EP0091308B1 - Alliage à base de nickel, résistant à la corrosion - Google Patents

Alliage à base de nickel, résistant à la corrosion Download PDF

Info

Publication number
EP0091308B1
EP0091308B1 EP83301891A EP83301891A EP0091308B1 EP 0091308 B1 EP0091308 B1 EP 0091308B1 EP 83301891 A EP83301891 A EP 83301891A EP 83301891 A EP83301891 A EP 83301891A EP 0091308 B1 EP0091308 B1 EP 0091308B1
Authority
EP
European Patent Office
Prior art keywords
weight
alloy
molybdenum
alloys
corrosion resistance
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.)
Expired
Application number
EP83301891A
Other languages
German (de)
English (en)
Other versions
EP0091308A3 (en
EP0091308A2 (fr
Inventor
Richard L. Kennedy
Ronald J. Gerlock
Clarence G. Bieber
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.)
TDY Industries LLC
Original Assignee
Teledyne Industries Inc
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 Teledyne Industries Inc filed Critical Teledyne Industries Inc
Priority to AT83301891T priority Critical patent/ATE30050T1/de
Publication of EP0091308A2 publication Critical patent/EP0091308A2/fr
Publication of EP0091308A3 publication Critical patent/EP0091308A3/en
Application granted granted Critical
Publication of EP0091308B1 publication Critical patent/EP0091308B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%

Definitions

  • This invention relates to a corrosion resistant nickel base alloy, and more particularly to an improved hot and cold workable nickel base alloy which has excellent corrosion resistance under a broad range of corrosive conditions, and which is particularly suited for use in highly corrosive deep sour gas well applications.
  • alloys used commercially in applications requiring good corrosion resistance are nickel base alloys. Such alloys generally contain relatively large amounts of chromium and molybdenum, and usually also contain substantial proportions of iron, copper or cobalt. Alloy C-276 for example, a well known corrosion resistant nickel base alloy used in a variety of corrosive applications, has a nominal composition of about 15.5% chromium, 15.5% molybdenum, 3.5% tungsten, 6% iron, 2% cobalt and the balance nickel.
  • alloy B-2 which has a nominal composition of about 28% molybdenum, 1% chromium, 2% iron, 1% cobalt, and the balance nickel
  • alloy 625 which contains about 21.5% chromium, 9% molybdenum, 4% iron, 3.6% niobium, and the balance nickel
  • alloy 718 which contains about 19% chromium, 3% molybdenum, 19% iron, 5.1% niobium, and the balance nickel.
  • nickel base alloy having outstanding corrosion resistance over a broad range of corrosive conditions ranging from oxidizing conditions to reducing conditions, and which performs particularly well in tests designed to simulate the extremely severe corrosive environment found in deep sour gas well operations. Additionally, this alloy exhibits excellent hot and cold workability, and has a relatively low content of expensive alloying elements.
  • the present invention consists in a nickel. base alloy containing chromium and molybdenum and having excellent hot and cold workability and superior corrosion resistance to a variety of media including deep sour gas well environments, said alloy being characterised in that it consists of 27 to 33% by weight of chromium, 8 to 12% by weight of molybdenum, and 0-4% by weight of tungsten, with or without up to '1.5% by weight of iron, up to 12% by weight of cobalt, up to 0.15% by weight of carbon, up to 1.5% by weight of aluminium, up to 1.5% by weight of titanium and up to 2% by weight of niobium, the balance apart from impurities being nickel.
  • the alloy may also contain incidental impurities and additions of other unspecified elements which do not materially affect the basic and novel characteristics of the alloy, particularly the corrosion resistance of the alloy.
  • Chromium is an essential element in the alloy of the present invention because of the added corrosion resistance that it contributes. It appears from testing that the corrosion resistance is at an optimum when the chromium is at about 31 % of the composition. When the chromium is raised above about 33%, both the hot workability and the corrosion resistance worsens. Corrosion resistance also worsens below about 27% chromium.
  • molybdenum provides improved pitting corrosion resistance.
  • An optimum content of about 10% molybdenum appears to yield the lowest corrosion rate in the solutions tested.
  • the molybdenum content is decreased below about 8%, the pitting and crevice corrosion increases significantly.
  • the molybdenum is increased above about 12%, and in addition, the hot and cold workability decrease noticeably.
  • Tungsten is not generally included in commercial alloys developed for corrosion resistant applications. This element is usually provided in applications where enhanced strength, particularly at high temperature, is of primary concern, and is not generally thought to have any beneficial effect on corrosion resistance.
  • the presence of tungsten has been found to significantly enhance the corrosion resistance. Corrosion testing shows that the absence of tungsten results in a significantly higher corrosion rate, while a tungsten content in excess of about 4% causes the material to corrode at a higher rate in certain solutions, as well as making the alloy more difficult to hot work.
  • the optimum tungsten content at the 10% molybdenum level appears to be about 2%, although replacement of some or all of the tungsten with additional molybdenum, for example, provides good corrosion resistance in some test media (see Table I, alloy M).
  • the alloy will normally also contain carbon at a level of up to 0.15% by weight, either as an incidental impurity or as a purposeful addition for forming stable carbides.
  • the carbon level should be maintained at a level up to a maximum of about 0.08% by weight, and most desirably to about 0.04%.
  • Aluminum may be present in small amounts to serve as a deoxidant. However, higher additions of aluminum adversely affect the workability of the alloy. Preferably, aluminum is present in amounts up to about 1.5% by weight, and most desirably up to about 0.25%.
  • Titanium and niobium may also be present in small amounts to serve as carbide formers. These elements are included at levels preferably up to about 1.5% by weight of titanium and about 2% by weight of niobium, and most desirably up to about 0.40% by weight. However, addition of significantly larger amounts of these elements has been found to have deleterious effects on hot workability.
  • Alloys in accordance with this invention may also contain minor amounts of other elements as impurities in the raw materials used or as deliberate additions to improve certain characteristics as is well known in the art.
  • minor proportions of magnesium, cerium, lanthanum, yttrium or misch metal may be optionally included to contribute to workability.
  • Tests have shown that magnesium can be tolerated up to about 0.10% by weight, preferably 0.07%, without significant loss of corrosion resistance.
  • Boron may be added, preferably up to about .005%, to contribute to high temperature strength and ductility.
  • Tantalum may be present at levels up to about 2% by weight without adversely affecting the corrosion resistance or workability, but the presence of tantalum at these levels has not been observed to benefit these properties of the alloy.
  • vanadium can be present up to about 1 % and zirconium up to 0.1% by weight.
  • Iron in significant amounts lowers the corrosion resistance of the alloy. Iron can be tolerated at levels up to about 1.5% by weight, but the corrosion resistance drops quite significantly at higher levels. Copper, manganese, and silicon, when present in small amounts or as impurities, can be tolerated. However, when added in significant amounts as alloying elements to the basic composition of this alloy, the elements have been found either to lower the corrosion resistance or to decrease the workability of the alloy or a combination of both. For example, the corrosion resistance of the alloy worsens significantly when copper is present at levels of about 1.5% by weight or greater, or manganese is present at levels of about 2% by weight or greater. Silicon is preferably. maintained at levels less than 1%.
  • Alloys in accordance with the invention are produced by introducing into a furnace metallic raw materials containing nickel and the other specified metallic elements within the percentage ranges stated. Heating the raw materials to form a melt, and pouring the melt from the furnace into a mould for solidification. Preferably, the melting is carried out under vacuum conditions. If desired, the thus formed alloy ingot may be further refined by remelting under vacuum conditions.
  • Test 1 is a standard test method for determining pitting and crevice corrosion resistance by the use of a ferric chloride solution.
  • the test specimens were immersed in a 10% by weight solution of ferric chloride for 72 hours at 50°C. This test method is similar to ASTM Standard Test Method G 48-76, except that the ASTM test uses 6% by weight ferric chloride.
  • test 2 the samples are immersed in a boiling aqueous solution of 10% sodium chloride and 5% ferric chloride for 24 hours.
  • Test 3 is a standard test method for detecting susceptibility to intergranular attack in wrought nickel-rich chromium bearing alloys (ASTM Test Method G 28-72). In this test, the samples are immersed in a boiling ferric sulfate-50% sulfuric acid solution for 24 hours. In test 4 the samples are immersed in boiling 65% nitric acid for 24 hours.
  • alloy N and alloy 0 Specimens of two alloys in accordance with the present invention were subjected to corrosion studies designed for evaluating performance in corrosive oilfield sour gas well hydrogen sulfide environments (Tests A, B and C) and simulated scrubber environments (Test D).
  • Alloys N and 0 had a nominal chemical composition as follows: 31% Cr, 10% Mo, 2% W, .40% Nb, .25% Ti, .25% Al, .001% max B,.10% max Fe,.10% max Cu, .04% C, .015% max S,.25% max Co, .015% max P, .10% max Ta,.10% max Zr, .10% max Mn, .01% max V, .25 max Si, balance nickel.
  • specimens of alloy C-276 were evaluated under similar conditions. All three materials were studied in the 500°F (260°C) aged and unaged conditions following unidirectional cold working.
  • Nickel-chrome wire was spot welded to the ends of beams stressed to 80 or 100 percent of yield strength. The beam specimens were then placed in the test solution and cathodically charged with hydrogen at a current of 25 mA/cm 2 . At the end of 13 days, alloy C-276 in the aged condition stressed at 100 percent of yield was found to have failed. Alloy C-276 in the unaged condition stressed to 100 percent yield strength failed after 21 days. Specimens of alloys N and 0 were retrieved unbroken at the end of the 28 day test.
  • Weight-loss corrosion coupons of each material were weighed, creviced, and placed in the "Green Death" solution. The coupons were cleaned and reweighed at 24 hours, 72 hours, and 168 hours. The coupons of alloys N and 0 had significantly less corrosion weight loss than the coupons of alloy C-276, as shown in Table IV.
  • the basic alloy composition (heat 367). was as follows: 31% Cr, 10% Mo, 2% W, .02% C, .25% Ti, .25% AI, .40% Nb, balance Ni.
  • chromium, molybdenum, tungsten, copper and iron heats were prepared with varying amounts of that element while holding all of the other specified elements constant.
  • Test specimens were prepared and tested as in Example 1 under the conditions of test #2 and test #3. The results are shown in Table V.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Resistance Heating (AREA)
  • Exhaust Silencers (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)

Claims (4)

1. Alliage à base de nickel, contenant du chrome et du molybdène et ayant une excellente aptitude au façonnage à chaud et à froid et une résistance supérieure à la corrosion vis-à-vis de toute une gamme de milieux, comprenant les environnements des puits profonds de gaz naturel acide, ledit alliage étant caractérisé en ce qu'il comprend de 27 à 33% en poids de chrome, de 8 à 12% en poids de molybdène et de 0 à 4% en poids de tungstène, avec ou sans jusqu'à 1,5% en poids de fer, jusqu'à 12% en poids de cobalt, jusqu'à 0,15% en poids de carbone, jusqu'à 1,5% en poids d'aluminium, jusqu'à 1,5% en poids de titane et jusqu'à 2% en poids de niobium, le reste, à part les impuretés, étant du nickel.
2. Alliage à base de nickel selon la revendication 1, caractérisé en outre en ce que la teneur en chrome est pratiquement de 31% et que la teneur en molybdène est pratiquement de 10% en poids.
3. Alliage à base de nickel selon l'une ou l'autre des revendications 1 ou 2, caractérisé en outre en ce que la teneur en tungstène est pratiquement de 2% en poids.
4. Alliage à base de nickel selon la revendication 1, caractérisé en ce qu'il contient pratiquement 12% en poids de molybdène, mais pas de tungstène.
EP83301891A 1982-04-05 1983-04-05 Alliage à base de nickel, résistant à la corrosion Expired EP0091308B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83301891T ATE30050T1 (de) 1982-04-05 1983-04-05 Korrosionsbestaendige legierung auf nickelbasis.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36577982A 1982-04-05 1982-04-05
US365779 1982-04-05

Publications (3)

Publication Number Publication Date
EP0091308A2 EP0091308A2 (fr) 1983-10-12
EP0091308A3 EP0091308A3 (en) 1984-09-05
EP0091308B1 true EP0091308B1 (fr) 1987-09-30

Family

ID=23440326

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83301891A Expired EP0091308B1 (fr) 1982-04-05 1983-04-05 Alliage à base de nickel, résistant à la corrosion

Country Status (13)

Country Link
EP (1) EP0091308B1 (fr)
JP (1) JPS58204145A (fr)
KR (1) KR900007118B1 (fr)
AR (1) AR231149A1 (fr)
AT (1) ATE30050T1 (fr)
AU (1) AU566664B2 (fr)
BR (1) BR8301735A (fr)
CA (1) CA1211961A (fr)
DE (1) DE3373921D1 (fr)
GB (1) GB2117793B (fr)
IN (1) IN157179B (fr)
MX (1) MX7543E (fr)
ZA (1) ZA832119B (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0092397A1 (fr) * 1982-04-20 1983-10-26 Huntington Alloys, Inc. Alliage nickel-chrome-molybdène
JPS60211030A (ja) * 1984-04-05 1985-10-23 Nippon Steel Corp 電気亜鉛メツキ用ロ−ル
IL82587A0 (en) * 1986-05-27 1987-11-30 Carpenter Technology Corp Nickel-base alloy and method for preparation thereof
US6740291B2 (en) * 2002-05-15 2004-05-25 Haynes International, Inc. Ni-Cr-Mo alloys resistant to wet process phosphoric acid and chloride-induced localized attack
JP4773773B2 (ja) * 2005-08-25 2011-09-14 東京電波株式会社 超臨界アンモニア反応機器用耐食部材
JP5096762B2 (ja) * 2007-02-26 2012-12-12 株式会社荏原製作所 遠心式ポンプ
CN104745882A (zh) * 2013-12-27 2015-07-01 新奥科技发展有限公司 一种镍基合金及其应用
CN115418529B (zh) * 2022-08-02 2023-04-07 常熟市良益金属材料有限公司 耐腐蚀镍基合金件及其制备方法及其连续抛光设备

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2681276A (en) * 1950-07-20 1954-06-15 Esterbrook Pen Co Pen nib alloy
IT505267A (fr) * 1952-10-25
US3008822A (en) * 1959-07-30 1961-11-14 Battelle Memorial Institute Nickel-base alloys
GB1210607A (en) * 1967-07-17 1970-10-28 Int Nickel Ltd Articles or parts of nickel-chromium or nickel-chromium-iron alloys
GB1288215A (fr) * 1968-10-07 1972-09-06
US3918964A (en) * 1973-12-21 1975-11-11 Sorcery Metals Inc Nickel-base alloys having a low coefficient of thermal expansion
US4184100A (en) * 1977-03-29 1980-01-15 Tokyo Shibaura Electric Co., Ltd. Indirectly-heated cathode device for electron tubes
JPS57203740A (en) * 1981-06-11 1982-12-14 Sumitomo Metal Ind Ltd Precipitation hardening alloy of high stress corrosion cracking resistance for high strength oil well pipe
JPS57207144A (en) * 1981-06-12 1982-12-18 Sumitomo Metal Ind Ltd Alloy for oil well pipe with superior stress corrosion cracking resistance and hot workability

Also Published As

Publication number Publication date
KR900007118B1 (ko) 1990-09-29
DE3373921D1 (en) 1987-11-05
MX7543E (es) 1989-09-06
BR8301735A (pt) 1983-12-13
IN157179B (fr) 1986-02-01
ZA832119B (en) 1984-04-25
AU566664B2 (en) 1987-10-29
ATE30050T1 (de) 1987-10-15
AR231149A1 (es) 1984-09-28
GB2117793A (en) 1983-10-19
JPS58204145A (ja) 1983-11-28
GB2117793B (en) 1986-04-16
EP0091308A3 (en) 1984-09-05
AU1312283A (en) 1983-10-13
JPH059503B2 (fr) 1993-02-05
KR840004180A (ko) 1984-10-10
EP0091308A2 (fr) 1983-10-12
CA1211961A (fr) 1986-09-30

Similar Documents

Publication Publication Date Title
US4788036A (en) Corrosion resistant high-strength nickel-base alloy
US5424029A (en) Corrosion resistant nickel base alloy
EP0066361B2 (fr) Alliage à base de nickel, résistant à la corrosion et possédant des caractéristiques mécaniques élevées
JP5661938B2 (ja) Ｎｉ−Ｆｅ−Ｃｒ−Ｍｏ−合金
EP0052941B1 (fr) Matériau pour tubage pour puits corrosifs de profondeur moyenne
US2777766A (en) Corrosion resistant alloys
KR20050044557A (ko) 슈퍼 오스테나이트계 스테인레스강
CA1213158A (fr) Alliage de nickel de fer resistant a la corrosion
JP2010508439A (ja) ２相ステンレス鋼およびこの鋼の使用
US4533414A (en) Corrosion-resistance nickel alloy
RU2282674C2 (ru) Дуплексная нержавеющая сталь, способ ее получения и промышленное изделие, выполненное из этой стали (варианты)
EP0091308B1 (fr) Alliage à base de nickel, résistant à la corrosion
JP4312408B2 (ja) 耐蝕性オーステナイト合金
US4840768A (en) Austenitic Fe-Cr-Ni alloy designed for oil country tubular products
US5026521A (en) Zirconium-titanium and/or tantalum oxygen alloy
US4033767A (en) Ductile corrosion resistant alloy
CA2070535A1 (fr) Acier austenitique
JPS62297443A (ja) 熱間加工性に優れる高耐食オ−ステナイトステンレス鋼
JPS6199656A (ja) ラインパイプ用高強度溶接鋼管
AU2015275299B2 (en) Ni-Fe-Cr-Mo alloy
JPH02138429A (ja) 耐食性および耐応力腐食割れ性に優れた高強度β系チタン合金
EP0184038A1 (fr) Alliage fer-nickel-chrome-molybdène

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT LI LU NL SE

17P Request for examination filed

Effective date: 19841211

17Q First examination report despatched

Effective date: 19860507

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR IT LI LU NL SE

REF Corresponds to:

Ref document number: 30050

Country of ref document: AT

Date of ref document: 19871015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3373921

Country of ref document: DE

Date of ref document: 19871105

ITF It: translation for a ep patent filed

Owner name: LUNATI & MAZZONI S.A.S.

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19910306

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19910320

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910417

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910425

Year of fee payment: 9

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910430

Year of fee payment: 9

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19920405

Ref country code: AT

Effective date: 19920405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19920430

Ref country code: CH

Effective date: 19920430

Ref country code: BE

Effective date: 19920430

BERE Be: lapsed

Owner name: TELEDYNE INDUSTRIES INC.

Effective date: 19920430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19921101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EAL Se: european patent in force in sweden

Ref document number: 83301891.4

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20020319

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20020320

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020418

Year of fee payment: 20

EUG Se: european patent has lapsed