações de alta temperatura, e método de produção desse tubo sem costura

Applications Claiming Priority (1)

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EP16179114.0A EP3269831B1 (en) 2016-07-12 2016-07-12 High chromium martensitic heat-resistant seamless steel tube or pipe with combined high creep rupture strength and oxidation resistance

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EP (2) EP3269831B1 (ja)
JP (1) JP7016343B2 (ja)
KR (1) KR102475025B1 (ja)
CN (1) CN109689901A (ja)
AU (1) AU2017297766B2 (ja)
BR (1) BR112019000376B1 (ja)
CA (1) CA3025133A1 (ja)
EA (1) EA036004B1 (ja)
ES (1) ES2846875T3 (ja)
MX (1) MX2019000517A (ja)
PL (1) PL3269831T3 (ja)
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US10772147B2 (en) 2016-12-22 2020-09-08 Intel Corporation Methods and apparatus for connection attempt failure avoidance with a wireless network
CN109594019A (zh) * 2018-12-27 2019-04-09 天津理工大学 一种9Cr马氏体耐热铸钢及消除该铸钢中δ-铁素体的方法
US11772206B2 (en) 2019-09-20 2023-10-03 Lincoln Global, Inc. High chromium creep resistant weld metal for arc welding of thin walled steel members
US11772207B2 (en) 2019-09-20 2023-10-03 Lincoln Global, Inc. High chromium creep resistant weld metal for arc welding of thick walled steel members
CN111057827B (zh) * 2019-11-27 2022-04-05 中国科学院金属研究所 调控超超临界机组用9Cr3W3CoB耐热钢中硼元素分布状态的方法
CN111041179B (zh) * 2019-12-03 2021-12-14 马鞍山钢铁股份有限公司 一种消除高Cr当量P92耐热钢高温铁素体的方法及高Cr当量P92耐热钢的制备方法
CN116949260B (zh) * 2023-09-20 2023-12-19 成都先进金属材料产业技术研究院股份有限公司 一种p91无缝钢管用钢锭及其热变形方法

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UA124766C2 (uk) 2021-11-17
BR112019000376A2 (pt) 2019-04-24
EA201990013A1 (ru) 2019-05-31
EA036004B1 (ru) 2020-09-11
US20190203313A1 (en) 2019-07-04
EP3269831A1 (en) 2018-01-17
KR102475025B1 (ko) 2022-12-07
WO2018011301A1 (en) 2018-01-18
BR112019000376B1 (pt) 2022-06-28
AU2017297766B2 (en) 2023-02-16
JP7016343B2 (ja) 2022-02-04
CA3025133A1 (en) 2018-01-18
EP3485046A1 (en) 2019-05-22
CN109689901A (zh) 2019-04-26
KR20190029654A (ko) 2019-03-20
ES2846875T3 (es) 2021-07-30
AU2017297766A1 (en) 2018-12-13
MX2019000517A (es) 2019-09-23
PL3269831T3 (pl) 2021-05-04
JP2019524996A (ja) 2019-09-05
EP3485046B1 (en) 2020-11-18

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