EP0558915B1 - Alliage de nickel austénitique - Google Patents

Alliage de nickel austénitique Download PDF

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Publication number
EP0558915B1
EP0558915B1 EP93101162A EP93101162A EP0558915B1 EP 0558915 B1 EP0558915 B1 EP 0558915B1 EP 93101162 A EP93101162 A EP 93101162A EP 93101162 A EP93101162 A EP 93101162A EP 0558915 B1 EP0558915 B1 EP 0558915B1
Authority
EP
European Patent Office
Prior art keywords
corrosion
chromium
nickel
alloy according
molybdenum alloy
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 - Lifetime
Application number
EP93101162A
Other languages
German (de)
English (en)
Other versions
EP0558915A3 (fr
EP0558915A2 (fr
Inventor
Michael Dr. Ing. Köhler
Ulrich Dr. Ing. Heubner
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.)
Krupp VDM GmbH
Original Assignee
Krupp VDM GmbH
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 Krupp VDM GmbH filed Critical Krupp VDM GmbH
Publication of EP0558915A2 publication Critical patent/EP0558915A2/fr
Publication of EP0558915A3 publication Critical patent/EP0558915A3/xx
Application granted granted Critical
Publication of EP0558915B1 publication Critical patent/EP0558915B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • 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

Definitions

  • the invention relates to an austenitic nickel-chromium-molybdenum alloy with high resistance to general corrosion, against crevice, pitting and stress corrosion cracking as well as against intergranular corrosion, and its use for components used in corrosive media.
  • NiMo16CrTi material Mr. 2.4610 according to the steel-iron list of the German Association Ironworkers; Verlag Stahleisen mbH, 7th edition, 1981 in accordance with the US material UNS N06455
  • vanadium for example as a stabilizing element for the known nickel-based materials NiMo16Cr15 (material Mr. 2.4819, according to UNS N10276) and NiCr21Mo14W (material No. 2.4602, according to UNS N06022) is required.
  • the material NiCr22Mo9Nb (material No. 2.4856, according to UNS N06625) is stabilized by the addition of niobium.
  • the level of the alloyed contents of these stabilizing elements is usually 10 to 20 times the carbon content, but also up to 50 to 100 times for the material NiCr22Mo9Nb.
  • the stabilization (binding of the carbon) guarantees the better corrosion resistance of welded components without additional heat treatment.
  • NiMo16CrTi is usually alloyed with 0.25 - 0.5% titanium.
  • titanium binds not only carbon but also nitrogen through the formation of nitrides.
  • the titanium is said to reduce the sensitivity of the material and thus facilitate further processing, for example welding.
  • the resulting titanium nitrides are scattered in the structure of the material and, particularly in the case of larger dimensions, in the form of cloud-like accumulations may be more concentrated locally. This then results in corresponding non-uniformities in the material, which can result in locally uneven removal in the event of greater corrosion and erosion stress.
  • the material loses the smooth-walled surface that is required in many process sequences, which is absolutely necessary to prevent caking, for example the deposit of gypsum in absorbers for flue gas desulfurization.
  • US-A-4 129 464 discloses Ni-Cr-Mo alloys which are corrosion resistant and have good ductility. However, at least the sum of C + Si + Al lies outside the upper limit of the alloy according to the invention specified in claim 1.
  • the invention has for its object to provide a corrosion-resistant and weldable nickel alloy in which locally uneven corrosion removal can be avoided.
  • an austenitic nickel-chromium-molybdenum alloy consisting of (in% mass content): Carbon: up to 0.01% Silicon: up to 0.05%
  • Calcium 0.001 to 0.010%
  • Aluminum 0.05 to 0.30%
  • the nickel alloy according to the invention is characterized by good weldability and corrosion resistance. When using this nickel alloy for objects that are used in corrosive media, locally uneven corrosion removal does not occur.
  • the nickel alloy according to the invention is therefore particularly suitable as a material for structural parts in electrolytic treatment plants for the surface finishing of metal strips, in particular as a material for the production of transport rolls and current rolls for electrolytic strip galvanizing plants, in which there is an absolutely smooth surface of the rolls with regard to the quality of the metal strip to be treated arrives.
  • rolls that were made from the known material 2.4610 it was found that uneven erosion corrosion and abrasive corrosion started on the surface of the rolls in metal strip treatment plants, which reduced the service life of the rolls.
  • the surface damage of the rolls was transferred to the surfaces of the metal strips to be treated and thus led to a severe impairment of the product quality, e.g. that of a galvanized metal strip. This error did not occur when using rollers made of the nickel alloy according to the invention.
  • the rolls had a service life that was previously unknown, which was 5 to 10 times longer than that of rolls made of the known alloy 2.4610.
  • the nickel alloy according to the invention is furthermore suitable as a material for handling chemical process media, such as solutions containing iron (III) and copper (II) chloride hot contaminated mineral acids, formic and acetic acid, with good resistance to moist chlorine gas, hypochlorite and chloride oxide solutions.
  • chemical process media such as solutions containing iron (III) and copper (II) chloride hot contaminated mineral acids, formic and acetic acid, with good resistance to moist chlorine gas, hypochlorite and chloride oxide solutions.
  • the nickel alloy according to the invention is also preferably used as a material for the production of absorber components for the cleaning and desulfurization of flue gases.
  • the nickel alloy according to the invention is also a suitable material for the production of pickling bath containers and associated components as well as systems for the regeneration of pickling media.
  • the general corrosion resistance is given by the chromium and molybdenum contents, which are each 14-18%.
  • the rate of elimination of intermetallic phases for example the so-called ⁇ phase, which is rich in molybdenum and chromium, is reduced by 0.05%.
  • precipitations of molybdenum-rich M6C carbides as well as titanium carbides, titanium nitrides and titanium carbonitrides are suppressed, which are observed with the known alloy 2.4610 and lead to surface damage in oxidizing and reducing media when used.
  • the nitrogen content must not exceed 0.02% to avoid titanium nitrides and titanium carbonitrides.
  • Table 1 shows the analyzes of 5 4.5 ton melts of the alloy according to the invention (alloys A to E) produced in comparison to an alloy corresponding to the material NiMo16Cr16Ti (material No. 2.4610).
  • the batches were produced by melting in an electric arc furnace with subsequent vacuum deoxidation treatment and by additional remelting in an electroslag remelting plant.
  • Hollow bodies with the dimensions: outer diameter 490 mm, inner diameter 290 mm, length 3200 mm were forged using the usual thermoforming processes. The forgings were then solution annealed and quenched in water.
  • the corrosion resistance of the nickel alloy according to the invention was compared to the material NiMo16Cr16Ti (2.4610 or UNS NO6455) in 50% sulfuric acid with the addition of 42 g / l Fe (SO4) 3 x 9 H2O and in 10% HCl each boiling over 24 Hours checked and the mass loss determined thereby converted to a corrosion rate (mm / year).

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  • 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)
  • Materials For Medical Uses (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Gas Separation By Absorption (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Fuel Cell (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Arc Welding In General (AREA)

Claims (6)

  1. Alliage austénitique de nickel-chrome-molybdène possédant une résistance élevée vis-à-vis de la corrosion générale, de la corrosion en fissures, de la corrosion par piqûres et d'une corrosion fissurante sous contrainte ainsi que vis-à-vis d'une corrosion intercristalline, constitué par (en % en poids) : carbone : jusqu'à 0,01 % silicium : jusqu'à 0,05 % manganèse : jusqu'à 0,50 % phosphore : jusqu'à 0,020 % soufre : jusqu'à 0,010 % chrome : 14,0 jusqu'à 18,0 % molybdène : 14,0 jusqu'à 18,0 % cobalt : jusqu'à 2,0 % tungstène : jusqu'à 0,5 % calcium : 0,001 à 0,010 % magnésium : 0,001 à 0,020 % aluminium : 0,05 à 0,30 % azote : jusqu'à 0,02 % fer : jusqu'à 3,0 % cuivre : jusqu'à 0,5 % titane : jusqu'à 0,01 %
    le reste étant formé de nickel et d'impuretés usuelles conditionnées par l'élaboration,
    la somme des teneurs en (carbone + silicium + titane) étant limitée au maximum à 0,05 %, et la somme des éléments (calcium + magnésium + aluminium) étant réglée dans les limites de 0,055 à 0,33 %.
  2. Utilisation d'un alliage austénitique de nickel-chrome-molybdène selon la revendication 1 en tant que matériau pour des pièces de construction dans des installations de traitement électrolytique pour l'ennoblissement de surfaces de feuillards métalliques.
  3. Utilisation d'un alliage austénitique de nickel-chrome-molybdène selon la revendication 1 en tant que matériau pour fabriquer des rouleaux de transport et des rouleaux de transmission de courant pour des installations d'étamage électrolytique de feuillards métalliques.
  4. Utilisation d'un alliage austénitique de nickel-chrome-molybdène selon la revendication 1 en tant que matériau pour la manipulation de milieux chimiques de traitement tels que des solutions contenant du chlorure ferrique et du chlorure cuivrique ainsi que des acides minéraux chauds impurs, de l'acide formique et de l'acide acétique, avec une bonne résistance vis-à-vis du chlore gazeux humide, de l'hypochlorite et de solutions d'oxychlorures.
  5. Utilisation d'un alliage austénitique de nickel-chrome-molybdène selon la revendication 1 en tant que matériau pour fabriquer de composants d'absorbeurs pour l'épuration et la désulfuration de gaz de fumées.
  6. Utilisation d'un alliage austénitique de nickel-chrome-molybdène selon la revendication 1 en tant que matériau pour la fabrication de récipients contenant des bains de décapage et des composants associés ainsi que des installations pour la régénération de bains de décapage.
EP93101162A 1992-02-06 1993-01-27 Alliage de nickel austénitique Expired - Lifetime EP0558915B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4203328A DE4203328C1 (fr) 1992-02-06 1992-02-06
DE4203328 1992-02-06

Publications (3)

Publication Number Publication Date
EP0558915A2 EP0558915A2 (fr) 1993-09-08
EP0558915A3 EP0558915A3 (fr) 1994-01-12
EP0558915B1 true EP0558915B1 (fr) 1995-09-27

Family

ID=6451036

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93101162A Expired - Lifetime EP0558915B1 (fr) 1992-02-06 1993-01-27 Alliage de nickel austénitique

Country Status (12)

Country Link
US (1) US5417918A (fr)
EP (1) EP0558915B1 (fr)
JP (1) JPH05271832A (fr)
KR (1) KR100193388B1 (fr)
AT (1) ATE128492T1 (fr)
BR (1) BR9300503A (fr)
CA (1) CA2087995A1 (fr)
DE (2) DE4203328C1 (fr)
DK (1) DK0558915T3 (fr)
ES (1) ES2081644T3 (fr)
FI (1) FI103286B (fr)
MX (1) MX9300537A (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0648850B1 (fr) * 1993-09-20 1997-08-13 Mitsubishi Materials Corporation Alliage à base de nickel
DE4446266C1 (de) * 1994-12-23 1996-08-14 Krupp Vdm Gmbh Nickellegierung
DE19723491C1 (de) * 1997-06-05 1998-12-03 Krupp Vdm Gmbh Verwendung einer Nickel-Chrom-Molybdän-Legierung
US5972289A (en) * 1998-05-07 1999-10-26 Lockheed Martin Energy Research Corporation High strength, thermally stable, oxidation resistant, nickel-based alloy
US6860948B1 (en) 2003-09-05 2005-03-01 Haynes International, Inc. Age-hardenable, corrosion resistant Ni—Cr—Mo alloys
US6544362B2 (en) 2001-06-28 2003-04-08 Haynes International, Inc. Two step aging treatment for Ni-Cr-Mo alloys
KR20030003017A (ko) * 2001-06-28 2003-01-09 하이네스인터내셔널인코포레이티드 Ｎｉ-Ｃｒ-Ｍｏ합금의 2-단계 에이징 처리방법 및 결과의합금
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
US7785532B2 (en) * 2006-08-09 2010-08-31 Haynes International, Inc. Hybrid corrosion-resistant nickel alloys
JP2021183719A (ja) 2020-05-22 2021-12-02 日本製鉄株式会社 Ｎｉ基合金管および溶接継手
JP2021183721A (ja) 2020-05-22 2021-12-02 日本製鉄株式会社 Ｎｉ基合金管および溶接継手
JP2021183720A (ja) 2020-05-22 2021-12-02 日本製鉄株式会社 Ｎｉ基合金管および溶接継手

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2005371B2 (de) * 1970-02-06 1974-01-17 Fried. Krupp Gmbh, 4300 Essen Verfahren zur Herstellung weichmagnetischer Eisen-Nickel-Legierungen
US4043810A (en) * 1971-09-13 1977-08-23 Cabot Corporation Cast thermally stable high temperature nickel-base alloys and casting made therefrom
BE788719A (fr) * 1971-09-13 1973-01-02 Cabot Corp Alliage a base de nickel resistant a l'oxydation aux temperatures elevees et thermiquement stables
ZA74490B (en) * 1973-02-06 1974-11-27 Cabot Corp Nickel-base alloys
JPS5129316A (fr) * 1974-09-06 1976-03-12 Nippon Steel Corp
US3969111A (en) * 1975-03-27 1976-07-13 Cabot Corporation Alloy compositions
US4129464A (en) * 1977-08-24 1978-12-12 Cabot Corporation High yield strength Ni-Cr-Mo alloys and methods of producing the same
JPH0674474B2 (ja) * 1986-01-07 1994-09-21 住友金属工業株式会社 耐食性に優れた高強度Ｎｉ基合金
JPH0639650B2 (ja) * 1986-01-07 1994-05-25 住友金属工業株式会社 靭性の優れた高耐食性Ｎｉ基合金
JPH0674473B2 (ja) * 1986-01-07 1994-09-21 住友金属工業株式会社 高耐食性Ｎｉ基合金
JPH028337A (ja) * 1988-06-24 1990-01-11 Nippon Stainless Steel Co Ltd 電気めっき用通電ロールおよびその製造方法

Also Published As

Publication number Publication date
FI103286B1 (fi) 1999-05-31
ATE128492T1 (de) 1995-10-15
FI930492A (fi) 1993-08-07
BR9300503A (pt) 1993-09-28
KR930018042A (ko) 1993-09-21
EP0558915A3 (fr) 1994-01-12
CA2087995A1 (fr) 1993-08-07
DE59300640D1 (de) 1995-11-02
FI930492A0 (fi) 1993-02-04
EP0558915A2 (fr) 1993-09-08
DE4203328C1 (fr) 1993-01-07
MX9300537A (es) 1994-07-29
ES2081644T3 (es) 1996-03-16
DK0558915T3 (da) 1995-12-27
FI103286B (fi) 1999-05-31
US5417918A (en) 1995-05-23
KR100193388B1 (ko) 1999-06-15
JPH05271832A (ja) 1993-10-19

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