US20100193083A1 - Hydrogen-resistant high strength material and method for producing the same - Google Patents

Hydrogen-resistant high strength material and method for producing the same Download PDF

Info

Publication number
US20100193083A1
US20100193083A1 US12/697,506 US69750610A US2010193083A1 US 20100193083 A1 US20100193083 A1 US 20100193083A1 US 69750610 A US69750610 A US 69750610A US 2010193083 A1 US2010193083 A1 US 2010193083A1
Authority
US
United States
Prior art keywords
hydrogen
hydrogen embrittlement
high strength
resistant high
strength material
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.)
Abandoned
Application number
US12/697,506
Inventor
Hironori KAMOSHIDA
Shinya Imano
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.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
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 Hitachi Ltd filed Critical Hitachi Ltd
Assigned to HITACHI, LTD. reassignment HITACHI, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAMOSHIDA, HIRONORI, IMANO, SHINYA
Publication of US20100193083A1 publication Critical patent/US20100193083A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • 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
    • 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
    • C21D6/001Heat treatment of ferrous alloys containing 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 by deformation combined with, or followed by, heat treatment
    • C21D8/10Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • 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
    • C21D9/08Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C21D9/14Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon

Definitions

  • the present invention relates to a hydrogen-resistant high strength material and a method for producing the same.
  • Hydrogen energy is attracting attention since it does not emit carbon dioxide (CO 2 ) having a high greenhouse effect responsible for global warming. Hydrogen energy results in discharging only water during usage thereof (after combustion). Accordingly, hydrogen has been studied as alternative energy of fossil fuels such as conventional gasoline or natural gas.
  • Metal materials are generally used for high-pressure containers, pipings, reactors and so on for storage, transportation and usage of the hydrogen gas.
  • metal materials are in general likely to be subjected to embrittlement under an environment that is exposed to hydrogen. The embrittlement problem is more remarkable as the material becomes to have higher strength.
  • an on-vehicle container of a high-pressure hydrogen container-mounted vehicle has been designed until recently to have a filling pressure of about 35 MPa.
  • the filling pressure is being attempted to increase up to about 70 MPa because of its short running distance.
  • the used container and piping are necessarily increased in thickness to obtain necessary strength, resulting in such a demerit that a total weight increases.
  • a Coriolis flowmeter is used as an example of a high-pressure hydrogen flowmeter of a hydrogen dispenser that is used in a hydrogen station.
  • a flow rate is measured by detecting a vibration caused when hydrogen gas flows in a piping bent in a U-shape. The thinner the piping is formed, the higher the accuracy is. Accordingly, it is impossible to secure the strength by making the thickness larger.
  • the material itself has high strength and excellent hydrogen embrittlement resistance.
  • JIS SUS316L (stainless steel) is used as a material for high-pressure hydrogen containers or pipings.
  • JIS SUH660 (superalloy generally referred to as A286) is used for components necessary to have tensile strength in particular. These materials are superior to other alloys in the mechanical characteristics such as the hydrogen embrittlement resistance in hydrogen or when hydrogen is absorbed. Still furthermore, it is studied to adopt high strength martensitic stainless steel such as JIS SCM435 in a storage tank.
  • the tensile strength is about 600 MPa for JIS SUS316L and about 1000 MPa for JIS SUH660. Accordingly, these materials cannot be applied to members requiring greater strength.
  • An outer circumference of a storage tank that uses martensitic stainless steel is reinforced with carbon fiber to deal with the embrittlement.
  • JP-A-2007-126688 discloses an austenitic high-Mn contained stainless steel that is superior to JIS SUS316L in hydrogen embrittlement resistance susceptibility and has low concentrations of Mo and Ni.
  • the austenitic high-Mn contained stainless steel can reduce amounts of Mo and Ni in comparison with JIS SUS316L and is advantageous in production at a low cost.
  • the tensile strength is substantially same as that of JIS SUS316L.
  • JP-A-2008-69435 di closes a high-strength steel excellent in the hydrogen embrittlement resistance, which contains a strain-induced martensitic structure therein and a part of or an entirety of a surface of which is made mainly art austenitic structure. It also discloses a method for producing the high-strength steel by induction-heating a surface of a steel having a strain-induced martensitic structure to cause a reverse transformation of the strain-induced martensitic structure on the surface into an austenitic structure.
  • these high-strength steels are based on an austenitic stainless steel, it is considered that the tensile strength is at most about 1000 MPa and applications to materials having a shape other than a round bar are difficult.
  • SP-A-7-278768 discloses a method for reducing the hydrogen embrittlement in order to effectively reduce or inhibit hydrogen embrittlement of alloy members such as a rocket engine that uses hydrogen as a fuel.
  • the method includes a step of irradiating a laser beam on a whole surface, which has been aged, to heat the irradiated surface to a temperature higher than the solvus temperature and dissolve precipitates generated in the alloy member by aging treatment, followed by quenching the irradiated portion to form a hydrogen embrittlement resistant portion that is devoid of precipitates on a surface of the irradiated portion and homogeneous in a structure.
  • This is a method where a ⁇ ′-phase that is a precipitation strengthening phase is locally dissolved with heating.
  • a saluted layer devoid of the ⁇ ′-phase may have decreased tensile strength.
  • JP-A-2006-9982 discloses a high-pressure container for high-pressure hydrogen, which includes a container body and a cap hermetically disposed to one end or both ends of the container body.
  • the container body is made of a steel and a metal film is coated on an inner surface of the container for inhibiting hydrogen from intruding.
  • the metal film for inhibiting hydrogen from intruding is spalled, the performance thereof is rapidly deteriorated.
  • the objective of the present invention is to provide a hydrogen embrittlement resistant piping having both hydrogen embrittlement resistance and high tensile strength, and inhibiting rapid deterioration caused by deterioration of surface characteristics and by spalling of a coating, and a method for producing the same.
  • a hydrogen-resistant high strength material according to the invention is made of a Ni-based alloy or an Fe—Ni-based alloy and includes an aged portion and a hydrogen embrittlement suppressing layer that is to be exposed to hydrogen.
  • the hydrogen embrittlement suppressing layer has a hydrogen embrittlement index of not less than 0.9.
  • the hydrogen embrittlement index is defined as a ratio of an elongation after hydrogen charging in relation to an elongation before hydrogen charging.
  • the aged portion has a tensile strength exceeding 1000 MPa.
  • a method for producing a hydrogen-resistant high strength material according to the invention includes the steps of applying an aging heat treatment to an entirety of a material made of a Ni-based alloy or an Fe—Ni-based alloy to form an aged portion; and applying a solution treatment locally to the aging-heat-treated material to form a hydrogen embrittlement suppressing layer.
  • a method for producing a hydrogen-resistant high strength material according to the invention includes the steps of applying a solution treatment to an entirety of a material made of a Ni-based alloy or an Fe—Ni-based alloy; and after the solution treatment step, while keeping a portion where a hydrogen embrittlement suppressing layer is formed cooled, applying an aging heat treatment to other portion to form an aging-treated portion.
  • an inner layer of a hydrogen embrittlement resistant piping bears hydrogen embrittlement resistance and an outer layer thereof bears tensile strength. Accordingly, the hydrogen embrittlement resistance and high tensile strength can be obtained.
  • FIG. 1 is a schematic sectional diagram showing a hydrogen embrittlement resistant piping of the invention
  • FIG. 2 is a graph showing a distribution of an amount of precipitated ⁇ ′-phase in a radial direction of the hydrogen embrittlement, resistant piping of the invention.
  • FIG. 3 is a graph showing hydrogen embrittlement index and relative strength in relation to an amount of precipitated ⁇ ′-phase of the hydrogen embrittlement resistant piping of the invention.
  • the present invention relates to a hydrogen embrittlement resistant piping (metal piping for hydrogen infrastructure) and a method for producing the same.
  • a ⁇ ′-phase precipitation strengthened Ni-based alloy or Fe—Ni-based alloy is used for a material of a hydrogen embrittlement resistant piping of the invention.
  • the Ni-based alloy or Fe—Ni-based alloy has a face-centered cubic lattice structure (referred to as FCC).
  • FCC face-centered cubic lattice structure
  • the ⁇ ′-phase is an L 1 2 ordered phase that precipitates in a ⁇ -matrix of FCC after the alloy is subjected to the aging heat treatment. That is, the ⁇ ′-phase is an FCC ordered phase finely precipitated in a ⁇ -phase having an FCC solid solution phase as a matrix.
  • a hydrogen embrittlement resistant piping is simply referred to as a piping in some cases.
  • tensile tests are carried out according to a thermal precharging method in high-pressure hydrogen gas with the ⁇ ′-phase precipitation strengthened Ni-based alloy. While the ductility was remarkably deteriorated in a material having high strength by a predetermined heat treatment, the ductility was remarkably inhibited from deteriorating when an amount of precipitated ⁇ ′-phase was reduced by applying the aging heat treatment at a temperature higher than the predetermined heat treatment. Accordingly, it was studied to apply this to a piping for high-pressure hydrogen gas.
  • a crack that becomes a starting point of fatigue or fracture starts from a surface of a material.
  • the hydrogen embrittlement is considered to progress with a fine crack initially formed as a starting point. Accordingly, it is considered effective to inhibit the initial fine crack from occurring.
  • the crack can be inhibited from generating and progressing by imparting the ductility and hydrogen embrittlement resistance only to a surface (the inside of a piping exposed to hydrogen as) to be in contact is gas.
  • FIG. 1 is a schematic sectional view showing a hydrogen embrittlement resistant piping of the invention.
  • a inner surface (inner layer) of a hydrogen embrittlement resistant piping 101 to be exposed to hydrogen is constituted of a hydrogen embrittlement suppressing layer 1 to be exposed to hydrogen and the outside (outer layer) thereof is constituted of an aging-treated phase 2 .
  • the aging-treated phase 2 may be referred to as an aging-treated portion.
  • the ductility can be maintained when an amount of the ⁇ ′-phase (precipitation amount) of the hydrogen embrittlement suppressing layer 1 is reduced to less than that of the aging-treated layer 2 , as is shown in the drawing.
  • FIG. 2 is a graph schematically showing a distribution of an amount of the ⁇ ′-phase precipitated in a matrix.
  • a horizontal axis in the drawing represents a radial direction of the piping and a vertical axis shows an amount of precipitated ⁇ ′-phase.
  • the amount of precipitated ⁇ ′-phase is highest in the aging-treated layer 2 , that is, the outer phase in FIG. 1 and low in the hydrogen embrittlement suppressing layer 1 , that is, the inner layer in FIG. 1 .
  • the amount of precipitated ⁇ ′-phase is equal to or lower than a limit value.
  • an allowable amount of precipitates in the inner surface is higher than 0% and equal to or less than a predetermined value lower than the limit value.
  • the amount of precipitated ⁇ ′-phase may be referred to as a ⁇ ′-concentration or a ⁇ ′-amount.
  • FIG. 3 is a graph showing a hydrogen embrittlement index and relative tensile strength in relation to a precipitation amount of the ⁇ ′-phase (also referred to as amount of precipitated ⁇ ′-phase) in a hydrogen embrittlement resistant piping of the invention.
  • a horizontal axis represents a precipitation amount of the ⁇ ′-phase and a vertical axis represents a hydrogen embrittlement index and a relative tensile strength.
  • the hydrogen embrittlement index is calculated from a formula (1) shown below.
  • the relative tensile strength is a relative value of tensile strength of each of the respective materials represented in relation to that of a solution treated material (also referred to as ST (solution treatment) material).
  • the tensile strength of the material can be heightened by increasing an amount of precipitated ⁇ ′-phase, while the hydrogen embrittlement index tends decrease.
  • the drawing shows that the ⁇ ′ concentration is not necessarily require to be zero.
  • the hydrogen embrittlement index has a higher value as the ⁇ ′ amount is smaller. That is, it is found that the ⁇ ′ amount has a permissible amount.
  • a practically usable piping desirably has the hydrogen embrittlement index shown by the formula (1) of not less than 0.9. Accordingly, when the limit ⁇ ′-amount (that is the limit value of amount of precipitated ⁇ ′-phase) where the hydrogen embrittlement index is not less than 0.9 is obtained for every materials, a range where both the tensile strength and the elongation (ductility) of the material are maintained can be set.
  • a material processed previously into a necessary shape is subjected to a solution treatment, by cooling to render an entirety of the piping a solution treated structure that is difficult to cause hydrogen embrittlement.
  • cooling air or cooling water is flowed inside of the piping, and, at the same time therewith, a heat treatment is externally applied, thereby an outer layer of the piping is rendered an aging-treated layer without changing the solution treated structure of an inner layer of the piping.
  • an entire piping is subjected to an aging heat treatment to render the entire piping an aging-treated layer, and an inner surface of the piping is locally heated by laser to dissolve the ⁇ ′-phase to make an amount of precipitated ⁇ ′-phase smaller than that of an outer layer.
  • a hydrogen embrittlement resistant piping having high tensile strength can be provided.
  • a material used in a hydrogen embrittlement resistant piping of the invention is a ⁇ ′-phase precipitation strengthening alloy and has the tensile strength exceeding 1000 MPa owing to a predetermined solution treatment and aging heat treatment of the alloy. This is because an A286 alloy can be used alternatively if the tensile strength is sufficient to be 1000 MPa or less.
  • the tensile strength is desirable to exceed 1200 MPa and more desirable to exceed 1400 MPa. It is appropriate that a hydrogen embrittlement suppressing layer is applied to an inner surface of the piping, that is directly exposed to a hydrogen gas. It is necessary that an amount of precipitated ⁇ ′-phase of the hydrogen embrittlement suppressing layer is larger than 0% and lower than a predetermined amount of the precipitated ⁇ ′-phase in the respective materials. In a completely solution treated structure (0%), the tensile strength is drastically lowered.
  • the upper limit of the amount of precipitated ⁇ ′-phase of the hydrogen embrittlement suppressing layer is preferably that represented by the hydrogen embrittlement index of not less than 0.9 and more preferably not less than 0.98 that shows a degree of embrittlement caused by hydrogen (that is, elongation after hydrogen charging/elongation before hydrogen charging).
  • 0.9 is a value of the hydrogen embrittlement index in A286 and this is because A786 is assumed to correspond to the lower limit of the hydrogen embrittlement index.
  • a thickness of the hydrogen embrittlement suppressing layer (inner layer) defined above is desirably 5 to 30% or less of a thickness of the piping.
  • the thickness the piping is a value obtained by total thicknesses of the inner layer and the outer layer. It can be also said that the thickness of the hydrogen embrittlement suppressing layer is from 5 to 30% of an total thickness obtained by adding a thickness of an aged portion (aging-treated phase) and a thickness of the hydrogen embrittlement suppressing layer. This is because in the case where the thickness of the hydrogen embrittlement suppressing layer is less than 5%, an generated initial crack immediately reaches an outer layer where a ⁇ ′-phase precipitates. When the thickness of the hydrogen embrittlement suppressing layer exceeds 30%, the tensile strength as the piping is largely deteriorated. A range from 10 to 20% is still more preferable.
  • a material to be used is processed into a necessary shape of a piping.
  • the method therefor is not particularly restricted.
  • a local heating device insertable into the inside of the piping such as laser is used to locally heat an inner surface of the piping to form a solid solution so that a ⁇ ′-phase having the predetermined concentration may remain.
  • laser is used to form a solid solution, it is desirable to previously set laser irradiation conditions, such as an output, a focus distance or a scanning speed, to a used material to study conditions capable of forming the hydrogen embrittlement suppressing layer such as mentioned above.
  • a material to be used is processed into a necessary shape of a piping.
  • the processing method is not particularly restricted. Thereafter, the material processed into a piping shape is subjected to a solution treatment, followed by rapidly cooling to impart a solution treated structure to an entire material.
  • cooling air or cooling water as a cooling medium is flowed inside of the piping and the piping is externally heated to apply the aging heat treatment.
  • cooling air for example, compressed air is used and the cooling water is supplied by use of a chiller unit or the like.
  • an electric furnace having capacity capable of uniformly heating a prepared piping raw material is desirable.
  • electromagnetic induction heating or laser may be used.
  • any of the producing methods it is desirable to determine in advance a temperature, a flow rate of the cooling medium and an externally heating temperature while measuring temperatures of an inner surface and an outer surface of the piping.
  • Table 1 shows compositions of samples prepared as Examples.
  • Ni-based alloys A-1 to A-3 and Fe—Ni-based alloy B were prepared.
  • An alloy A-0 is a material having the same composition as that of the alloy A-1 and is obtained by solution treating the alloy A-1.
  • the alloy A-3 is a material having the same composition as that of JIS SUH660 (A286).
  • an alloy B is a material which is improved in heat resistance.
  • the alloys A-1 to A-3 and the alloy B were assigned to Examples 1 to 4 respectively.
  • Ni-based alloys A-1 to A-3 (Examples 1 to 3), three kinds of alloys A-1 to A-3 were prepared by varying compositions of Al and Ti to vary amounts of precipitated ⁇ ′-phase.
  • the heat treatment of the Ni-based alloys A-1 to A-3 was performed at 980° C. for 2 hours and an aging heat treatment was performed at 720° C. for 8 hours.
  • tensile test pieces prepared from these alloys were subjected to the hydrogen charging in a hydrogen gas at 450° C. and under 20 MPa, followed by performing the tensile test at room temperature and in atmosphere, further followed by measuring elongation and tensile strength each of the test pieces.
  • the tensile speed at this time was set at 0.3 mm/min with use of a displacement gauge. Based on measurements, hydrogen embrittlement indices (elongation after hydrogen charging/elongation before hydrogen charging) were calculated.
  • FIG. 3 is a graph showing results of the above-mentioned tensile tests as the hydrogen embrittlement indices and relative tensile strengths in relation to amounts of precipitated ⁇ ′-phase in hydrogen embrittlement resistant pipings.
  • the tensile strengths are represented by relative values or relative strengths where the tensile strength as solution treatment is assigned to 1.
  • the relative tensile strength increases depending on an amount of precipitated ⁇ ′-phase that increases strength.
  • the hydrogen embrittlement index decreases depending on an amount of precipitated ⁇ ′-phase.
  • the embrittlement can be suppressed when the amount of precipitated ⁇ ′-phase is lower than a predetermined value.
  • the upper limit of the amount of precipitated ⁇ ′-phase which can suppress the embrittlement, is about 10% for the alloy A and about 7% for the alloy B. These were defined as the limit values of amounts of precipitated ⁇ ′-phase in the respective alloys.
  • Piping materials having an outer diameter of 10 mm and a thickness of 1.5 mm were prepared with the alloy A-1 and the alloy B.
  • the piping from the alloy A-1 was subjected to a solution treatment at 980° C. for 2 hours and an aging heat treatment at 720° C. for 8 hours.
  • the piping from the alloy B was subjected to a solution treatment at 980° C. for 2 hours and an aging heat treatment at 740° C. for 8 hours.
  • an aging heat treatment is applied at 740° C. for 8 hours, the tensile strength of 1300 MPa class can be imparted for those subjected to an ordinary heat treatment.
  • Each of these pipings was heat-treated by irradiating laser on an inner surface of the piping.
  • the piping of which surface was heat-treated by irradiating laser was sliced into rings to observe a cross-section thereof, and an amount of precipitated ⁇ ′-phase was calculated by image analysis.
  • an amount of precipitated ⁇ ′-phase was 9.6% by average at a position about 300 ⁇ m from an inner surface (referred to as “inside surface”) in a piping of the alloy A-1, and an amount of precipitated ⁇ ′-phase was 1.1% by average in the vicinity of the inner surface of the piping.
  • an outer surface referred to as “outside surface” of the piping, and an amount of precipitated ⁇ ′-phase was 12% that is substantially equal to a value obtained by thermodynamic equilibrium calculation.
  • an amount of precipitated ⁇ ′-phase was 6.2% by average at a position about 300 ⁇ m from the inner surface of a piping of the alloy B, and an amount of precipitated ⁇ ′-phase was 0.9% by average in the vicinity of the inner surface of the piping.
  • an amount of precipitated ⁇ ′-phase was about 20% that is substantially equal to a value obtained by thermodynamic equilibrium calculation.
  • Piping materials having an outer diameter of 10 mm and a thickness of 1.5 mm were prepared from the alloy A-1 and the alloy B.
  • Both of the alloy A-1 and the alloy B were solution treated at 980° C. for 2 hours and thereafter cooled with water to maintain the solution-treated state.
  • the aging heat treatment was performed with cooling the inside of the piping with water as a cooling medium.
  • a piping from the alloy A-1 was subjected to the aging heat treatment in an electric furnace at 730° C. for 8 hours.
  • a piping from the alloy B was subjected to the aging heat treatment in an electric furnace at 755° C. for 8 hours.
  • Thermocouples were attached to inner and outer surfaces of the pipings of both materials, and surface temperatures during the heat treatment were monitored.
  • inner surface temperature, of the alloys A-1 and B were about 583° C. and about 609° C. respectively, and outer surface temperatures thereof were 720° C. and 740° C. respectively.
  • each of the pipings was sliced in rings to observing a structure thereof, followed by calculating amounts of precipitated ⁇ ′-phase by image analysis.
  • an amount of precipitated ⁇ ′-phase was 9% by average at a position about 400 ⁇ m from an inner surface of the piping of the alloy A-1, and an amount of precipitated ⁇ ′-phase was 1.5% by average in the vicinity of the inner surface of the piping.
  • an amount of precipitated ⁇ ′-phase was 12%. This is substantially same value as that obtained by thermodynamic equilibrium calculation.
  • an amount of precipitated ⁇ ′ phase was 6% by average at a position about 350 ⁇ m from an inner surface of the piping of the alloy B, and an amount of precipitated ⁇ ′-phase was 2% by average in the vicinity of the inner surface of the piping. On an outside surface of the piping, an amount of precipitated ⁇ ′-phase was about 20%. This is substantially same value as that obtained by thermodynamic equilibrium calculation.
  • a range of application of the hydrogen embrittlement resistant technology of the invention is not restricted to hydrogen embrittlement resistant pipings.
  • the technology can be applied also to hydrogen producing equipments (reactors) at hydrogen stations, holders (hydrogen tanks (high-pressure containers)), compressors, accumulators, hydrogen dispensers (hydrogen supply equipments), high-pressure hydrogen flowmeter for hydrogen dispenser (such as Coriolis flowmeter), hydrogen vehicles and so on.

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)
  • Manufacturing & Machinery (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

A hydrogen-resistant high strength material made of a Ni-based alloy or an Fe—Ni-based alloy includes an aged portion and a hydrogen embrittlement suppressing layer that is to be exposed to hydrogen. The hydrogen embrittlement suppressing layer has a hydrogen embrittlement index of not less than 0.9, wherein the hydrogen embrittlement index is defined as a ratio of an elongation after hydrogen charging in relation to an elongation before hydrogen charging. The aged portion has a tensile strength exceeding 1000 MPa.

Description

    TECHNICAL FIELD
  • The present invention relates to a hydrogen-resistant high strength material and a method for producing the same.
  • BACKGROUND OF THE INVENTION
  • In recent years, prevention of global warming is noted. Hydrogen energy is attracting attention since it does not emit carbon dioxide (CO2) having a high greenhouse effect responsible for global warming. Hydrogen energy results in discharging only water during usage thereof (after combustion). Accordingly, hydrogen has been studied as alternative energy of fossil fuels such as conventional gasoline or natural gas.
  • In order to promote usage of hydrogen energy, studies and developments for putting fuel cell vehicles and hydrogen vehicles into practical use are under way. As well, developments for building infrastructures such as hydrogen stations are in progress in order to make them widely available.
  • Metal materials are generally used for high-pressure containers, pipings, reactors and so on for storage, transportation and usage of the hydrogen gas. However, metal materials are in general likely to be subjected to embrittlement under an environment that is exposed to hydrogen. The embrittlement problem is more remarkable as the material becomes to have higher strength.
  • For example, an on-vehicle container of a high-pressure hydrogen container-mounted vehicle has been designed until recently to have a filling pressure of about 35 MPa. However, the filling pressure is being attempted to increase up to about 70 MPa because of its short running distance. In this case, the used container and piping are necessarily increased in thickness to obtain necessary strength, resulting in such a demerit that a total weight increases.
  • Furthermore, a Coriolis flowmeter is used as an example of a high-pressure hydrogen flowmeter of a hydrogen dispenser that is used in a hydrogen station. In the Coriolis flowmeter, a flow rate is measured by detecting a vibration caused when hydrogen gas flows in a piping bent in a U-shape. The thinner the piping is formed, the higher the accuracy is. Accordingly, it is impossible to secure the strength by making the thickness larger.
  • From these requirements, it is necessary that the material itself has high strength and excellent hydrogen embrittlement resistance.
  • At present, JIS SUS316L (stainless steel) is used as a material for high-pressure hydrogen containers or pipings. Furthermore, JIS SUH660 (superalloy generally referred to as A286) is used for components necessary to have tensile strength in particular. These materials are superior to other alloys in the mechanical characteristics such as the hydrogen embrittlement resistance in hydrogen or when hydrogen is absorbed. Still furthermore, it is studied to adopt high strength martensitic stainless steel such as JIS SCM435 in a storage tank.
  • However, the tensile strength is about 600 MPa for JIS SUS316L and about 1000 MPa for JIS SUH660. Accordingly, these materials cannot be applied to members requiring greater strength. An outer circumference of a storage tank that uses martensitic stainless steel is reinforced with carbon fiber to deal with the embrittlement.
  • JP-A-2007-126688 discloses an austenitic high-Mn contained stainless steel that is superior to JIS SUS316L in hydrogen embrittlement resistance susceptibility and has low concentrations of Mo and Ni. The austenitic high-Mn contained stainless steel can reduce amounts of Mo and Ni in comparison with JIS SUS316L and is advantageous in production at a low cost. However, the tensile strength is substantially same as that of JIS SUS316L.
  • JP-A-2008-69435 di closes a high-strength steel excellent in the hydrogen embrittlement resistance, which contains a strain-induced martensitic structure therein and a part of or an entirety of a surface of which is made mainly art austenitic structure. It also discloses a method for producing the high-strength steel by induction-heating a surface of a steel having a strain-induced martensitic structure to cause a reverse transformation of the strain-induced martensitic structure on the surface into an austenitic structure. However, since these high-strength steels are based on an austenitic stainless steel, it is considered that the tensile strength is at most about 1000 MPa and applications to materials having a shape other than a round bar are difficult.
  • SP-A-7-278768 discloses a method for reducing the hydrogen embrittlement in order to effectively reduce or inhibit hydrogen embrittlement of alloy members such as a rocket engine that uses hydrogen as a fuel. The method includes a step of irradiating a laser beam on a whole surface, which has been aged, to heat the irradiated surface to a temperature higher than the solvus temperature and dissolve precipitates generated in the alloy member by aging treatment, followed by quenching the irradiated portion to form a hydrogen embrittlement resistant portion that is devoid of precipitates on a surface of the irradiated portion and homogeneous in a structure. This is a method where a γ′-phase that is a precipitation strengthening phase is locally dissolved with heating. However, there is fear that a saluted layer devoid of the γ′-phase may have decreased tensile strength.
  • JP-A-2006-9982 discloses a high-pressure container for high-pressure hydrogen, which includes a container body and a cap hermetically disposed to one end or both ends of the container body. The container body is made of a steel and a metal film is coated on an inner surface of the container for inhibiting hydrogen from intruding. However, there is a concern that when the metal film for inhibiting hydrogen from intruding is spalled, the performance thereof is rapidly deteriorated.
  • SUMMARY OF THE INVENTION
  • As mentioned above, a material having high hydrogen embrittlement resistance has not been developed at present, and there are problems when a surface treatment or coating is applied since surface characteristics are deteriorated and rapid functional deterioration is caused by spalling of the coating.
  • The objective of the present invention is to provide a hydrogen embrittlement resistant piping having both hydrogen embrittlement resistance and high tensile strength, and inhibiting rapid deterioration caused by deterioration of surface characteristics and by spalling of a coating, and a method for producing the same.
  • A hydrogen-resistant high strength material according to the invention is made of a Ni-based alloy or an Fe—Ni-based alloy and includes an aged portion and a hydrogen embrittlement suppressing layer that is to be exposed to hydrogen. The hydrogen embrittlement suppressing layer has a hydrogen embrittlement index of not less than 0.9. The hydrogen embrittlement index is defined as a ratio of an elongation after hydrogen charging in relation to an elongation before hydrogen charging. The aged portion has a tensile strength exceeding 1000 MPa.
  • A method for producing a hydrogen-resistant high strength material according to the invention includes the steps of applying an aging heat treatment to an entirety of a material made of a Ni-based alloy or an Fe—Ni-based alloy to form an aged portion; and applying a solution treatment locally to the aging-heat-treated material to form a hydrogen embrittlement suppressing layer.
  • A method for producing a hydrogen-resistant high strength material according to the invention includes the steps of applying a solution treatment to an entirety of a material made of a Ni-based alloy or an Fe—Ni-based alloy; and after the solution treatment step, while keeping a portion where a hydrogen embrittlement suppressing layer is formed cooled, applying an aging heat treatment to other portion to form an aging-treated portion.
  • According to the invention, an inner layer of a hydrogen embrittlement resistant piping bears hydrogen embrittlement resistance and an outer layer thereof bears tensile strength. Accordingly, the hydrogen embrittlement resistance and high tensile strength can be obtained.
  • Furthermore, according to the invention, there is no concern about spelling of the coating and also strength deterioration caused by completely solution treating can be inhibited.
  • Other objects, features and advantages of the invention will become apparent from the following description of the embodiments of the invention taken in conjunction with the accompanying drawings.
  • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a schematic sectional diagram showing a hydrogen embrittlement resistant piping of the invention;
  • FIG. 2 is a graph showing a distribution of an amount of precipitated γ′-phase in a radial direction of the hydrogen embrittlement, resistant piping of the invention; and
  • FIG. 3 is a graph showing hydrogen embrittlement index and relative strength in relation to an amount of precipitated γ′-phase of the hydrogen embrittlement resistant piping of the invention.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention relates to a hydrogen embrittlement resistant piping (metal piping for hydrogen infrastructure) and a method for producing the same.
  • A γ′-phase precipitation strengthened Ni-based alloy or Fe—Ni-based alloy is used for a material of a hydrogen embrittlement resistant piping of the invention. In this case, the Ni-based alloy or Fe—Ni-based alloy has a face-centered cubic lattice structure (referred to as FCC). Here, the γ′-phase is an L1 2 ordered phase that precipitates in a γ-matrix of FCC after the alloy is subjected to the aging heat treatment. That is, the γ′-phase is an FCC ordered phase finely precipitated in a γ-phase having an FCC solid solution phase as a matrix.
  • A hydrogen embrittlement resistant piping is simply referred to as a piping in some cases.
  • According to a study of the inventors, tensile tests are carried out according to a thermal precharging method in high-pressure hydrogen gas with the γ′-phase precipitation strengthened Ni-based alloy. While the ductility was remarkably deteriorated in a material having high strength by a predetermined heat treatment, the ductility was remarkably inhibited from deteriorating when an amount of precipitated γ′-phase was reduced by applying the aging heat treatment at a temperature higher than the predetermined heat treatment. Accordingly, it was studied to apply this to a piping for high-pressure hydrogen gas.
  • A crack that becomes a starting point of fatigue or fracture starts from a surface of a material. The hydrogen embrittlement is considered to progress with a fine crack initially formed as a starting point. Accordingly, it is considered effective to inhibit the initial fine crack from occurring.
  • Accordingly, it is considered that the crack can be inhibited from generating and progressing by imparting the ductility and hydrogen embrittlement resistance only to a surface (the inside of a piping exposed to hydrogen as) to be in contact is gas.
  • FIG. 1 is a schematic sectional view showing a hydrogen embrittlement resistant piping of the invention.
  • A inner surface (inner layer) of a hydrogen embrittlement resistant piping 101 to be exposed to hydrogen is constituted of a hydrogen embrittlement suppressing layer 1 to be exposed to hydrogen and the outside (outer layer) thereof is constituted of an aging-treated phase 2. By considering applications other than the piping, in general, the aging-treated phase 2 may be referred to as an aging-treated portion.
  • The ductility can be maintained when an amount of the γ′-phase (precipitation amount) of the hydrogen embrittlement suppressing layer 1 is reduced to less than that of the aging-treated layer 2, as is shown in the drawing.
  • FIG. 2 is a graph schematically showing a distribution of an amount of the γ′-phase precipitated in a matrix. A horizontal axis in the drawing represents a radial direction of the piping and a vertical axis shows an amount of precipitated γ′-phase.
  • The amount of precipitated γ′-phase is highest in the aging-treated layer 2, that is, the outer phase in FIG. 1 and low in the hydrogen embrittlement suppressing layer 1, that is, the inner layer in FIG. 1. In the inner layer, the amount of precipitated γ′-phase is equal to or lower than a limit value. Furthermore, an allowable amount of precipitates in the inner surface is higher than 0% and equal to or less than a predetermined value lower than the limit value. The amount of precipitated γ′-phase may be referred to as a γ′-concentration or a γ′-amount.
  • FIG. 3 is a graph showing a hydrogen embrittlement index and relative tensile strength in relation to a precipitation amount of the γ′-phase (also referred to as amount of precipitated γ′-phase) in a hydrogen embrittlement resistant piping of the invention.
  • A horizontal axis represents a precipitation amount of the γ′-phase and a vertical axis represents a hydrogen embrittlement index and a relative tensile strength. Herein, the hydrogen embrittlement index is calculated from a formula (1) shown below. The relative tensile strength is a relative value of tensile strength of each of the respective materials represented in relation to that of a solution treated material (also referred to as ST (solution treatment) material).
  • From the drawing, it is found that the tensile strength of the material can be heightened by increasing an amount of precipitated γ′-phase, while the hydrogen embrittlement index tends decrease.

  • (Hydrogen embrittlement index)=(elongation after hydrogen charging)/(elongation before hydrogen charging)  (1)
  • Here, the elongation and the tensile strength of the were measured based on JIS Z2241.
  • As the formula (1) shows, the larger the numerical value of the index is, the smaller or zero a decrease of elongation is even when the hydrogen charging is performed. In other words, a material having a larger hydrogen embrittlement index is more difficult to be embrittled by hydrogen.
  • That is, the drawing shows that the γ′ concentration is not necessarily require to be zero.
  • From the drawing, it is found that the hydrogen embrittlement index has a higher value as the γ′ amount is smaller. That is, it is found that the γ′ amount has a permissible amount.
  • A practically usable piping desirably has the hydrogen embrittlement index shown by the formula (1) of not less than 0.9. Accordingly, when the limit γ′-amount (that is the limit value of amount of precipitated γ′-phase) where the hydrogen embrittlement index is not less than 0.9 is obtained for every materials, a range where both the tensile strength and the elongation (ductility) of the material are maintained can be set.
  • Furthermore, through a study of a method for producing the hydrogen embrittlement resistant piping, it is found that there are two methods.
  • In the first method, a material processed previously into a necessary shape is subjected to a solution treatment, by cooling to render an entirety of the piping a solution treated structure that is difficult to cause hydrogen embrittlement. Next, cooling air or cooling water is flowed inside of the piping, and, at the same time therewith, a heat treatment is externally applied, thereby an outer layer of the piping is rendered an aging-treated layer without changing the solution treated structure of an inner layer of the piping.
  • In the second method, an entire piping is subjected to an aging heat treatment to render the entire piping an aging-treated layer, and an inner surface of the piping is locally heated by laser to dissolve the γ′-phase to make an amount of precipitated γ′-phase smaller than that of an outer layer.
  • According to the two methods, a hydrogen embrittlement resistant piping having high tensile strength can be provided.
  • Exemplary embodiments of the invention will be specifically described below.
  • It is desirable that a material used in a hydrogen embrittlement resistant piping of the invention is a γ′-phase precipitation strengthening alloy and has the tensile strength exceeding 1000 MPa owing to a predetermined solution treatment and aging heat treatment of the alloy. This is because an A286 alloy can be used alternatively if the tensile strength is sufficient to be 1000 MPa or less.
  • Furthermore, the tensile strength is desirable to exceed 1200 MPa and more desirable to exceed 1400 MPa. It is appropriate that a hydrogen embrittlement suppressing layer is applied to an inner surface of the piping, that is directly exposed to a hydrogen gas. It is necessary that an amount of precipitated γ′-phase of the hydrogen embrittlement suppressing layer is larger than 0% and lower than a predetermined amount of the precipitated γ′-phase in the respective materials. In a completely solution treated structure (0%), the tensile strength is drastically lowered.
  • The upper limit of the amount of precipitated γ′-phase of the hydrogen embrittlement suppressing layer is preferably that represented by the hydrogen embrittlement index of not less than 0.9 and more preferably not less than 0.98 that shows a degree of embrittlement caused by hydrogen (that is, elongation after hydrogen charging/elongation before hydrogen charging). Here, 0.9 is a value of the hydrogen embrittlement index in A286 and this is because A786 is assumed to correspond to the lower limit of the hydrogen embrittlement index.
  • A thickness of the hydrogen embrittlement suppressing layer (inner layer) defined above is desirably 5 to 30% or less of a thickness of the piping. The thickness the piping is a value obtained by total thicknesses of the inner layer and the outer layer. It can be also said that the thickness of the hydrogen embrittlement suppressing layer is from 5 to 30% of an total thickness obtained by adding a thickness of an aged portion (aging-treated phase) and a thickness of the hydrogen embrittlement suppressing layer. This is because in the case where the thickness of the hydrogen embrittlement suppressing layer is less than 5%, an generated initial crack immediately reaches an outer layer where a γ′-phase precipitates. When the thickness of the hydrogen embrittlement suppressing layer exceeds 30%, the tensile strength as the piping is largely deteriorated. A range from 10 to 20% is still more preferable.
  • Next, a method for producing a hydrogen embrittlement resistant piping will be described below.
  • Firstly, a material to be used is processed into a necessary shape of a piping. The method therefor is not particularly restricted.
  • Then, according to predetermined processes suitable for the material, a solution treatment and an aging heat treatment are carried out.
  • Thereafter, a local heating device insertable into the inside of the piping such as laser is used to locally heat an inner surface of the piping to form a solid solution so that a γ′-phase having the predetermined concentration may remain. When the laser is used to form a solid solution, it is desirable to previously set laser irradiation conditions, such as an output, a focus distance or a scanning speed, to a used material to study conditions capable of forming the hydrogen embrittlement suppressing layer such as mentioned above.
  • Furthermore, another method of the invention for producing a piping will be described.
  • Firstly, a material to be used is processed into a necessary shape of a piping. The processing method is not particularly restricted. Thereafter, the material processed into a piping shape is subjected to a solution treatment, followed by rapidly cooling to impart a solution treated structure to an entire material.
  • Then, cooling air or cooling water as a cooling medium is flowed inside of the piping and the piping is externally heated to apply the aging heat treatment. As the cooling air, for example, compressed air is used and the cooling water is supplied by use of a chiller unit or the like.
  • As a heating unit, an electric furnace having capacity capable of uniformly heating a prepared piping raw material is desirable. Furthermore, electromagnetic induction heating or laser may be used.
  • In any of the producing methods, it is desirable to determine in advance a temperature, a flow rate of the cooling medium and an externally heating temperature while measuring temperatures of an inner surface and an outer surface of the piping.
  • EXAMPLES
  • The present invention will be described with reference to Examples.
  • Table 1 shows compositions of samples prepared as Examples.
  • TABLE 1
    Compositions of samples
    Ni Fe Cr Al Ti Nb Mo C Remarks
    Alloy A A-0 26 Bal 15 0.3 2.1 1.3 0.04 Solution-treated
    material of A-1
    A-1 (Example 1) 26 Bal 15 0.3 2.1 1.3 0.04
    A-2 (Example 2) 26 Bal 15 0.4 3 1.3 0.04
    A-3 (Example 3) 26 Bal 15 0.35 2.5 1.3 0.04
    Alloy B (Example 4) Bal 37 16 1.3 1.7 2 0.03 Final aging temperature:
    625, 730, 910° C.
  • As is shown in the table, γ′-phase precipitation strengthening Ni-based alloys A-1 to A-3 and Fe—Ni-based alloy B were prepared. An alloy A-0 is a material having the same composition as that of the alloy A-1 and is obtained by solution treating the alloy A-1. Furthermore, the alloy A-3 is a material having the same composition as that of JIS SUH660 (A286). Still furthermore, an alloy B is a material which is improved in heat resistance. The alloys A-1 to A-3 and the alloy B were assigned to Examples 1 to 4 respectively.
  • For the Ni-based alloys A-1 to A-3 (Examples 1 to 3), three kinds of alloys A-1 to A-3 were prepared by varying compositions of Al and Ti to vary amounts of precipitated γ′-phase.
  • The heat treatment of the Ni-based alloys A-1 to A-3 was performed at 980° C. for 2 hours and an aging heat treatment was performed at 720° C. for 8 hours.
  • For an Fe—Ni-based alloy B (Example 4), amounts of precipitated γ′-phase were varied by varying a final aging heat treatment temperature (referred to as the final aging temperature) in a range of 625 to 910° C. The solution treatment is performed for 2 hours and the aging time is 8 hours.
  • Thereafter, tensile test pieces prepared from these alloys were subjected to the hydrogen charging in a hydrogen gas at 450° C. and under 20 MPa, followed by performing the tensile test at room temperature and in atmosphere, further followed by measuring elongation and tensile strength each of the test pieces. The tensile speed at this time was set at 0.3 mm/min with use of a displacement gauge. Based on measurements, hydrogen embrittlement indices (elongation after hydrogen charging/elongation before hydrogen charging) were calculated.
  • FIG. 3 is a graph showing results of the above-mentioned tensile tests as the hydrogen embrittlement indices and relative tensile strengths in relation to amounts of precipitated γ′-phase in hydrogen embrittlement resistant pipings.
  • The tensile strengths are represented by relative values or relative strengths where the tensile strength as solution treatment is assigned to 1.
  • It is found that the relative tensile strength increases depending on an amount of precipitated γ′-phase that increases strength. On the other hand, it is found that the hydrogen embrittlement index decreases depending on an amount of precipitated γ′-phase. Furthermore, it is found that the embrittlement can be suppressed when the amount of precipitated γ′-phase is lower than a predetermined value. The upper limit of the amount of precipitated γ′-phase, which can suppress the embrittlement, is about 10% for the alloy A and about 7% for the alloy B. These were defined as the limit values of amounts of precipitated γ′-phase in the respective alloys.
  • Piping materials having an outer diameter of 10 mm and a thickness of 1.5 mm were prepared with the alloy A-1 and the alloy B. The piping from the alloy A-1 was subjected to a solution treatment at 980° C. for 2 hours and an aging heat treatment at 720° C. for 8 hours. The piping from the alloy B was subjected to a solution treatment at 980° C. for 2 hours and an aging heat treatment at 740° C. for 8 hours. When an aging heat treatment is applied at 740° C. for 8 hours, the tensile strength of 1300 MPa class can be imparted for those subjected to an ordinary heat treatment.
  • Each of these pipings was heat-treated by irradiating laser on an inner surface of the piping. The piping of which surface was heat-treated by irradiating laser was sliced into rings to observe a cross-section thereof, and an amount of precipitated γ′-phase was calculated by image analysis.
  • As the results, an amount of precipitated γ′-phase was 9.6% by average at a position about 300 μm from an inner surface (referred to as “inside surface”) in a piping of the alloy A-1, and an amount of precipitated γ′-phase was 1.1% by average in the vicinity of the inner surface of the piping. On an outer surface (referred to as “outside surface”) of the piping, and an amount of precipitated γ′-phase was 12% that is substantially equal to a value obtained by thermodynamic equilibrium calculation.
  • Similarly, an amount of precipitated γ′-phase was 6.2% by average at a position about 300 μm from the inner surface of a piping of the alloy B, and an amount of precipitated γ′-phase was 0.9% by average in the vicinity of the inner surface of the piping. On an outside surface of the piping, an amount of precipitated γ′-phase was about 20% that is substantially equal to a value obtained by thermodynamic equilibrium calculation.
  • Piping materials having an outer diameter of 10 mm and a thickness of 1.5 mm were prepared from the alloy A-1 and the alloy B.
  • Both of the alloy A-1 and the alloy B were solution treated at 980° C. for 2 hours and thereafter cooled with water to maintain the solution-treated state.
  • Thereafter, the aging heat treatment was performed with cooling the inside of the piping with water as a cooling medium. A piping from the alloy A-1 was subjected to the aging heat treatment in an electric furnace at 730° C. for 8 hours. A piping from the alloy B was subjected to the aging heat treatment in an electric furnace at 755° C. for 8 hours. Thermocouples were attached to inner and outer surfaces of the pipings of both materials, and surface temperatures during the heat treatment were monitored.
  • As the results, it was found that inner surface temperature, of the alloys A-1 and B were about 583° C. and about 609° C. respectively, and outer surface temperatures thereof were 720° C. and 740° C. respectively.
  • After the heat treatments, each of the pipings was sliced in rings to observing a structure thereof, followed by calculating amounts of precipitated γ′-phase by image analysis.
  • As the results, an amount of precipitated γ′-phase was 9% by average at a position about 400 μm from an inner surface of the piping of the alloy A-1, and an amount of precipitated γ′-phase was 1.5% by average in the vicinity of the inner surface of the piping. On an outer surface of the piping, an amount of precipitated γ′-phase was 12%. This is substantially same value as that obtained by thermodynamic equilibrium calculation.
  • On the other hand, an amount of precipitated γ′ phase was 6% by average at a position about 350 μm from an inner surface of the piping of the alloy B, and an amount of precipitated γ′-phase was 2% by average in the vicinity of the inner surface of the piping. On an outside surface of the piping, an amount of precipitated γ′-phase was about 20%. This is substantially same value as that obtained by thermodynamic equilibrium calculation.
  • As mentioned above, the heat treatments of the pipings were mainly described. However, a produced hydrogen-resistant high strength material is not restricted thereto and a kind of a product is not questioned as long as a hydrogen embrittlement suppressing layer is formed in a portion that is exposed to hydrogen and an aging-treated phase is formed in other portion.
  • A range of application of the hydrogen embrittlement resistant technology of the invention is not restricted to hydrogen embrittlement resistant pipings. The technology can be applied also to hydrogen producing equipments (reactors) at hydrogen stations, holders (hydrogen tanks (high-pressure containers)), compressors, accumulators, hydrogen dispensers (hydrogen supply equipments), high-pressure hydrogen flowmeter for hydrogen dispenser (such as Coriolis flowmeter), hydrogen vehicles and so on.
  • It should be further understood by those skilled in the art that although the foregoing description has been made on embodiments of the invention, the invention is not limited thereto and various changes and modifications may be made without departing from the spirit of the invention and the scope of the appended claims.

Claims (15)

1. A hydrogen-resistant high strength material made of a Ni-based alloy or an Fe—Ni-based alloy, comprising:
an aging-treated portion; and
a hydrogen embrittlement suppressing layer that is to be exposed to hydrogen,
wherein the hydrogen embrittlement suppressing layer has a hydrogen embrittlement index of not less than 0.9, the hydrogen embrittlement index being defined as a ratio of an elongation after hydrogen charging in relation to an elongation before hydrogen charging, and
wherein the aged portion has a tensile strength exceeding 1000 MPa.
2. The hydrogen-resistant high strength material according to claim 1, wherein the Ni-based alloy or the Fe—Ni-based alloy has a face-centered cubic lattice structure.
3. The hydrogen-resistant high strength material according to claim 1, wherein a thickness of the hydrogen embrittlement suppressing layer is from 5 to 30% of a total thickness of the aged portion and the hydrogen embrittlement suppressing layer.
4. A hydrogen embrittlement resistant piping, comprising the hydrogen-resistant high strength material according to claim 1.
5. A reactor, comprising the hydrogen-resistant high strength material according to claim 1.
6. A high-pressure container, comprising the hydrogen-resistant high strength material according to claim 1.
7. A compressor, comprising the hydrogen-resistant high strength material according to claim 1.
8. An accumulator, comprising the hydrogen-resistant high strength material according to claim 1.
9. A hydrogen dispenser, comprising the hydrogen-resistant high strength material according to claim 1.
10. A high-pressure hydrogen flowmeter, comprising the hydrogen-resistant high strength material according to claim 1.
11. A hydrogen vehicle, comprising the hydrogen-resistant high strength material according to claim 1.
12. A method for producing a hydrogen-resistant high strength material, comprising the steps of:
applying an aging heat treatment to an entirety of a material made of a Ni-based alloy or an Fe—Ni-based alloy to form an aged portion; and,
applying a solution treatment locally to the aging-heat-treated material to form a hydrogen embrittlement suppressing layer.
13. The method according to claim 12, wherein a thickness of the hydrogen embrittlement suppressing layer is from 5 to 30% of a total thickness of the aged portion and the hydrogen embrittlement suppressing layer.
14. A method for producing a hydrogen-resistant high strength material, comprising the steps of:
applying a solution treatment to an entirety of a material made of a Ni-based alloy or an Fe—Ni-based alloy; and,
after the solution treatment step, while keeping a portion where a hydrogen embrittlement suppressing layer is to be formed cooled, applying an aging heat treatment to other portion to form an aged portion.
15. The method according to claim 14, wherein a thickness of the hydrogen embrittlement suppressing layer is from 5 to 30% of a total thickness of the aged portion and the hydrogen embrittlement suppressing layer.
US12/697,506 2009-02-02 2010-02-01 Hydrogen-resistant high strength material and method for producing the same Abandoned US20100193083A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009021195A JP2010174360A (en) 2009-02-02 2009-02-02 Hydrogen embrittlement resistant material, and method for producing the same
JP2009-021195 2009-02-02

Publications (1)

Publication Number Publication Date
US20100193083A1 true US20100193083A1 (en) 2010-08-05

Family

ID=42396728

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/697,506 Abandoned US20100193083A1 (en) 2009-02-02 2010-02-01 Hydrogen-resistant high strength material and method for producing the same

Country Status (2)

Country Link
US (1) US20100193083A1 (en)
JP (1) JP2010174360A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5599850B2 (en) 2012-08-24 2014-10-01 株式会社日本製鋼所 Ni-base alloy excellent in hydrogen embrittlement resistance and method for producing Ni-base alloy material excellent in hydrogen embrittlement resistance
JP5786830B2 (en) * 2012-09-03 2015-09-30 新日鐵住金株式会社 High-strength austenitic stainless steel for high-pressure hydrogen gas

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278768A (en) * 1994-04-08 1995-10-24 Ishikawajima Harima Heavy Ind Co Ltd Method for decreasing hydrogen embrittlement

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G. P. Sabol and R. Stickler, Microstructure of nickel-based superalloys, Phys. Stat. Sol, 1969, Vol 35, Page 11-52. *
Hirose et al. Decrease in hydrogen embrittlement sensitivity of INCONEL 718 by laser surface softening, Materials Science and Engineering, 1996, Vol. A219, Page 71-79. *
Nakanishi et al., Machine translation of JP 07278768 A. 10-1995. *

Also Published As

Publication number Publication date
JP2010174360A (en) 2010-08-12

Similar Documents

Publication Publication Date Title
JP6039774B2 (en) Manufacturing method of high nitrogen stainless steel pipe for manufacturing high pressure hydrogen gas storage container with high strength, high ductility and excellent corrosion resistance and heat resistance
CN103154291B (en) The component of austenitic high mn stainless steel and manufacture method and this steel of use
Komoda et al. Inhibitory effect of oxygen on hydrogen‐induced fracture of A333 pipe steel
Wang et al. Combined effects of prior plastic deformation and sensitization on hydrogen embrittlement of 304 austenitic stainless steel
JP7349776B2 (en) High-pressure hydrogen containers and steel materials for high-pressure hydrogen
Omura et al. Hydrogen embrittlement properties of stainless and low alloy steels in high pressure gaseous hydrogen environment
CA2715814A1 (en) Austenitic stainless steel, and method for removing hydrogen therefrom
Nam et al. Low-temperature tensile and impact properties of hydrogen-charged high-manganese steel
JP2011068919A (en) Fe-ni based alloy with high-strength hydrogen embrittlement resistant
JP2016044332A (en) Stainless steel for low temperature application
JPWO2015098981A1 (en) Base material for hydrogen equipment and method for producing the same
US11168375B2 (en) Steel pipe or tube for pressure vessels, method of producing steel pipe or tube for pressure vessels, and composite pressure vessel liner
Nakamura et al. Degradation of fatigue properties in high pressure gaseous hydrogen environment evaluated by cyclic pressurization tests
Grajcar Corrosion resistance of high-Mn austenitic steels for the automotive industry
Cheng et al. Cryogenic work-hardening behavior for a metastable austenitic stainless steel at liquid nitrogen temperature
US20100193083A1 (en) Hydrogen-resistant high strength material and method for producing the same
Ogata Hydrogen environment embrittlement evaluation in fatigue properties of stainless steel SUS304L at cryogenic temperatures
Matsunaga et al. Hydrogen-assisted cracking of Cr-Mo steel in slow strain rate tensile test with high-pressure gaseous hydrogen
JP2010121210A (en) High purity iron alloy for hydrogen storage vessel, and hydrogen storage vessel
JP2019090070A (en) Nickel steel for high-pressure hydrogen
EP3498875B1 (en) Composite pressure vessel liner, composite pressure vessel, and method for producing composite pressure vessel liner
US20230146009A1 (en) Molded Parts for Low Temperature Applications, Especially for Liquid Hydrogen
JP5930145B2 (en) Hydrogen-resistant fatigue ferritic steel and its manufacturing method
Yamabe et al. Hydrogen Safety Fundamentals
WO2023189563A1 (en) Martensite stainless steel for high-pressure hydrogen component, high-pressure hydrogen component using same, and method for producing same

Legal Events

Date Code Title Description
AS Assignment

Owner name: HITACHI, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KAMOSHIDA, HIRONORI;IMANO, SHINYA;SIGNING DATES FROM 20100106 TO 20100112;REEL/FRAME:023897/0472

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION