EP0257167B1 - Aluminium base alloy for hollow bodies for pressure containers - Google Patents

Aluminium base alloy for hollow bodies for pressure containers Download PDF

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Publication number
EP0257167B1
EP0257167B1 EP86420225A EP86420225A EP0257167B1 EP 0257167 B1 EP0257167 B1 EP 0257167B1 EP 86420225 A EP86420225 A EP 86420225A EP 86420225 A EP86420225 A EP 86420225A EP 0257167 B1 EP0257167 B1 EP 0257167B1
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European Patent Office
Prior art keywords
hollow bodies
alloy
base alloy
aluminium base
pressure containers
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EP86420225A
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German (de)
French (fr)
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EP0257167A1 (en
Inventor
Philippe Meyer
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Metallurgigue de Gerzat
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Metallurgigue de Gerzat
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/14—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of aluminium; constructed of non-magnetic steel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0104—Shape cylindrical
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/058—Size portable (<30 l)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0646—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0648—Alloys or compositions of metals
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2209/00—Vessel construction, in particular methods of manufacturing
    • F17C2209/21—Shaping processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/01—Improving mechanical properties or manufacturing
    • F17C2260/011—Improving strength
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/01—Improving mechanical properties or manufacturing
    • F17C2260/017—Improving mechanical properties or manufacturing by calculation

Definitions

  • the invention relates to an alloy of AI for hollow bodies under pressure containing Zn, Cu, Mg as main alloying elements (series 7000 according to the designations of the Aluminum Association) and intended, in particular, for manufacturing metal cylinders for pressurized gas.
  • EP-A-81441 also discloses an aluminum alloy containing Zn, Mg, Cu and between 0.08 and 0.14% of Zr having high ductility and tenacity.
  • the contents are preferably held in the following field, individually or in combination
  • the alloys according to the invention are pourable by conventional methods such as semi-continuous casting and the characteristics required on the bottles are met.
  • FIGS. 1 and 2 The invention will be better understood using the following examples, illustrated by FIGS. 1 and 2.
  • This composition is therefore not suitable for reliable industrial production, despite its good compromise between toughness and mechanical strength.
  • the reference 1 and 14 castings also have good resistance to corrosion under stress (non-rupture in 30 days under the conditions indicated).
  • FIG. 2 shows that only the alloys according to the invention make it possible to comply with all of the criteria imposed.
  • Zone 1 corresponds to an acceptable burst behavior with sufficient mechanical characteristics.
  • Zone II corresponds to sufficient mechanical characteristics but to poor burst behavior.
  • Zone III corresponds to insufficient mechanical characteristics and good bursting behavior.
  • zone IV corresponds to insufficient mechanical characteristics and poor bursting behavior.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Engineering & Computer Science (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Pressure Vessels And Lids Thereof (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Air Bags (AREA)

Abstract

The invention relates to hollow bodies for gas under pressure manufactured from an aluminum alloy containing Zn, Cu and Mg as principal alloying elements and intended in particular for the production of metal bottles for pressurized gas. The hollow bodies are manufactured from an alloy consisting essentially of (in % by weight): -6.25 </= Zn </= 8.0 Mn </= 0.20 -1.2 </= Mg </= 1.95 Zr </= 0.05 -1.7 </= Cu </= 2.8 Ti </= 0.05 -0.15 </= Cr </= 0.28 Others each </=0.05 -Fe </= 0.20 Others total </=0.15 -Si + Fe </= 0.40 Balance Al. - The alloy in state T73 complies with the very severe technical requirements in respect of strength and ductility which are imposed in relation to use for hollow bodies under pressure.

Description

L'invention se rapporte à un alliage d'AI pour corps creux sous pression contenant du Zn, Cu, Mg comme éléments d'alliage principaux (série 7000 selon les désignations de l'Aluminium Association) et destiné, en particulier, à la fabrication des bouteilles métalliques pour gaz sous pression.The invention relates to an alloy of AI for hollow bodies under pressure containing Zn, Cu, Mg as main alloying elements (series 7000 according to the designations of the Aluminum Association) and intended, in particular, for manufacturing metal cylinders for pressurized gas.

Jusqu'ici aucun des alliages d'Al connus, à haute résistance, n'a pu satisfaire de manière sure et reproductible les exigences techniques sévères correspondant à cette dernière application et qui sont les suivantes :

  • - Caractéristiques mécaniques : Rp 0,2 > 370 MPa (sens long) Rm > 460 MPa A% ≥ 12%
  • - Tenue à la corrosion sous tension, sous 75% de R0,2 garanti, soit 280 MPa, durée supérieure à 30 jours en immersion - émersion alternée 10 min/50 min dans une solution aqueuse à 3,5% NaCI à température ambiante sur éprouvette en C dans les conditions de la norme ASTM G-38-73 (réapprouvée en 1984)
  • - Déchirure ductile du corps creux de forme cylindrique à la suite d'une épreuve d'éclatement hydrau-.lique à l'eau ; la déchirure doit être :
  • - longitudinale dans sa plus grande partie (parallèle aux génératrices)
  • - ne pas être ramifiée
  • - ne pas s'étendre de plus de 90° de part et d'autre de la partie principale de la déchirure
  • - ne pas s'étendre dans une partie du corps dont l'épaisseur dépasse 1,5 fois l'épaisseur maximale mesurée au milieu du corps.
Up to now, none of the known high-strength Al alloys has been able to safely and reproducibly meet the severe technical requirements corresponding to this latter application, which are as follows:
  • - Mechanical characteristics: Rp 0.2> 370 MPa (long direction) Rm> 460 MPa A% ≥ 12%
  • - Resistance to corrosion under tension, under 75% of guaranteed R0.2, i.e. 280 MPa, duration greater than 30 days in immersion - alternating emersion 10 min / 50 min in a 3.5% NaCl aqueous solution at room temperature on C specimen under the conditions of ASTM G-38-73 (re-approved in 1984)
  • - Ductile tearing of the cylindrical hollow body following a hydrau-.lique burst test with water; the tear must be:
  • - longitudinal for the most part (parallel to the generators)
  • - not to be branched
  • - do not extend more than 90 ° on either side of the main part of the tear
  • - do not extend into a part of the body whose thickness exceeds 1.5 times the maximum thickness measured in the middle of the body.

On a tenté de résoudre ce problème par utilisation d'un alliage type 7475 (selon la nomenclature de l'Aluminium Association) mais cet alliage s'est révélé non fiable lors d'essais industriels étendus (voir FR-A-2 510 231), et ce, malgré son niveau de ténacité très élevée, sa bonne résistance mécanique et sa remarquable tenue à la corrosion sous tension à l'état T73.We tried to solve this problem by using an alloy type 7475 (according to the nomenclature of the Aluminum Association) but this alloy proved to be unreliable during extensive industrial tests (see FR-A-2 510 231) , despite its very high level of toughness, its good mechanical resistance and its remarkable resistance to corrosion under tension in the T73 state.

On connait aussi de EP-A-81441 un alliage d'aluminium contenant du Zn, du Mg, du Cu et entre 0,08 et 0,14% de Zr présentant une ductilité et une tenacité élevées.EP-A-81441 also discloses an aluminum alloy containing Zn, Mg, Cu and between 0.08 and 0.14% of Zr having high ductility and tenacity.

Le problème difficile mentionné plus haut est résolu selon l'invention par l'utilisation d'un alliage de composition suivante (en poids%) :

Figure imgb0001
The difficult problem mentioned above is solved according to the invention by the use of an alloy of the following composition (by weight%):
Figure imgb0001

Les teneurs sont tenues, de préférence, dans le domaine suivant, individuellement ou en combinaison

Figure imgb0002
Figure imgb0003
 The contents are preferably held in the following field, individually or in combination
Figure imgb0002
Figure imgb0003

Les alliages selon l'invention sont coulables par les procédés classiques tel que la coulée semi-continue et les caractéristiques exigées sur les bouteilles sont respectées.The alloys according to the invention are pourable by conventional methods such as semi-continuous casting and the characteristics required on the bottles are met.

L'invention sera mieux comprise à l'aide des exemples suivants, illustrés par les fig. 1 et 2.The invention will be better understood using the following examples, illustrated by FIGS. 1 and 2.

  • La fig. 1 représente le compromis limite élastique - ténacité (Klc sens travers court) d'alliages d'AI à haute résistance connus et résistant à la corrosion sous tension.Fig. 1 shows the compromise between elastic limit and toughness (K lc short cross direction) of known high-strength AI alloys resistant to stress corrosion.
  • La fig. 2 représente les résultats des caractéristiques charge de rupture (Rm) - longueur de fissure lors des essais d'éclatement sur bouteilles pour divers alliages.Fig. 2 represents the results of the breaking load (Rm) - crack length characteristics during burst tests on bottles for various alloys.
Exemple n°1 (hors l'invention - fig. 1)Example n ° 1 (outside the invention - fig. 1)

Des alliages 7475 dont les compositions chimiques sont reportées au tableau ont été élaborés et transformés en bouteilles de 6 litres suivant la gamme de fabrication rapportée ci-après :

  • Coulée de billettes 0 164,5 mm en semi-continu
  • Sciage des lopins
  • Réchauffage des lopins
  • Filage inverse d'étuis
  • Etirages à chaud et à froid
  • Usinage du fond
  • Mise à longueur
  • Ogivage à chaud
  • Perçage du goulot et usinage
  • Décapage
  • Mise en solution
  • Trempe à l'eau froide
  • Revenu type T73
7475 alloys, the chemical compositions of which are given in the table, were developed and transformed into 6-liter bottles according to the production range reported below:
  • Billet casting 0 164.5 mm semi-continuous
  • Sawing plots
  • Reheating of plots
  • Reverse wiring of cases
  • Hot and cold drawing
  • Bottom machining
  • Cut to length
  • Hot icing
  • Bottom drilling and machining
  • Pickling
  • Dissolution
  • Cold water quenching
  • Income type T73

Les résultats d'essais de traction sens long (moyenne de 6 éprouvettes x 2 bouteilles), de corrosion sous tension (1 bouteille) et d'éclatement hydraulique (3 bouteilles) sont reportés au tableau Il.The results of long-term tensile tests (average of 6 test pieces x 2 bottles), stress corrosion (1 bottle) and hydraulic burst (3 bottles) are shown in Table II.

On peut constater le comportement instable de cet alliage en particulier en ce qui concerne l'aspect de la déchirure.We can see the unstable behavior of this alloy in particular with regard to the appearance of the tear.

Cette composition ne convient donc pas à une production industrielle fiable, malgré son bon compromis ténacité - résistance mécanique.This composition is therefore not suitable for reliable industrial production, despite its good compromise between toughness and mechanical strength.

Exemple 2Example 2

On a coulé en billettes, 7 alliages dont les compositions sont reportées au tableau III ; celles ci ont été transformées en bouteilles de 6 litres (hauteur totale : 565 mm ; 0 extérieur : 152 mm ; 0 intérieur : 127 mm) selon la gamme de fabrication analogue à celle de l'exemple 1, sauf en ce qui concerne le revenu. Deux des alliages (repérés 1 et 14) sont conformes à l'invention, les autres sont hors l'invention.7 alloys were cast in billets, the compositions of which are given in Table III; these were transformed into 6 liter bottles (total height: 565 mm; outside 0: 152 mm; inside 0: 127 mm) according to the manufacturing range similar to that of Example 1, except as regards income . Two of the alloys (marked 1 and 14) are in accordance with the invention, the others are outside the invention.

Trois revenus ont été pratiqués :

  • Ri-6 h 105°C + 5 h 30 177°C (surrevenu peu poussé)
  • R2-6 h 105°C + 9 h 177°C (fortement surrevenu)
  • R3-6 h 105°C + 24h 177°C (très fortement surrevenu, dans un cas)
Three incomes were practiced:
  • R i -6 h 105 ° C + 5 h 30 177 ° C (overgrown little push)
  • R 2 -6 h 105 ° C + 9 h 177 ° C (highly occured)
  • R 3 -6 h 105 ° C + 24h 177 ° C (very strongly occurring, in one case)

Les résultats d'essais de caractéristiques mécaniques (sens long) et des essais d'éclatement sont reportés au tableau IV. On peut constater que seules les compositions selon l'invention permettent de satisfaire toutes les exigences techniques.The results of mechanical characteristics tests (long sense) and burst tests are given in Table IV. It can be seen that only the compositions according to the invention make it possible to satisfy all the technical requirements.

Les coulées repères 1 et 14 ont également une bonne tenue à la corrosion sous tension (non rupture en 30 jours dans les conditions indiquées).The reference 1 and 14 castings also have good resistance to corrosion under stress (non-rupture in 30 days under the conditions indicated).

Les longueurs moyennes des fissures développées sur les 3 bouteilles d'essais par cas sont reportées au tableau V.The average lengths of the cracks developed on the 3 test bottles per case are shown in Table V.

La figure 2 fait apparaître que seuls les alliages selon l'invention permettent de respecter l'ensemble des critères imposés.FIG. 2 shows that only the alloys according to the invention make it possible to comply with all of the criteria imposed.

La zone 1 correspond à un comportement acceptable à l'éclatement avec des caractéristiques mécaniques suffisantes.Zone 1 corresponds to an acceptable burst behavior with sufficient mechanical characteristics.

La zone Il correspond à des caractéristiques mécaniques suffisantes mais à un mauvais comportement à l'éclatement.Zone II corresponds to sufficient mechanical characteristics but to poor burst behavior.

La zone III correspond à des caractéristiques mécaniques insuffisantes et à un bon comportement à l'éclatement.Zone III corresponds to insufficient mechanical characteristics and good bursting behavior.

et la zone IV correspond à des caractéristiques mécaniques insuffisantes et à un mauvais comportement à l'éclatement.and zone IV corresponds to insufficient mechanical characteristics and poor bursting behavior.

Figure imgb0004
Figure imgb0004
Figure imgb0005
Figure imgb0005
Figure imgb0006
Figure imgb0006
Figure imgb0007
Figure imgb0007
Figure imgb0008
Figure imgb0008

Claims (5)

1. An AI alloy for hollow bodies under pressure which can be cast by semi -continuous casting characterised in that it contains (in % by weight) :
Figure imgb0019
2. An AI alloy according to Claim 1 characterised in that
Figure imgb0020
3. An AI alloy according to one of claims 1 and 2 characterised in that
Figure imgb0021
4. An alloy according to one of claims 1 to 3 characterised in that
Figure imgb0022
5. An alloy according to one of claims 1 to 4 characterised in that
Figure imgb0023
EP86420225A 1986-07-24 1986-09-09 Aluminium base alloy for hollow bodies for pressure containers Expired - Lifetime EP0257167B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86420225T ATE60809T1 (en) 1986-07-24 1986-09-09 ALUMINUM BASED ALLOY FOR HOLLOW BODY FOR PRESSURE TANKS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8610930A FR2601967B1 (en) 1986-07-24 1986-07-24 AL-BASED ALLOY FOR HOLLOW BODIES UNDER PRESSURE.
FR8610930 1986-07-24

Publications (2)

Publication Number Publication Date
EP0257167A1 EP0257167A1 (en) 1988-03-02
EP0257167B1 true EP0257167B1 (en) 1991-02-06

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US (1) US4747890A (en)
EP (1) EP0257167B1 (en)
JP (1) JPS6333539A (en)
AT (1) ATE60809T1 (en)
AU (1) AU587069B2 (en)
BR (1) BR8703823A (en)
CA (1) CA1307140C (en)
CH (1) CH671237A5 (en)
DE (1) DE3677512D1 (en)
DK (1) DK166689B1 (en)
ES (1) ES2001145A6 (en)
FR (1) FR2601967B1 (en)
IE (1) IE59322B1 (en)

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JPS6058299B2 (en) * 1982-06-08 1985-12-19 株式会社神戸製鋼所 Method for producing Al-Zn-Mg-Cu alloy material with excellent formability
JPS59129750A (en) * 1983-01-18 1984-07-26 Mitsubishi Alum Co Ltd High strength composite al material for water storage vessel having pitting resistance

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10301710B2 (en) 2005-01-19 2019-05-28 Otto Fuchs Kg Aluminum alloy that is not sensitive to quenching, as well as method for the production of a semi-finished product

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AU587069B2 (en) 1989-08-03
DK457686A (en) 1988-01-25
DE3677512D1 (en) 1991-03-14
US4747890A (en) 1988-05-31
CH671237A5 (en) 1989-08-15
ES2001145A6 (en) 1988-04-16
JPH0575815B2 (en) 1993-10-21
CA1307140C (en) 1992-09-08
BR8703823A (en) 1988-03-29
JPS6333539A (en) 1988-02-13
DK457686D0 (en) 1986-09-25
FR2601967B1 (en) 1992-04-03
IE862531L (en) 1988-01-24
ATE60809T1 (en) 1991-02-15
IE59322B1 (en) 1994-02-09
DK166689B1 (en) 1993-06-28
FR2601967A1 (en) 1988-01-29
AU6329186A (en) 1988-01-28
EP0257167A1 (en) 1988-03-02

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