EP4547882A1 - Austenitic stainless steel and method for producing a strip product thereof - Google Patents

Austenitic stainless steel and method for producing a strip product thereof

Info

Publication number
EP4547882A1
EP4547882A1 EP23733932.0A EP23733932A EP4547882A1 EP 4547882 A1 EP4547882 A1 EP 4547882A1 EP 23733932 A EP23733932 A EP 23733932A EP 4547882 A1 EP4547882 A1 EP 4547882A1
Authority
EP
European Patent Office
Prior art keywords
stainless steel
austenitic stainless
equal
less
hydrogen
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23733932.0A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ulrika BORGGREN
Tomas Antonsson
Christina HARALDSSON
Ulf KIVISÄKK
Anna FALLBERG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alleima Striptech AB
Original Assignee
Alleima Striptech AB
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
Application filed by Alleima Striptech AB filed Critical Alleima Striptech AB
Publication of EP4547882A1 publication Critical patent/EP4547882A1/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26Methods of annealing
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236Cold rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273Final recrystallisation annealing
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt

Definitions

  • the present disclosure relates in general to an austenitic stainless steel. More specifically, the present disclosure relates in general to an austenitic stainless steel suitable for use in hydrogen storage applications. The present disclosure also relates in general to a method for producing a product of the austenitic stainless steel. BACKGROUND
  • the efforts made within the automotive industry to reduce harmful emissions has led to an increased interest in development of vehicles which are, at least in part, powered by hydrogen as fuel.
  • a fuel cell vehicle In addition to requiring storage of hydrogen onboard such vehicles, this also means that hydrogen needs to be stored at for example hydrogen fueling stations.
  • Hydrogen may be stored physically as either a gas or a liquid. Storage of hydrogen as a gas typically requires high-pressure tanks, and may be achieved at ambient temperatures. In the case of liquid form, hydrogen may be stored in pure liquid form or in cryo-compressed form, wherein both alternatives require storage at very low temperatures. Hydrogen may alternatively be stored by usage of solids, either by adsorption of hydrogen on surfaces of the solid or by absorption of hydrogen in such a solid. However, storage of hydrogen by usage of solids increases the weight of the storage and thus the vehicle, and/or may increase the necessary size of the storage container, and is therefore often not desirable. Components to be used in conjunction with storage in the form of hydrogen gas, i.e.
  • components configured to contain and/or be exposed to hydrogen gas may be constructed of stainless steel.
  • One of the most important properties when selecting which stainless steel to use for such components is the stainless steel’s resistance to hydrogen embrittlement.
  • Hydrogen embrittlement is a phenomenon that may occur when a steel is exposed to hydrogen diffusing into the steel in combination with stresses in the steel. Hydrogen embrittlement may lead to loss of ductility and/or toughness and a reduction in load bearing capability of the steel, even at stress levels below the yield strength of the steel. Furthermore, hydrogen embrittlement may lead to sudden development of cracks without any warning, and may thus lead to catastrophic failure. It is well known that ferritic and duplex stainless steels are susceptible to hydrogen embrittlement.
  • martensitic stainless steels also have a relatively low resistance to hydrogen embrittlement. Therefore, it appears that austenitic stainless steels are the most promising candidates.
  • austenitic stainless steels In addition to high resistance to hydrogen embrittlement, it is also desired that the austenitic stainless steel has a high tensile strength in order to resist high pressures. Moreover, higher tensile strengths may enable reduced thickness of the steel and thereby also a reduction of weight of the components, which is important within the automotive industry.
  • the austenitic stainless steel needs to have sufficient properties to be used within the temperature range of from -50 °C to + 85°C in order to be a suitable option.
  • An austenitic stainless steel used in these types of applications today is SS 316L because of its resistance to hydrogen embrittlement.
  • SS 316L has a relatively low tensile strength and may therefore not always be a suitable option.
  • EP 1605073 A1 discloses another example of an austenitic stainless steel intended to be used in high- pressure hydrogen gas environments.
  • US 2017/314092 A1 discloses an austenitic stainless steel described to have high strength as well as good hydrogen embrittlement resistance.
  • SUMMARY The object of the present invention is to provide an austenitic stainless steel with high tensile strength and good hydrogen embrittlement resistance such that it is suitable for hydrogen storage applications. The object is achieved by the subject-matter of the appended independent claim(s).
  • an austenitic stainless steel has the following composition, in percent by weight (wt.-%): C equal to or less than 0.06, Si 0.1 – 1, Mn 3 – 5, Cr 20.5 – 23.5, Ni 11 – 15, Mo 1 – 4, Nb 0.50-0.70, N 0.40-0.60, P equal to or less than 0.050, S equal to or less than 0.005, optionally W equal to or less than 3, optionally Co equal to or less than 0.50, optionally V equal to or less than 0.30, optionally Cu equal to or less than 0.30, optionally B equal to or less than 0.005, optionally Al equal to or less than 0.25, optionally one of Ca or Mg equal to or less than 0.05 or REM equal to or less than 0.5 balance consisting of Fe and normally occurring impurities; wherein the composition fulfils the criterion [wt.-% Mo]+2*[wt.-% W] ⁇ 3.
  • the austenitic stainless steel according to the present disclosure has a high tensile strength in combination with an excellent hydrogen embrittlement resistance. It is furthermore possible to obtain very good toughness and weldability. This makes this austenitic stainless steel an excellent candidate for use in components configured to contain and/or be exposed to hydrogen gas and/or liquid hydrogen.
  • the composition of the austenitic stainless steel fulfils the criterion [wt.-% Mo] + [wt.-% W] ⁇ 3.0. This further contributes to a high tensile strength of the austenitic stainless steel.
  • the composition of the austenitic stainless steel as described above means that the sum of the niobium content and 2.5 times the nitrogen content (i.e.
  • the composition of the austenitic stainless steel may suitably comprise niobium and nitrogen in such amounts that the criterion [wt.-% Nb] + 2.5 *[wt.-% N] ⁇ 1.55 is fulfilled. Thereby, the tensile strength may be further increased.
  • the austenitic stainless steel may suitably be in a solution annealed condition. When in a solution annealed condition, the austenitic stainless steel according to the present disclosure may have a tensile strength of at least 930 MPa.
  • the austenitic stainless steel according to the present disclosure is a Z-phase strengthened stainless steel.
  • the present disclosure further provides a method for producing a product of the austenitic stainless steel as described above.
  • the method comprises: casting a melt having the composition to obtain a cast material, hot working the cast material to an intermediate product, cold working the intermediate product to intended final thickness, or intended final diameter, of the product, and solution annealing the cold worked product at a temperature above 1000 ⁇ C.
  • the solution annealing of the cold worked product is performed at a temperature equal to or above 1050 ⁇ C, preferably equal to or above 1080 ⁇ C.
  • the present disclosure also relates to the use of the above described austenitic stainless steel for constructing a component adapted to contain and/or be exposed to an environment comprising, or consisting of, hydrogen gas and/or liquid hydrogen.
  • the component may for example be a container configured for storing pressurized hydrogen gas, a valve in an arrangement for storing or transporting pressurized hydrogen gas, or another component of an arrangement for storing or transporting pressurized hydrogen gas (for example a conduit, a pipe, a tube or a machined part).
  • the component may be a container configured for storage of hydrogen in pure liquid or cryo-compressed form, or a component of an arrangement for storing or transporting of hydrogen in liquid or cryo-compressed form.
  • the present disclosure also relates to a component adapted to contain and/or be exposed to hydrogen gas and/or liquid hydrogen, in particular pressurized hydrogen gas, said component being constructed of the austenitic stainless steel described hereinabove or hereinafter.
  • Fig.1 illustrate tensile strength, as a function of [wt.-% Nb]+2.5*[wt.-% N], of solution annealed samples according to experimental results
  • Fig.2 illustrates the effect of the sum of [wt.-% Mo] and [wt.-% W] as well as [wt.-% Nb]+2.5*[wt.-% N] on tensile strength of solution annealed samples according to experimental results
  • Fig.3 shows a SEM image of a sample of an austenitic stainless steel according to the present disclosure when annealed at 965 °C
  • Fig.4 shows a SEM image of a sample of the same austenitic stainless steel as shown in Figure
  • the austenitic stainless steel may also be used in other forms, such as bars, tubes, or forgings, if desired. Such bars may be extruded bars or rolled bars. Similarly, such tubes may be extruded tubes or rolled tubes. Manufacturing of for example storage containers from stainless steel strips requires welding. It is therefore important that the present austenitic stainless steel has a good weldability. This may be achieved if the austenitic stainless steel is in solution annealed condition. Therefore, the present austenitic stainless steel has been developed with the aim to obtain a high strength and a good hydrogen embrittlement resistance when being in solution annealed condition.
  • the austenitic stainless steel has a high impact toughness in order to avoid that the material cracks if subjected to sudden impact, such as in a collision. Furthermore, the austenitic stainless steel should be able to retain a good balance between the above-mentioned properties within the temperature range of -50 °C to at least +85 °C to make it a truly appropriate candidate for components associated with storage of pressurized hydrogen gas.
  • the austenitic stainless steel according to the present disclosure is primarily developed for use in products associated with storage of high-pressure hydrogen gas at ambient temperatures (here meaning temperatures in the range of -50 °C to at least +85 °C), the austenitic stainless steel is also suitable for use in cryo-applications.
  • the austenitic stainless steel as described herein may also be used in a component (such as a tank, a pipe, a tube or a valve) of an arrangement for storage of hydrogen in pure liquid form or in cryo-compressed form.
  • a component such as a tank, a pipe, a tube or a valve
  • an austenitic stainless steel capable of forming thermodynamically stable Z-phase is provided.
  • Z-phase may be described as a stochiometric phase of niobium, chromium and nitrogen.
  • vanadium may also be enriched in the Z-phase.
  • an austenitic stainless steel which may easily be welded and which, in a solution annealed condition, has the following properties: - tensile strength of at least 930 MPa, suitably at least 935 MPa, when tested according to SS- EN ISO 6892-1 at room temperature, - impact toughness (Charpy-V) at -50 °C of at least 25 J, suitably above 40 J, when tested according to SS-EN ISO 148-1, and - a resistance to hydrogen embrittlement, represented by a ratio of reduction in area between hydrogen charged and inert environment, of equal to or above 0.90, evaluated through Slow Strain Rate Testing (SSRT), at a temperature of 4°C and with a strain rate of 1 x 10 -5 s -1 , with electrochemical charging, wherein electrochemical charging is performed in 0.5 M H 2 SO 4 purged with N 2 with a cathodic current density of 5 mA/cm 2 applied and in
  • the austenitic stainless steel comprises at least 0.1% Si.
  • silicon is present in an amount of at least 0.2 %.
  • excessive contents of silicon may lead to precipitation of unwanted intermetallic phases, such as sigma phase. Presence of sigma phase may for example lead to a reduction of hot workability and should therefore be avoided.
  • the austenitic stainless steel comprises at most 1 % Si.
  • silicon is present in an amount of equal to or less than 0.6 %. More preferably, silicon is present in an amount of equal to or less than 0.45 %.
  • Manganese is an austenite stabilizing element and reduces the risk of forming ferrite that can form intermetallic phases after cooling. Manganese contributes to increased strength as well as improved ductility and toughness. Moreover, manganese is a less expensive alloying element than nickel. An increase of manganese also contributes to an increase in solubility of nitrogen in austenitic stainless steels and may thereby contribute to an increased strength. Therefore, the austenitic stainless steel according to the present disclosure comprises equal to or more than 3 % Mn.
  • manganese is present in an amount of equal to or more than 3.2 %. In the present austenitic stainless steel, manganese may be present in an amount of equal to or more than 3.5 %. Too high contents of manganese may in some cases have a negative impact on the weldability of the austenitic stainless steel and/or the corrosion resistance. Furthermore, a manganese content of above 5 % is not needed and the present austenitic stainless steel therefore comprises equal to or less than 5 % manganese. In the present austenitic stainless steel, manganese may be present in an amount of equal to or less than 4.6 %, or equal to or less than 4.4 %.
  • Chromium is an element added to provide sufficient corrosion resistance in austenitic stainless steels. Furthermore, chromium contributes to the possibility of adding the desired amount of nitrogen to the austenitic stainless steel as it increases the solubility of nitrogen. Furthermore, chromium contributes to the formation of Z-phase and should therefore be present in a relatively high amount. Therefore, the austenitic stainless steel comprises at least 20.5 % Cr.
  • the austenitic stainless steel of the present disclosure may comprise at least 21 % Cr, such as at least 21.5 % Cr.
  • too high contents of chromium increase the risk for formation of unwanted intermetallic phases which may lead to a decrease of ductility and/or toughness.
  • chromium is present in an amount of at most 23.5 %.
  • the upper limit for the chromium content may be 23 %.
  • Chromium may according to one alternative be present in an amount of at most 22.8 %.
  • Nickel (Ni): 11 – 15 % Nickel improves the austenite stability and results in low contents of ferrite. Ferrite may form intermetallic phases during cooling which reduces impact toughness and hydrogen embrittlement resistance and is therefore not desirable. Nickel also contributes to increased ductility. Therefore, the austenitic stainless steel comprises at least or equal to 11 % nickel.
  • nickel is present in an amount of equal to or more than 12 %, or in an amount of equal to or more than 12.5 %.
  • nickel is a relatively expensive alloying element and additions above 15 % are not needed in the present austenitic stainless steel. Too high contents of nickel may also reduce the tensile strength. Therefore, nickel is present in an amount of equal to or less than 15 %. Suitably, nickel may be present in an amount of equal to or less than 14 %, such as in an amount of equal to or less than 13.5 %.
  • the present austenitic stainless steel comprises equal to or more than 1 % Mo.
  • molybdenum is present in an amount of equal to or more than 1.2 %.
  • the austenitic stainless steel needs to comprise enough solution strengthening elements to obtain sufficient strength. Therefore, the composition at least needs to fulfil the criterion of [wt.-% Mo]+2*[wt.-% W] ⁇ 3.
  • molybdenum is present in an amount of at least 3 %. Too high contents of molybdenum may however lead to a decrease in ductility and should therefore be avoided. Therefore, molybdenum is present in an amount of equal to or less than 4 %. Suitably, molybdenum is present in an amount of equal to or less than 3.2 %. In case tungsten is present in a sufficient amount to fulfil the above criterion, molybdenum may be present in an amount of equal to or less than 2.0 %.
  • Niobium is an essential element to the austenitic stainless steel according to the present disclosure as it contributes to formation of Z-phase and thereby the strength.
  • niobium is present in an amount of at least 0.50 %, preferably in an amount of above 0.50 %.
  • Such amounts of niobium are considerably higher than what is added to conventional austenitic stainless steels for the purpose of forming carbides and/or nitrides (including carbonitrides).
  • niobium is added for forming Z- phase, thus niobium is not added for the purpose of forming nitrides and/or carbides.
  • niobium is present in an amount of equal to or above 0.51 %.
  • the presence of niobium and nitrogen in the austenitic stainless steel according to the present disclosure means that the austenitic stainless steel fulfills the criterion of [wt.-% Nb]+2.5*[wt.-% N] being equal to or above 1.5. It has been found that this criterion is important for achieving the high tensile strength since it reflects the contribution of the formed Z-phase based on the stochiometric composition thereof.
  • Nitrogen may also contribute to solution strengthening. Therefore, nitrogen is present in an amount of equal to or more than 0.40 %. Suitably, nitrogen is present in an amount of equal to or more than 0.42 %. As mentioned above with regard to niobium, it is preferred that the austenitic stainless steel comprises nitrogen in an amount such that the criterion [wt.-% Nb]+2.5*[wt.-% N] ⁇ 1.55 is fulfilled. However, too high amounts of nitrogen may lead to formation of chromium nitrides, which reduces the ductility, which will cause an increase in the deformation hardening and thus an increase in needed forces during cold working. The latter may result in a need for intermediate annealing during cold working, which may increase the production costs.
  • tungsten has a similar contribution to the strength of the steel when used as a replacement of molybdenum as described above, tungsten has the advantage of resulting in a lower risk of formation of sigma phase compared to molybdenum.
  • a reduced amount of sigma phase leads to more atoms available for solution strengthening of the austenitic stainless steel and is therefore advantageous. Therefore, additions of tungsten may lead to easier process control during manufacture of the present austenitic stainless steel compared to if only molybdenum is present.
  • the austenitic stainless steel needs to comprise a sufficient amount of solution strengthening elements as it has been found that if the total sum of the molybdenum content and the tungsten content is equal to or above 3.0, very high tensile strength may be achieved. Therefore, according to embodiments, the austenitic stainless steel fulfills the criterion [wt.-% Mo] + [wt.-% W] ⁇ 3.0.
  • the austenitic stainless steel comprises equal to or above 1 % of W.
  • the austenitic stainless steel comprises at least 1.4 % tungsten. However, too high amounts of tungsten may negatively affect the properties of the present steel and should therefore be avoided.
  • Copper (Cu) optionally equal to or less than 0.30 %
  • the austenitic stainless steel does not need to comprise copper, but additions of equal to or less than 0.30 % may be allowed without negatively affecting the properties. Copper is an austenite stabilizing element and may in some cases be added for the purpose of increasing strength. However, higher amounts of copper may lead to a risk for formation of unwanted intermetallic phases and should therefore be avoided. It should here also be noted that, even if not purposively added, copper may still be present as an impurity as a result of the raw material used for producing the austenitic stainless steel. Suitably, the copper content is equal to or lower than 0.25 %.
  • the austenitic stainless steel does not need to comprise boron, but boron may be added to improve the hot ductility. It can also be added as a grain refiner and thereby increasing the strength of the austenitic stainless steel. However, too high contents should be avoided so as to not adversely affect hot workability. If added, boron may be present in amounts equal to or less than 50 ppm, preferably equal to or less than 30 ppm. Aluminium (Al): optionally equal to or less than 0.25 % The austenitic stainless steel does not need to comprise aluminum, but aluminium may be added as a deoxidation agent during steel production.
  • Normally occurring impurities is herein intended to mean both impurities and trace elements.
  • austenitic stainless steels do not comprise more than about 1.5 wt.-% in total, usually at most about 1 wt.-% in total, of normally occurring impurities.
  • a normally occurring impurity is phosphorus (P). Too high contents of phosphorus may adversely affect for example hot workability and toughness. Therefore, the phosphorus content should suitably be equal to or less than 0.050 %, preferably equal to or less than 0.030 %.
  • S sulfur
  • Too high contents of sulfur may for example deteriorate hot workability and/or toughness as well as weldability.
  • the sulfur content should suitably be equal to or less than 0.005 %, preferably equal to or less than 0.003 %.
  • Another examples of normally occurring impurities are Tin (Sn), Arsenic (As), Lead (Pb), Bismuth (Bi) and Titanium (Ti).
  • solution annealing is performed at a temperature equal to or less than 1200 °C, such as equal to or less than 1150 °C, for the purpose of limiting excessive grain growth and reduced tensile strength. Higher temperatures are however also possible in case of relatively short duration of the solution annealing step. The duration of the solution annealing step depends on the dimension of the austenitic stainless steel.
  • a suitable duration of solution annealing could typically be 1 to 5 minutes per mm of the thickness/diameter of the cold worked product, such as 1 to 2 minutes per mm of the thickness/diameter of the cold worked product, although the present disclosure is not limited thereto.
  • the suitable maximum temperature of the solution annealing step is dependent of the duration of solution annealing. For example, solution annealing of a strip product having a thickness of less than 10 mm at about 1200 °C with a relatively long duration of about 1 hour may lead to a reduction of tensile strength in the order of 50-100 MPa compared to the maximum obtainable tensile strength according to the present method.
  • the method comprises: - casting a melt, having the above described composition, to obtain a cast material; - hot rolling the cast material to an intermediate hot rolled product, - cold rolling the intermediate hot rolled product to intended final thickness of the strip product, and - solution annealing the cold rolled product at a temperature above 1000 °C, preferably at a temperature equal to or above 1050 °C (more preferably at a temperature equal to or above 1080 °C).
  • Grain size number was determined according to ASTM E112. Microstructure characterization The microstructure was assessed by Scanning Electron Microscopy (SEM), combined with electron backscatter diffraction (EBSD). The number of Z-phase particles per ⁇ m 2 was determined by image analysis performed at pictures obtained in SEM at 10000X magnification in BSE mode. For all heats, the number of particles in the size range 0.05 to 1 ⁇ m was determined, for some heats also the number of particles larger than 1 ⁇ m were determined. The results obtained from the above described tests are presented in Table 2.
  • FIG. 3 shows a SEM image of a sample of Heat No.12 when annealed at 965 °C
  • Figure 4 shows a SEM image of a sample of Heat No.12 when solution annealed at 1100 °C. The images shown in Figures 3 and 4 are taken at the same magnification.
  • the image shown in Figure 3 clearly shows presence of chromium nitrides, which are the dark particles illustrated by arrow A, as well as Z-phase particles as illustrated by arrow B. Chi phase is present at the grain boundaries, said chi phase visible as small white particles illustrated by arrow C.
  • the image shown in Figure 4 representing the solution annealed sample, does not show any presences of nitrides or other intermetallic phases. There is however a presence of Z-phase, which are the light particles, illustrated by arrow D.
  • the assessment of the microstructure showed that all samples being subjected to solution annealing were essentially free from nitrides and intermetallic phases.
  • the austenitic stainless steel according to the present disclosure has a good weldability when solution annealed as described above.
  • each of the samples subjected to annealing at 965 °C had intermetallic phases present. More specifically, Heat Nos.10 and 11 contained sigma phase, and Heats Nos.12-14 contained chi phase, after annealing at 965 °C.
  • Heat Nos.1-9 have a lower impact toughness than Heat Nos. 10-14 in the solution annealed condition. This is believed to be due to the lower temperature during solution annealing (1065 °C for Heats No.1-9, compared to 1100 °C for Heat Nos.10-14).
  • Rolling billets were produced from the bar, and hot and cold rolled to 7 mm thickness. Thereafter, the cold rolled 316L-1 and 316L-2 materials were subjected to solution annealing at 1100 °C followed by water quenching. The resistance to hydrogen embrittlement of Heat No.6, as well as Heat No.2, 316L-1 and 316L-2, were tested during Slow Strain Rate Testing (SSRT) at -40 °C and 87.5 MPa H 2 . A strain rate of 5 x 10 -5 s -1 was used, and the testing was performed in a vessel with cooling blocks clamped on the specimens, which were cooled with liquid nitrogen. The testing was performed according to ASMT G- 129.
  • Heat No.6 has a higher resistance to hydrogen embrittlement than both Heat No.2 and 316L-1. Moreover, the resistance to hydrogen embrittlement of Heat No.6 is comparable to the resistance to hydrogen embrittlement of 316L-2. Furthermore, resistance to hydrogen embrittlement of Heat No.6, Heat No.12, 316L-1 and 316L-2 were evaluated through Slow Strain Rate Testing (SSRT) with electrochemical charging. The SSRT with electrochemical charging was performed in 0.5 M H 2 SO 4 purged with N 2 at 4°C with a cathodic current density of 5 mA/cm 2 applied.
  • SSRT Slow Strain Rate Testing
  • 316L-1 has a tensile strength of 591 MPa and 316-2 has a tensile strength of 566 MPa (tested according to SS-EN ISO 6892-1 at room temperature) when produced as described above.
  • the results of the hydrogen embrittlement tests of the herein described austenitic stainless steel show that the reduction of area when subjected to hydrogen charging is similar to in the inert environment. The ratio between the hydrogen charged specimens and the inert environment is close to 1. Normally a ratio of 0.90 or above is considered as no effect of hydrogen embrittlement being observed. No brittle failure or secondary cracks were observed in the tested samples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)
EP23733932.0A 2022-06-29 2023-06-16 Austenitic stainless steel and method for producing a strip product thereof Pending EP4547882A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22181824 2022-06-29
PCT/EP2023/066337 WO2024002728A1 (en) 2022-06-29 2023-06-16 Austenitic stainless steel and method for producing a strip product thereof

Publications (1)

Publication Number Publication Date
EP4547882A1 true EP4547882A1 (en) 2025-05-07

Family

ID=82483194

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23733932.0A Pending EP4547882A1 (en) 2022-06-29 2023-06-16 Austenitic stainless steel and method for producing a strip product thereof

Country Status (4)

Country Link
EP (1) EP4547882A1 (https=)
JP (1) JP2025522617A (https=)
CN (1) CN119365621A (https=)
WO (1) WO2024002728A1 (https=)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117660849B (zh) * 2024-01-31 2024-06-04 成都先进金属材料产业技术研究院股份有限公司 一种控磷00Cr21Ni13Mn5N高氮奥氏体不锈钢及其生产方法
JP7546803B1 (ja) 2024-02-19 2024-09-06 日本冶金工業株式会社 オーステナイト系ステンレス鋼帯または鋼板およびそれらの製造方法、ならびに、高圧水素ガス用機器または液体水素用機器

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3304001B2 (ja) * 1993-07-09 2002-07-22 日立金属株式会社 耐孔食性の優れたオーステナイト系ステンレス鋼およびその製造方法
KR100617465B1 (ko) 2003-03-20 2006-09-01 수미도모 메탈 인더스트리즈, 리미티드 고압 수소 가스용 스테인레스강, 그 강으로 이루어지는 용기 및 기기
CA2839128C (en) * 2011-07-06 2016-08-09 Nippon Steel & Sumitomo Metal Corporation Austenitic steel welded joint
EP3112082B1 (en) * 2014-02-26 2018-08-15 Nippon Steel & Sumitomo Metal Corporation Method for producing welded joint
CA2944847C (en) * 2014-04-17 2019-07-16 Nippon Steel & Sumitomo Metal Corporation Austenitic stainless steel and method for producing the same
WO2016068009A1 (ja) 2014-10-29 2016-05-06 新日鐵住金株式会社 オーステナイトステンレス鋼及びその製造方法
CA2997895C (en) * 2015-09-30 2020-03-10 Nippon Steel Corporation Austenitic stainless steel and method of manufacturing austenitic stainless steel
US20190112694A1 (en) * 2016-04-07 2019-04-18 Nippon Steel & Sumitomo Metal Corporation Austenitic Stainless Steel Material

Also Published As

Publication number Publication date
CN119365621A (zh) 2025-01-24
JP2025522617A (ja) 2025-07-15
WO2024002728A1 (en) 2024-01-04

Similar Documents

Publication Publication Date Title
CA2824463C (en) High-strength austenitic stainless steel for high-pressure hydrogen gas
CN106795606B (zh) 奥氏体不锈钢及其制造方法
US7749431B2 (en) Stainless steel for high-pressure hydrogen gas
EP3524705B1 (en) Ni-cr-fe alloy
EP1605072B1 (en) Stainless steel for high pressure hydrogen gas, vessel and equipment comprising the steel
KR100663720B1 (ko) 오스테나이트계강 용접 조인트
EP3575427B1 (en) Dual-phase stainless clad steel and method for producing same
EP1471158A1 (en) Austenitic stainless steel
EP3693486B1 (en) Austenitic stainless steel welding metal and welded structure
WO2024002728A1 (en) Austenitic stainless steel and method for producing a strip product thereof
JP7761861B2 (ja) オーステナイト系ステンレス鋼及びオーステナイト系ステンレス鋼の製造方法
CA3159934A1 (en) Alloy
JP2000204434A (ja) 高温強度に優れたフェライト系耐熱鋼およびその製造方法
JPH07150289A (ja) 高温強度に優れたCr系耐熱鋼
WO2022112607A1 (en) Steel composition, wrought article and manufacturing method of a seamless pressure vessel for compressed gas
JP7421054B2 (ja) オーステナイト系耐熱合金部材
JP2020084265A (ja) オーステナイト系耐熱合金及びオーステナイト系耐熱合金部品
WO2025012182A1 (en) A duplex stainless steel and use thereof
KR20250047201A (ko) 오스테나이트계 스테인레스강 및 내수소성 부재
KR20250154483A (ko) 오스테나이트계 내열 합금 부재
JP2020164896A (ja) オーステナイト系耐熱合金部材

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20250129

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)