EP2850215B1 - Reduced cost steel for hydrogen technology with high resistance to hydrogen-induced imbrittlement - Google Patents

Reduced cost steel for hydrogen technology with high resistance to hydrogen-induced imbrittlement Download PDF

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EP2850215B1
EP2850215B1 EP13731695.6A EP13731695A EP2850215B1 EP 2850215 B1 EP2850215 B1 EP 2850215B1 EP 13731695 A EP13731695 A EP 13731695A EP 2850215 B1 EP2850215 B1 EP 2850215B1
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hydrogen
steel
mass
percent
induced
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French (fr)
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EP2850215A1 (en
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Wolfgang Leistner
Thorsten Michler
Werner Theisen
Mauro Sebastián MARTIN
Sebastian Weber
Sascha RIEDNER
Jörg Naumann
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Bayerische Motoren Werke AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/001—Heat treatment of ferrous alloys containing Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0203—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels characterised by the type of gaseous fuel
    • F02M21/0206—Non-hydrocarbon fuels, e.g. hydrogen, ammonia or carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0218—Details on the gaseous fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0218—Details on the gaseous fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F02M21/0296—Manufacturing or assembly; Materials, e.g. coatings
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

Description

Die Erfindung bezieht sich auf die Verwendung eines austenitischen korrosionsbeständigen Stahls für die Wasserstofftechnik in Kraftfahrzeugen mit hoher Beständigkeit gegen wasserstoffinduzierte Versprödung insbesondere im Temperaturbereich zwischen - 100 °C und Raumtemperatur (+25°C). Sie ist für alle mit Wasserstoff in Kontakt stehenden metallischen Bauteile eines Kraftfahrzeugs geeignet, wie zum Beispiel Wasserstofftanks, Ventile, Leitungen, Fittings, Boss, Liner Federn, Wärmetauscher oder Faltenbälge.The invention relates to the use of an austenitic stainless steel for hydrogen technology in motor vehicles with high resistance to hydrogen-induced embrittlement, in particular in the temperature range between -100 ° C and room temperature (+ 25 ° C). It is suitable for all hydrogen in contact with metallic components of a motor vehicle, such as hydrogen tanks, valves, pipes, fittings, Boss, liner springs, heat exchangers or bellows.

Stahl, der über längere Zeit einer mechanischen Belastung in Wasserstoffatmosphäre ausgesetzt ist, unterliegt der Wasserstoffversprödung. Eine Ausnahme bilden austenitische Edelstähle mit hohem Nickelgehalt wie der Werkstoff 1.4435, X2CrNiMo18-14-3. Ein Nickelgehalt von mindestens 12,5 Masse-% wird bei diesen austenitischen Stählen als notwendig erachtet, um eine ausreichende Beständigkeit gegen Wasserstoffversprödung im gesamten Temperaturbereich von -253 bis mindestens +100°C und Druckbereich von 0,1 bis 100 MPa zu erzielen. Nickel ist jedoch, wie auch Molybdän, ein sehr teures Legierungselement, so dass vor allem für eine Massenfertigung z.B. von Tankkomponenten im Kfz-Bereich kostengünstige wasserstoffbeständige Stähle fehlen.Steel subjected to mechanical stress in a hydrogen atmosphere for a long time undergoes hydrogen embrittlement. One exception is austenitic stainless steels with a high nickel content such as 1.4435, X2CrNiMo18-14-3. A nickel content of at least 12.5 mass% is considered necessary for these austenitic steels to provide sufficient resistance to hydrogen embrittlement over the entire temperature range of -253 to at least + 100 ° C and pressure range of 0.1 to 100 MPa. However, nickel, like molybdenum, is a very expensive alloying element, so that, especially for mass production, e.g. Tank components in the automotive sector lack cost-effective hydrogen-resistant steels.

Aus US 2009/0159602 A1 ist ein austenitischer Stahl mit einer Zusammensetzung gemäß der Formel − 120 < Md 30 < 20

Figure imgb0001
mit Md30(°C): 551-462(C+N)-9,2Si-8,lMn-13,7Cr-29(Ni+Cu)-18,2Mo bekannt.Out US 2009/0159602 A1 is an austenitic steel having a composition according to the formula - 120 < Md 30 < 20
Figure imgb0001
 with Md30 (° C): 551-462 (C + N) -9.2Si-8, lMn-13.7Cr-29 (Ni + Cu) -18.2Mo.

Aufgabe der Erfindung ist es, zur Verwendung für die Wasserstofftechnik in Kraftfahrzeugen einen kostengünstigen Stahl bereitzustellen, der gegen wasserstoffinduzierte Versprödung im gesamten Temperaturbereich zwischen mindestens +100°C und -253°C und hohem Druck resistent ist, Korrosionsbeständigkeit aufweist und sich gut warm- und kaltumformen sowie schweißen lässt.The object of the invention is to provide for use for the hydrogen technology in motor vehicles, a cost-effective steel that is resistant to hydrogen-induced embrittlement throughout the temperature range between at least + 100 ° C and -253 ° C and high pressure resistant, has corrosion resistance and good warm and cold forming and welding.

Dies wird erfindungsgemäß mit einem austenitischen Stahl erreicht, der eine Zusammensetzung gemäß dem Patentanspruch aufweist:

  • Der Stahl kann ohne Zusatz von Aluminium hergestellt sein. Das heißt, er kann bis zu 0,3 Masse-% Aluminium als erschmelzungsbedingtes Stahlbegleitelement enthalten. Gleiches gilt für Stickstoff. Auch kann Molybdän nur als Stahlbegleitelement in dem Stahl enthalten sein.
This is achieved according to the invention with an austenitic steel having a composition according to the claim:
  • The steel can be made without the addition of aluminum. That is, it may contain up to 0.3% by mass of aluminum as a steel-accompanying element caused by melting. The same applies to nitrogen. Also, molybdenum can be included only as a steel accompanying element in the steel.

Die erschmelzungsbedingten Stahlbegleitelemente umfassen weitere übliche produktionsbedingte Elemente (z.B. Schwefel und Phosphor) sowie weitere nicht gezielt hinzulegierte Elemente. Dabei beträgt vorzugsweise der Phosphorgehalt ≤ 0,05 Masse-%, der Schwefelgehalt ≤0,4 Masse-%, insbesondere < 0,04 Masse-%. Der Gehalt aller weiteren erschmelzungsbedingten Stahlbegleitelemente beträgt pro Element maximal. 0,3 Masse-%.The melting-related steel accompanying elements comprise further customary production-related elements (eg sulfur and phosphorus) as well as other elements which are not specifically added. In this case, the phosphorus content is preferably ≦ 0.05 mass%, the sulfur content ≦ 0.4 mass%, in particular <0.04 mass%. The content of all other melting-related steel accompanying elements is maximum per element. 0.3 mass%.

Durch die Herabsetzung des Nickelgehaltes auf 6 bis 9 Masse-% und den fehlenden Molybdän-Gehalt können die Kosten herabgesetzt werden.By reducing the nickel content to 6 to 9% by weight and the lack of molybdenum content, the costs can be reduced.

Trotz der Herabsenkung des Nickelgehaltes und des geringen Molybdän-Gehaltes oder fehlendem Molybdän (also ohne Molybdän-Zusatz) weist der Stahl sehr gute mechanische Eigenschaften in einer Wasserstoffatmosphäre im gesamten Temperaturbereich von -253 bis mindestens +100°C und Druckbereich von 0,1 bis 100 MPa auf.Despite the decrease in the nickel content and the low molybdenum content or lack of molybdenum (ie without molybdenum additive), the steel has very good mechanical properties in a hydrogen atmosphere over the entire temperature range of -253 to at least + 100 ° C and pressure range from 0.1 to 100 MPa.

So weist der Stahl im lösungsgeglühten Zustand (AT) bei einer Prüftemperatur von -50°C und einem Gasdruck von 40 MPa Wasserstoff im Zugversuch bei einer Dehnrate von 5x10-5 1/s eine "Relative Reduction of Area" (RAA) oder relative Brucheinschnürung (= Brucheinschnürung Z in Luft oder Helium/Brucheinschnürung Z in Wasserstoff x 100%) von mindestens 90% auf. Die entsprechende relative Zugfestigkeit R_Rm, relative Streckgrenze R_Rp 0,2 und relative Bruchdehnung R_A5 betragen ebenfalls mindestens 90%. Zudem ist die hohe Streckgrenze des Stahls von 300 bis 400 MPa von wesentlicher Bedeutung.Thus, the steel in the solution-annealed condition (AT) at a test temperature of -50 ° C and a gas pressure of 40 MPa hydrogen in the tensile test at a strain rate of 5x10-5 1 / s, a Relative Reduction of Area (RAA) or relative Brucheinschnürung (= Fractional Z in air or helium / Fractional Z in hydrogen x 100%) of at least 90%. The corresponding relative tensile strength R_Rm, relative yield strength R_Rp0.2 and relative elongation at break R_A5 are also at least 90%. In addition, the high yield strength of the steel of 300 to 400 MPa is essential.

Der Stahl kann lösungsgeglüht (AT) sein. Er kann auch kaltverformt, insbesondere kaltgezogen oder kaltgewalzt verwendet werden.The steel can be solution annealed (AT). It can also be cold formed, in particular cold drawn or cold rolled used.

Der Stahl besitzt eine sehr gute Schweißbarkeit und eine gute Korrosionsbeständigkeit.The steel has a very good weldability and good corrosion resistance.

Der Stahl weist eine hohe Beständigkeit gegen Wasserstoffversprödung im gesamten Temperaturbereich von -253°C bis mindestens +100°C und Druckbereich von 0,1 bis 100 MPa auf.The steel has a high resistance to hydrogen embrittlement in the entire temperature range from -253 ° C to at least + 100 ° C and pressure range from 0.1 to 100 MPa.

Der Stahl stellt damit einen kostengünstigen wasserstoffbeständigen Werkstoff für die Wasserstofftechnik dar.The steel thus represents a cost-effective hydrogen-resistant material for hydrogen technology.

Das heißt, der Stahl kann in der Wasserstofftechnik von Kraftfahrzeugen für Vorrichtungen und Bauteile von Systemen zur Erzeugung, Speicherung, Verteilung und Nutzung von Wasserstoff eingesetzt werden, insbesondere wenn die Vorrichtungen bzw. Bauteile mit Wasserstoff in Berührung kommen. Dies gilt insbesondere für Leitungen, Regeleinrichtungen, Ventile und andere Absperrorgane, Behälter, Fittings, Boss und Liner, Wärmetauscher, Drucksensoren usw. einschließlich Teile dieser Einrichtungen, wie z.B. Federn und Faltenbälge.That is, the steel can be used in the hydrogen technology of automobiles for devices and components of systems for generating, storing, distributing and using hydrogen, especially when the devices come into contact with hydrogen. This is especially true for piping, control devices, valves and other shut-off devices, containers, fittings, bosses and liners, heat exchangers, pressure sensors, etc., including parts of these devices, such as e.g. Feathers and bellows.

Dabei kann zur Wasserstoffspeicherung ein (Hoch-)Druckbehälter, ein Kryo-(Hoch-)Druck-Behälter, oder ein Flüssigwasserstoffbehälter aus dem Stahl eingesetzt werden.In this case, for hydrogen storage, a (high) pressure vessel, a cryogenic (high) pressure vessel, or a liquid hydrogen tank from the steel can be used.

Der Stahl weist ein stabil austenitisches Gefüge auf. Der δ-Ferritgehalt der Stähle beträgt dabei weniger als 5 VolumenProzent vorzugsweise ist sogar kein δ-Ferrit vorhanden.The steel has a stable austenitic structure. The δ-ferrite content of the steels is less than 5% by volume, preferably even no δ-ferrite is present.

Im lösungsgeglühten Zustand (AT) beträgt die Streckgrenze Rp0,2 im Zugversuch mit einer Dehnrate von 5x10-5 1/s bei -50°C in einer Wasserstoffatmosphäre von 40 MPa für Stahl Nr. 1 200 bis 300 MPa und für Stahl Nr. 2 300 bis 400 MPa. Die relative Brucheinschnürung (= Brucheinschnürung Z in Helium geteilt durch die/ Brucheinschnürung Z in Wasserstoff x 100%) beträgt für beide Stähle mehr als 85%.In the solution-annealed condition (AT), the yield strength Rp0.2 in the tensile test at a strain rate of 5x10-5 is 1 / s at -50 ° C in a hydrogen atmosphere of 40 MPa for Steel No. 1 200 to 300 MPa and for Steel No. 2 300 to 400 MPa. The relative Brucheinschnürung (= Brucheinschnürung Z in helium divided by the / Fractional Z in hydrogen x 100%) is more than 85% for both steels.

Durch den relativ geringen Nickelgehalt von maximal 9 Masse-% und das Fehlen von Molybdän ist der Stahl sehr kostengünstig.Due to the relatively low nickel content of up to 9% by mass and the absence of molybdenum, the steel is very cost-effective.

Der Stahl mit stabil austenitischem Gefüge stellt damit einen kostengünstigen wasserstoffbeständigen Werkstoff für die Wasserstofftechnik in Kraftfahrzeugen dar.The steel with stable austenitic structure thus represents a cost-effective hydrogen-resistant material for hydrogen technology in motor vehicles.

Claims (1)

  1. Use of an austenitic steel having the following composition:
    0.01 to 0.12 percent by mass of carbon,
    0.05 to 0.5 percent by mass of silicon,
    9 to 13 percent by mass of manganese,
    16 to 20 percent by mass of chromium,
    6 to 9 percent by mass of nickel,
    0.01 to 0.5 percent by mass of aluminum,
    1 to 4 percent by mass of copper,
    ≤ 0.04 percent by mass of boron,
    the remainder being iron and melting-related steel companion elements for hydrogen technology in motor vehicles in the temperature range from -253 °C to +100 °C and pressure range from 0.1 to 100 MPa.
EP13731695.6A 2012-05-16 2013-05-15 Reduced cost steel for hydrogen technology with high resistance to hydrogen-induced imbrittlement Active EP2850215B1 (en)

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DE102012104260A DE102012104260A1 (en) 2012-05-16 2012-05-16 Cost-reduced steel for hydrogen technology with high resistance to hydrogen-induced embrittlement
PCT/EP2013/060084 WO2013171277A1 (en) 2012-05-16 2013-05-15 Reduced cost steel for hydrogen technology with high resistance to hydrogen-induced imbrittlement

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Publication number Priority date Publication date Assignee Title
US20090159602A1 (en) * 2005-11-01 2009-06-25 Masaharu Hatano Austenitic High Mn Stainless Steel for High Pressure Hydrogen Gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4032999A1 (en) 2021-01-20 2022-07-27 Poppe & Potthoff GmbH Low weight hydrogen distribution system and components
WO2022157247A1 (en) 2021-01-20 2022-07-28 Poppe + Potthoff Gmbh Hydrogen distribution system and components having low weight

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WO2013171277A1 (en) 2013-11-21
US10513764B2 (en) 2019-12-24
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DE102012104260A1 (en) 2013-11-21
US20150167134A1 (en) 2015-06-18

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