EP0066361B1 - Alliage à base de nickel, résistant à la corrosion et possédant des caractéristiques mécaniques élevées - Google Patents

Alliage à base de nickel, résistant à la corrosion et possédant des caractéristiques mécaniques élevées Download PDF

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Publication number
EP0066361B1
EP0066361B1 EP82301929A EP82301929A EP0066361B1 EP 0066361 B1 EP0066361 B1 EP 0066361B1 EP 82301929 A EP82301929 A EP 82301929A EP 82301929 A EP82301929 A EP 82301929A EP 0066361 B1 EP0066361 B1 EP 0066361B1
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Prior art keywords
alloy
cold
titanium
niobium
age
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EP82301929A
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German (de)
English (en)
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EP0066361A2 (fr
EP0066361A3 (en
EP0066361B2 (fr
Inventor
Herbert Louis Eiselstein
Jerry Ardon Harris
Darrel Franklyn Smith, Jr.
Edward Frederick Clatworthy
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Huntington Alloys Corp
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Inco Alloys International Inc
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Priority to AT82301929T priority Critical patent/ATE18260T1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%

Definitions

  • the present invention relates to the use of nickel based alloys which have a combination of high strength and corrosion resistance.
  • Alloys having high strength are required in some applications for sustaining stress in load-bearing service in chemically adverse environments. Some plastic ductility is also needed for enduring or permitting modest amounts of deformation without sudden fracture, for example to safeguard against accidental bending, or to enable cold forming to be carried out. Alloys having this desirable combination of properties are particularly useful for use in petroleum production tubing for oil wells, in contact with chemically adverse media such as chlorides, acids and such compounds as hydrogen sulphide. The alloys must therefore exhibit resistance to corrosive pitting, stress corrosion cracking and hydrogen embrittlement, as well as high strength.
  • the prior art includes numerous disclosures, for example in GB-A-1 385 755, of age-hardenable nickel-iron-chromium alloys that are said to be very resistant to oxidation at elevated temperatures and to be suitable for fabricated parts such as aeronautical turbines or turbine casings.
  • INCONEL alloy 718 as disclosed and claimed in US-A-3 046 108, is an age-hardenable high strength alloy for service over a wide temperature range, from -250°C to 700°C, and offers good resistance to a wide variety of corrosive environments. Since the alloy also offers excellent stress rupture properties and fatigue strength, it has been used in down-hole service in oil wells. However, the alloy has insufficient resistance to hydrogen embrittlement in the harsh environments found in "sour well” conditions and, although having high as-cold-drawn strength, has low ductility.
  • the present invention is based on the discovery that certain alloy compositions, developed from alloy 718, have an excellent combination of strength and ductility in the wrought and age-hardened condition and also excellent resistance to hydrogen embrittlement and chloride stress cracking.
  • an alloy consisting, by weight, of from 15 to 22% chromium, 10 to 28% iron, 6 to 9% molybdenum, 2.5 to 5% niobium, 1 to 2% titanium, and up to 1% aluminium, the balance, apart from impurities and incidental elements, being nickel in a proportion of from 45 to 55% of the alloy, is used for wrought and age-hardened articles and parts requiring high resistance in use to corrosive conditions such as obtain in deep oil or gas wells or in environments containing sulphur dioxide.
  • Further elements which may be present in small amounts include up to 0.1% carbon, up to 0.35% silicon, up to 0.35% manganese, up to 0.01% boron, and also residual small amounts of cerium, calcium, lanthanum, mischmetal, neodymium and zirconium such as can remain from additions totalling up to 0.2% of the furnace charge.
  • Impurities present may include up to 0.5% copper, up to 0.015% sulphur and up to 0.015% phosphorus.
  • molybdenum and niobium are often associated with tungsten and tantalum, which may be present at levels of about 0.1% tungsten and 0.1% tantalum.
  • the tungsten must be controlled at a low level to avoid the formation of undesired phases such as Laves phase.
  • tantalum may be substituted for niobium in equiatomic percentages, its presence is not desirable because of its high atomic weight.
  • chromium iron, molybdenum, niobium, titanium, aluminium and nickel gives rise to desirable properties of strength, ductility, fabricability and durability in highly corrosive environments.
  • a preferred composition for use according to the invention contains from 18.5 to 20.5% chromium, 13.5 to 18% iron, 6.5 to 7.5% molybdenum, 1.3 to 1.7% titanium, 0.05 to 0.5% aluminium, balance (apart from impurities and incidental elements) nickel.
  • the titanium and niobium contents of the alloy are closely controlled such that Preferably the alloy contains 1.3% to 1.7% titanium and 3.6% to 4.4% Nb, and most preferably 1.5% Ti and 4% Nb.
  • the alloy has good workability, both hot and cold, for production into wrought articles such as cold rolled strip and extruded tubing.
  • Appropriate process treatments may be used to enhance the strengths of articles manufactured from the alloy. Such treatments include cold working, age-hardening and combinations of the two.
  • the alloy may be annealed at a temperature of 871°C to 1149°C, and aged at 593°C to 760°C, or even 816°C. Direct aging treatments of heating the cold-worked alloy at 649°C to 760°C for from 0.5 to 5 hours directly after cold working are particularly beneficial for obtaining desirable combinations of high strength and ductility.
  • Alloys of the present invention after appropriate thermomechanical processing exhibit yield strength (0.2% offset) of in excess of 1034 MN/m 2 , with an elongation of 8%, and preferred alloys have strengths of more than 1310 MN/m 2 and elongation of around 15%.
  • Alloy 1 was prepared by vacuum induction melting and was cast to ingot form. Ingots of alloy 1 were heated at 1121°C for 16 hours for homogenization and then forged flat from 1121°C. Flats were hot rolled at 1121°C to reduce about 4 mm (0.16 gauge), annealed at 1066°C for 1 hour and cold rolled to 2.5 mm (0.1 gauge) strip, which was again annealed at 1066°C for 1 hour.
  • Hardenability including work hardenability and age hardenability, of alloy 1 was confirmed with hardness measurements, as shown in Table 11, on specimens of the 1.27 mm (0.05 gauge) strip before and after heat treatments with temperatures and times referred to in the Heat Treatment Schedule (Table III).
  • Annealed hardnesses of 20% CR strip on Rockwell B scale after treatments of 954°C for hour, 1038°C for 1 hour and 1149°C for hour were 97,93 and 78.
  • Corresponding results with 40% CR strip were 23.5.
  • Alloy 2 and alloy 3 were air induction melted and centrifugally cast with protection of an argon shroud in a metal mould having a 10.8 cm I.D. and 1300 rpm rotation speed to produce cast centrifugally solidified tube shells of alloy 2 and 3. Cast dimensions were 10.8 cm O.D. and 1.9 cm wall thickness. The shell was cleaned up to 10.2 cm O.D. and 1.11 cm wall thickness.
  • a leader tube was welded onto the shell and processing proceeded as follows.
  • the tube shell was annealed at 1149°C, pickled and cold drawn (about 15.8%) to 9.525 cm O.D.x0.99 cm wall, re-annealed at 1149°C and pickled, then cold drawn to 8.89 cm O.D.xO.889 cm wall (also 15.8% reduction), re-annealed at 1149°C and pickled, then tube reduced to 6.668 cm O.D.xO.762 cm wall (about 36.7% reduction in area).
  • a transverse specimen taken from the extruded and 704°C direct aged product of alloy 3 was of ASTM grain size No. 32; optical microscopy of the specimen showed an absence of intergranular carbides and indicated that the extruded, cold-reduced and heat-treated microstructure did not contain any intra- granular phases resolvable at 1000x.
  • Alloys 2, 3 and E were melted, and centrifugally cast to tube shells and processed to 6.67 cm O.D. tube with 0.762 cm wall thickness by the process described in Example 2.
  • Table VI compares chloride stress corrosion cracking data for these alloys at 177°C and 204°C.
  • the alloy samples were prepared as stressed C-ring specimens and subjected to a simulated deep sour gas well environment comprising a 25% solution of sodium chloride plus 0.5% acetic acid and 1 g/l sulphur, the solution saturated with hydrogen sulphide to an H 2 S overpressure of 861 KN/m 2 .-
  • test conditions chosen for alloy E were those considered to be less prone to hydrogen embrittlement than the cold worked+aged samples of alloys 2 and 3. Despite testing at lower stress the comparative alloy failed earlier than alloys of the invention.
  • the room temperature tensile data corresponding to the above corrosion data is summarised in Table VIII.
  • alloys 2, 3 of the present invention exhibit a desirable combination of strength and ductility.
  • Alloys of the present invention are useful for tubes, vessels, casings and supports, needed for sustaining heavy loads and shocks in rough service while exposed to corrosive media, and particularly for production tubing to tap deep natural reservoirs of hydrocarbon fuels.
  • the alloys are beneficial for resistance to media such as hydrogen sulphide, carbon dioxide, organic acids and concentrated brine solutions sometimes present with petroleum.
  • the alloys provide good resistance to corrosion in sulphur dioxide gas scrubbers and are useful for seals, ducting, fans, and stack lines in such environments.
  • Articles of the alloy can provide useful strength at elevated temperatures up to 648°C and possibly higher.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Gas Separation By Absorption (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Adornments (AREA)
  • Conductive Materials (AREA)

Claims (8)

1. Utilisation d'un alliage comprenant, en poids, de 15 à 22% de chrome, de 10 à 28% de fer, de 6 à 9% de molybdène, de 2,5 à 5% de niobium, de 1 à 2% de titane, jusqu'à 1 % d'aluminium, jusqu'à 0,1% de carbone, jusqu'à 0,35% de silicium, jusqu'à 0,35% de manganèse, jusqu'à 0,01% de bore, avec ou sans quantités résiduelles ne dépassant pas 0,2% au total de cérium, calcium, lanthane, mischmetale, magnésium, néodymium et zirconium, le complément étant, outre les impuretés, le nickel en une proportion de 45 à 55% de l'alliage, pour des articles travaillés et durcis par vieillissement et des pièces exigeant en service une haute résistance aux conditions corrosives, telles qu'on les obtient dans des puits profonds de pétrole ou de gaz ou dans des environnements contenant de l'anhydride sulfureux.
2. Utilisation selon la revendication 1 d'un alliage tel que défini dans celle-ci, selon laquelle les quantités de titane et de niobium sont en corrélation conformément à la relation:
Figure imgb0012
3. Utilisation selon la revendication 1 d'un alliage tel que défini dans la revendication 2, contenant 1,3 à 1,7% de titane et 3,6 à 4,4% de niobium.
4. Utilisation selon la revendication 1, d'un alliage tel que défini dans l'une quelconque des revendications précédentes qui contient de 18,5 à 20,5% de chrome, de 13,5 à 18% de fer, de 6,5 à 7,5% de molybdène, de 1,3 à 1,7% de titane et de 0,05 à 0,5% d'aluminium.
5. Utilisation selon la revendication 1, d'un alliage tel que défini dans l'une quelconque des revendications précédentes, qui a été travaillé à chaud ou écroui et traité par la chaleur pour obtenir une limite élastique (0,2% de déformation) de plus de 1034 MN/m2 et un allongement de plus de 8%.
6. Utilisation selon la revendication 1, d'un alliage tel que défini dans la revendication 5 qui a été thermiquement traité par recuit à une température entre 871 et 1149°C et par vieillissement à une température de 593 à 816°C.
7. Utilisation selon la revendication 1, d'un alliage tel que défini dans la revendication 5 qui a été écroui et ensuite vieilli à une température de 649 à 760°C pendant 0,5 à 5 heures.
8. Utilisation d'un alliage selon l'une quelconque des revendications précédentes pour la production par forgeage et durcissement par vieillissement de tubes pour les puits profonds de pétrole et de gaz.
EP82301929A 1981-04-17 1982-04-14 Alliage à base de nickel, résistant à la corrosion et possédant des caractéristiques mécaniques élevées Expired - Lifetime EP0066361B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82301929T ATE18260T1 (de) 1981-04-17 1982-04-14 Korrosionsbestaendige hochfeste nickellegierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25515881A 1981-04-17 1981-04-17
US255158 1981-04-17

Publications (4)

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EP0066361A2 EP0066361A2 (fr) 1982-12-08
EP0066361A3 EP0066361A3 (en) 1983-01-19
EP0066361B1 true EP0066361B1 (fr) 1986-02-26
EP0066361B2 EP0066361B2 (fr) 1990-10-10

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EP (1) EP0066361B2 (fr)
JP (1) JPS57203741A (fr)
AT (1) ATE18260T1 (fr)
CA (1) CA1194346A (fr)
DE (1) DE3269304D1 (fr)
ES (1) ES511490A0 (fr)

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JPS58174538A (ja) * 1982-04-02 1983-10-13 Hitachi Ltd 原子炉用隙間構造部材に用いられる耐応力腐食割れ性に優れたＮｉ基合金製部材
US4788036A (en) * 1983-12-29 1988-11-29 Inco Alloys International, Inc. Corrosion resistant high-strength nickel-base alloy
JP2554049B2 (ja) * 1986-01-20 1996-11-13 三菱重工業株式会社 Ｎｉ基合金及びその製造法
JP2554048B2 (ja) * 1986-01-20 1996-11-13 三菱重工業株式会社 Ｎｉ基合金及びその製造方法
IL82587A0 (en) * 1986-05-27 1987-11-30 Carpenter Technology Corp Nickel-base alloy and method for preparation thereof
US5556594A (en) * 1986-05-30 1996-09-17 Crs Holdings, Inc. Corrosion resistant age hardenable nickel-base alloy
JPS63137133A (ja) * 1986-11-28 1988-06-09 Sumitomo Metal Ind Ltd 高耐食性析出硬化型Ｎｉ基合金
FR2653451B1 (fr) * 1989-10-20 1993-08-13 Tecphy Procede d'amelioration de la resistance a la corrosion d'un alliage a base de nickel et alliage ainsi realise.
FR2820197B1 (fr) * 2001-01-30 2006-01-06 Elf Antar France Dispositif reducteur d'encrassement d'un echangeur thermique tubulaire
US7837812B2 (en) 2004-05-21 2010-11-23 Ati Properties, Inc. Metastable beta-titanium alloys and methods of processing the same by direct aging
US10053758B2 (en) 2010-01-22 2018-08-21 Ati Properties Llc Production of high strength titanium
US9255316B2 (en) 2010-07-19 2016-02-09 Ati Properties, Inc. Processing of α+β titanium alloys
US8499605B2 (en) 2010-07-28 2013-08-06 Ati Properties, Inc. Hot stretch straightening of high strength α/β processed titanium
US9206497B2 (en) 2010-09-15 2015-12-08 Ati Properties, Inc. Methods for processing titanium alloys
US8613818B2 (en) 2010-09-15 2013-12-24 Ati Properties, Inc. Processing routes for titanium and titanium alloys
US10513755B2 (en) 2010-09-23 2019-12-24 Ati Properties Llc High strength alpha/beta titanium alloy fasteners and fastener stock
US8652400B2 (en) * 2011-06-01 2014-02-18 Ati Properties, Inc. Thermo-mechanical processing of nickel-base alloys
US10253382B2 (en) 2012-06-11 2019-04-09 Huntington Alloys Corporation High-strength corrosion-resistant tubing for oil and gas completion and drilling applications, and process for manufacturing thereof
US9050647B2 (en) 2013-03-15 2015-06-09 Ati Properties, Inc. Split-pass open-die forging for hard-to-forge, strain-path sensitive titanium-base and nickel-base alloys
US9869003B2 (en) 2013-02-26 2018-01-16 Ati Properties Llc Methods for processing alloys
US9192981B2 (en) 2013-03-11 2015-11-24 Ati Properties, Inc. Thermomechanical processing of high strength non-magnetic corrosion resistant material
US9777361B2 (en) 2013-03-15 2017-10-03 Ati Properties Llc Thermomechanical processing of alpha-beta titanium alloys
US11111552B2 (en) 2013-11-12 2021-09-07 Ati Properties Llc Methods for processing metal alloys
US10094003B2 (en) 2015-01-12 2018-10-09 Ati Properties Llc Titanium alloy
US10502252B2 (en) 2015-11-23 2019-12-10 Ati Properties Llc Processing of alpha-beta titanium alloys
CN107541618A (zh) * 2017-10-12 2018-01-05 河钢股份有限公司 一种热压烧结模具用合金材料

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DE1250642B (fr) * 1958-11-13 1967-09-21
US2994605A (en) * 1959-03-30 1961-08-01 Gen Electric High temperature alloys
GB999439A (en) * 1962-05-10 1965-07-28 Allegheny Ludlum Steel Improvements in or relating to an austenitic alloy
GB1083432A (en) * 1963-12-26 1967-09-13 Gen Electric Improvements in nickel-iron-chromium base alloy
FR2154871A5 (fr) * 1971-09-28 1973-05-18 Creusot Loire
JPS57123948A (en) * 1980-12-24 1982-08-02 Hitachi Ltd Austenite alloy with stress corrosion cracking resistance

Also Published As

Publication number Publication date
ES8306801A1 (es) 1983-06-01
EP0066361A2 (fr) 1982-12-08
CA1194346A (fr) 1985-10-01
EP0066361A3 (en) 1983-01-19
EP0066361B2 (fr) 1990-10-10
DE3269304D1 (en) 1986-04-03
JPS57203741A (en) 1982-12-14
ATE18260T1 (de) 1986-03-15
JPS6134498B2 (fr) 1986-08-08
ES511490A0 (es) 1983-06-01

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