EP3797179B1 - New austenitic alloy - Google Patents

New austenitic alloy Download PDF

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Publication number
EP3797179B1
EP3797179B1 EP19724876.8A EP19724876A EP3797179B1 EP 3797179 B1 EP3797179 B1 EP 3797179B1 EP 19724876 A EP19724876 A EP 19724876A EP 3797179 B1 EP3797179 B1 EP 3797179B1
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Prior art keywords
austenitic alloy
content
melt
intermetallic phases
austenitic
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EP19724876.8A
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German (de)
English (en)
French (fr)
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EP3797179A1 (en
EP3797179C0 (en
Inventor
Karin ANTONSSON
Ulf KIVISÄKK
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Alleima Tube AB
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Alleima Tube AB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C38/40—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 disclosure relates to an austenitic alloy having a high content of Ni, Mo and Cr which will, after solidification, have a low content of intermetallic phases (less than 0.3 %).
  • the present disclosure also relates to the use of the austenitic alloy in different products and to a method for manufacturing such an alloy.
  • Nickel-base alloys are used in many corrosive applications where the corrosion resistance and the stability of the microstructure of today's stainless steels are insufficient. However, there are problem associated with these alloys as they are prone to form microsegregations during the solidification process and thereby form unwanted intermetallic phases. These will, in turn, cause poor ductility and poor corrosion properties. The content of intermetallic phases may be reduced by using certain manufacturing methods, such as remelting and soaking, but these methods are very expensive.
  • the present provides an austenitic alloy consisting of, in weight% (wt%): C ⁇ 0 .03; Si ⁇ 1 .0; Mn ⁇ 1 .5; S ⁇ 0 .03; P ⁇ 0 .03; Cr 25.5 to 32.0; Ni 42.0 to 52.0; Mo 6.0 to 9.0; N 0 .07 ⁇ 0 .11; Cu ⁇ 0 .4; balance Fe and unavoidable impurities;
  • the austenitic alloy as defined hereinabove or hereinafter will have a good corrosion resistance and a high ductility as the austenitic alloy will comprise less than 0.3 % intermetallic phases after solidification which means that there will be less intermetallic phases present in the austenitic alloy.
  • the intermetallic phases have a negative impact on any of the processes performed after solidification.
  • the present disclosure also relates to an object comprising the austenitic alloy as defined hereinabove or hereinafter.
  • an object is a tube, a pipe, a bar, a rod, a hollow, a billet, a bloom, a strip, a wire, a plate and a sheet.
  • the present disclosure also provides a method for manufacturing an austenitic alloy consisting of, in weight%: C ⁇ 0.03 ; Si ⁇ 1.0 ; Mn ⁇ 1.5 ; S ⁇ 0.03 ; P ⁇ 0.03 ; Cr 25.5 to 32.0; Ni 42.0 to 52.0; Mo 6.0 to 9.0; N 0.07 ⁇ 0.11 ; Cu ⁇ 0.4 ;
  • the austenitic alloy will have an intermetallic phase content of less than 0.3 % after solidification, wherein said method comprises the steps of:
  • the obtained final object will have a low content of intermetallic phases, such as ⁇ 0.3%.
  • the present disclosure relates to an austenitic alloy consisting of the following elements in weight%: C ⁇ 0 .03; Si ⁇ 1 .0; Mn ⁇ 1 .5; S ⁇ 0 .03; P ⁇ 0 .03; Cr 25.5 to 32.0; Ni 42.0 to 52.0; Mo 6.0 to 9.0; N 0 .07-0 .11; Cu ⁇ 0 .4;
  • the austenitic alloy of the present disclosure will have a low fraction (amount) of intermetallic phases (less than 0.3%) formed in the interdendritic areas during the solidification process.
  • the fraction is calculated by dividing the volume of intermetallic phases in the interdendritic areas with the total volume of the material. Examples of intermetallic phases are sigma phase, laves phases and chi-phase.
  • Solidification is a phase transformation wherein an alloy will transform from a liquid phase to a solid crystalline structure phase.
  • the solidification process starts with the formation of dendrites and during the solidification process microsegregation will occur.
  • Microsegregation is an uneven distribution of alloying elements between the solidified dendrites which will promote the formation of unwanted intermetallic phases.
  • the area between the dendrites is called interdendritic area.
  • Typical solidification processes, but not limited to, are casting such as ingot casting, continuous casting and remelting.
  • the austenitic alloy as defined hereinabove or hereinafter will due to the low content of intermetallic phases in the intermetallic areas have a good corrosion resistance and a very good ductility.
  • the austenitic alloy will therefore be very suitable for use in applications wherein high resistance to corrosion is necessary, such as in oil and gas industry, petrochemical industry and chemical industry.
  • the austenitic alloy as defined hereinabove or hereinafter also fulfill the condition of having a critical pitting temperature (CPT) greater than 88°C.
  • CPT critical pitting temperature
  • the present disclosure also relates an object comprising the austenitic alloy as defined hereinabove or hereinafter.
  • an object but not limited thereto, is a tube, a bar, a pipe, a rod, a hollow, a billet, a bloom, a strip, a wire, a plate and a sheet.
  • Further examples include production tubing and heat exchanger tubing.
  • C is an impurity contained in austenitic alloys.
  • the content of C exceeds 0.03 wt%, the corrosion resistance is reduced due to the precipitation of chromium carbide in the grain boundaries.
  • the content of C is ⁇ 0.03 wt%, such as ⁇ 0.02 wt%.
  • Si is an element which may be added for deoxidization. However, Si will promote the precipitation of the intermetallic phases, such as the sigma phase, therefore Si is contained in a content of ⁇ 1.0 wt%, such as ⁇ 0.5 wt%, such as ⁇ to 0.3 wt%. According to one embodiment the lower limit of Si is 0.01 wt%.
  • Mn is often used to for binding sulphur by forming MnS and thereby increasing the hot ductility of the austenitic alloy. Mn will also improve deformation hardening of the austenitic alloy during cold working. However, a too high content of Mn will reduce the strength of the austenitic alloy. Accordingly, the content of Mn is set at ⁇ 1.5 wt%, such as ⁇ 1.2 wt%. According to one embodiment, the lower limit of Mn is lower 0.01 wt%.
  • P is an impurity contained in the austenitic alloy and is well known to have a negative effect on the hot workability and the resistance to hot cracking. Accordingly, the content of P is ⁇ 0.03 wt%, such as ⁇ 0.02 wt%.
  • S is an impurity contained in the austenitic alloy, and it will deteriorate the hot workability. Accordingly, the allowable content of S is ⁇ 0.03 wt%, such ⁇ 0.02 wt%.
  • Cu may reduce the corrosion rate in sulphuric acids. However, Cu will reduce the hot workability, therefore the maximum content of Cu is ⁇ 0.4 wt%, such as ⁇ 0.25 wt%. According to one embodiment, the lower limit of Cu is 0.01 wt%.
  • Ni is an austenite stabilizing element. Furthermore, Ni will also contribute to the resistance to stress corrosion cracking in both chlorides and hydrogen sulfide environments. Thus, a content of Ni of 42.0 wt% or more is required. However, an increased Ni content will decrease the solubility of N, therefore the maximum content of Ni is 52.0 wt%. According to one embodiment of the present austenitic alloy, the content of Ni is of from 43.0 to 51.0 wt%, such as of from 44.0 to 51.0 wt%.
  • Cr is an alloying element that will improve the pitting corrosion resistance. Furthermore, the addition of Cr will increase the solubility of N. When the content of Cr is less than 25.5 wt%, the effect of Cr is not sufficient for corrosion resistance, and when the content of Cr exceeds 32.0 wt%, secondary phases as nitrides and intermetallic phases will be formed, which will affect the corrosion resistance negatively. Accordingly, the content of Cr is of from 25.5 to 32.0 wt%.
  • Mo is an alloying element which is effective in stabilizing the passive film formed on the surface of the austenitic alloy. Furthermore, Mo is effective in improving the pitting corrosion, .
  • the content of Mo is less than 6.0 wt%, the resistance for pitting corrosion in harsh environments is not high enough and when the content of Mo is more than 9.0 wt%, the hot workability is deteriorated. Accordingly, the content of Mo is of from 6.0 to 9.0 wt%, such as of from 6.1 to 9.0 wt%, such as 6.4 to 9.0 wt%, such as of from 6.4 to 8.0 wt%.
  • N is an effective alloying element for increasing the strength of the austenitic alloy by using solution hardening and it is also beneficial for the improving the structure stability.
  • the addition of N will also improve the deformation hardening during cold working.
  • the content of N must be above 0.07 wt%.
  • the content of N is more than 0.11 wt%, then the flow stress will be too high for efficient hot working and the resistance against pitting corrosion will be reduced.
  • the content of N is of from 0.07 to 0.11 wt%.
  • the austenitic alloy as defined hereinabove or herein after may optionally comprise one or more of the following elements Al, Mg, Ca, Ce, and B. These elements may be added during the manufacturing process in order to enhance e.g. deoxidation, corrosion resistance, hot ductility or machinability. However, as known in the art, the addition of these elements and the amount thereof will depend on which alloying elements are present in the alloy and which effects are desired. Thus, if added the total content of these elements is ⁇ 1.0 wt%, such as ⁇ 0.5 wt%.
  • the austenitic alloy consists of all the alloying elements mentioned hereinabove or hereinafter in the ranges mentioned hereinabove or hereinafter.
  • impurities means substances that will contaminate the austenitic alloy when it is industrially produced, due to the raw materials, such as ores and scraps, and due to various other factors in the production process and are allowed to contaminate within the ranges not adversely affecting the properties of the austenitic alloy as defined hereinabove or hereinafter.
  • allying elements which are considered to be impurities are Co and Sn.
  • Carbide formers, such as Nb and W are considered in the present disclosure to be impurities and/or trace elements and if present they are only present in very low levels, meaning they will not form any carbides, and thus will not have an impact on the final properties of the austenitic alloy.
  • the present disclosure also provides a method for manufacturing an austenitic alloy having the composition consisting of the following elements in weight% (wt%): C ⁇ 0 .03; Si ⁇ 1.0 ; Mn ⁇ 1.5 ; S ⁇ 0.03 ; P ⁇ 0.03 ; Cr 25.5 to 32.0; Ni 42.0 to 52.0; Mo 6.0 to 9.0; N 0 . 07 ⁇ 0.11 ; Cu ⁇ 0.4 ;
  • the inventors have by thorough investigations surprisingly found that by integrating this method into conventional metallurgical manufacturing processes, the object obtained thereof will have a low content of intermetallic phases after solidification which will have a positive impact on the outcome of other metallurgically processes used.
  • the equation of may also be used when designing the austenitic alloy, i.e. before the austenitic alloy is melted.
  • the analyzing of the melt may be performed using e.g. X-ray fluorescence spectrometry, Spark discharge optical emission spectrometry, Combustion analysis, Extraction analysis and Inductively coupled plasma optical emission spectrometry.
  • the obtained element content from the analyze is then inserted into the equation. If the condition (equation) is not fulfilled, then alloying elements are added until the equation is fulfilled. When the additional alloying elements have been added, the melt may be analyzed again, and these steps may be repeated several times until the equation (condition) is fulfilled.
  • samples may be taken from the austenitic alloy after solidifying for measuring and verifying the intermetallic phases.
  • the solidifying method is casting.
  • the method may comprise conventional metal manufacturing steps such as hot working and/or cold working.
  • the method may optionally comprise heat treatment steps and/or aging steps.
  • hot working processes are hot rolling, forging and extrusion.
  • cold working processes are pilgering, drawing and cold rolling.
  • heat treatment processes are soaking and annealing, such as solution annealing or quench annealing.
  • objects which may be obtained by the method as defined hereinabove or hereinafter is a tube, a pipe, a bar, a, rod, a hollow, a billet, a bloom, a strip, a wire, a plate and a sheet.
  • the alloys of Table 1 were made by melting in a HF (High Frequency) induction furnace of 270 kg and thereafter they were made into ingots by casting into 9"mould. After casting and solidification, the moulds were removed and the ingots were quenched in water.
  • the compositions of the experimental heats, Cr- and Ni-equivalents and fraction of intermetallic phases in interdendric areas are given in Tables 1 and 2.
  • FIG. 2A shows (sample 3) which is outside the present invention and as can been seen it has intermetallic phases in an amount which is more than 0.3% after solidification.
  • Figure 2B shows (sample 2) which is according to the present invention and as can be seen it has no intermetallic phases after solidification. Further examples are shown in Figure 3A to 3B , wherein Figure 3A of (sample 4) is outside the scope of the present invention whereas Figure 3B of (sample 7) is inside the scope of the present invention and has no intermetallic phase.
  • the Cr- and Ni-equivalents of the heats are plotted in Figure 1 , which shows a DeLong diagram wherein the X- and Y-axis are the Cr-equivalent (E Cr ) and the Ni-equivalent (E Ni ).
  • the unfilled squares in the figure are the heats with less than 0.3% intermetallic phases in interdendritic areas after solidification, i.e. alloys which fulfill the condition of the present invention.
  • Table 1 Chemical analysis of the experimental heats, in weight%, and calculated Cr- and Ni-equivalents. The balance is Fe and unavoidable impurities.
  • Samples marked with a "*" is within the present invention
  • No 2* 0.006 0.25 1.08 0.006 0.0010 30.19 50.24 6.50 0.10 0.21 37.1 54.1 49.2 Yes 3 0.010 0.21 1.04 0.006 0.0010 34.78 43.03 6.55 0.12 0.19 41.6 47.5 57.7 No 4 0.008 0.22 1.03 0.006 ⁇ 0.000 5 34.76 49.56 6.48 0.12 0.18 41.6 54.0 57.6
  • CPT corrosion pitting temperature

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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)
EP19724876.8A 2018-05-23 2019-05-23 New austenitic alloy Active EP3797179B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18173865 2018-05-23
PCT/EP2019/063297 WO2019224287A1 (en) 2018-05-23 2019-05-23 New austenitic alloy

Publications (3)

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EP3797179A1 EP3797179A1 (en) 2021-03-31
EP3797179B1 true EP3797179B1 (en) 2024-01-17
EP3797179C0 EP3797179C0 (en) 2024-01-17

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EP19724876.8A Active EP3797179B1 (en) 2018-05-23 2019-05-23 New austenitic alloy

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US (1) US20210079499A1 (ja)
EP (1) EP3797179B1 (ja)
JP (1) JP2021525310A (ja)
KR (1) KR20210014631A (ja)
CN (1) CN112154220B (ja)
ES (1) ES2973764T3 (ja)
WO (1) WO2019224287A1 (ja)

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400210A (en) * 1981-06-10 1983-08-23 Sumitomo Metal Industries, Ltd. Alloy for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking
JPS57203736A (en) * 1981-06-10 1982-12-14 Sumitomo Metal Ind Ltd Alloy of high stress corrosion cracking resistance for high-strength oil well pipe
JPS57210938A (en) * 1981-06-17 1982-12-24 Sumitomo Metal Ind Ltd Precipitation hardening type alloy for high strength oil well pipe with superior stress corrosion cracking resistance
US4400211A (en) * 1981-06-10 1983-08-23 Sumitomo Metal Industries, Ltd. Alloy for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking
JPS57207150A (en) * 1981-06-17 1982-12-18 Sumitomo Metal Ind Ltd Precipitation hardening type alloy for high strength oil well pipe with superior stress corrosion cracking resistance
JPS5811736A (ja) * 1981-07-13 1983-01-22 Sumitomo Metal Ind Ltd 耐応力腐食割れ性に優れた高強度油井管の製造法
US4421571A (en) * 1981-07-03 1983-12-20 Sumitomo Metal Industries, Ltd. Process for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking
JP3397169B2 (ja) * 1999-04-22 2003-04-14 住友金属工業株式会社 固体高分子型燃料電池セパレータ用オーステナイト系ステンレス鋼および固体高分子型燃料電池
JP2000328200A (ja) * 1999-05-13 2000-11-28 Sumitomo Metal Ind Ltd 通電電気部品用オーステナイト系ステンレス鋼および燃料電池
CN100554475C (zh) * 2004-06-30 2009-10-28 住友金属工业株式会社 Fe-Ni合金管坯及其制造方法
JP4506958B2 (ja) * 2004-08-02 2010-07-21 住友金属工業株式会社 溶接継手およびその溶接材料
EP2119802B1 (en) * 2007-01-15 2019-03-20 Nippon Steel & Sumitomo Metal Corporation Austenitic stainless steel welded joint and austenitic stainless steel welding material
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CA2780655C (en) * 2009-12-10 2014-04-01 Sumitomo Metal Industries, Ltd. Austenitic heat resistant alloy
EP2455504A1 (en) * 2010-11-19 2012-05-23 Schmidt + Clemens GmbH + Co. KG Nickel-chromium-iron-molybdenum alloy
EP3070184B1 (en) * 2013-11-12 2018-06-13 Nippon Steel & Sumitomo Metal Corporation Ni-Cr ALLOY MATERIAL AND OIL WELL SEAMLESS PIPE USING SAME
KR20190022724A (ko) * 2016-06-28 2019-03-06 신닛테츠스미킨 카부시키카이샤 오스테나이트 합금재 및 오스테나이트 합금관

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Publication number Publication date
KR20210014631A (ko) 2021-02-09
CN112154220A (zh) 2020-12-29
JP2021525310A (ja) 2021-09-24
EP3797179A1 (en) 2021-03-31
CN112154220B (zh) 2022-07-08
US20210079499A1 (en) 2021-03-18
EP3797179C0 (en) 2024-01-17
ES2973764T3 (es) 2024-06-24
WO2019224287A1 (en) 2019-11-28

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