EP0251295B1 - Nickellegierung mit hohem Chromgehalt - Google Patents

Nickellegierung mit hohem Chromgehalt Download PDF

Info

Publication number
EP0251295B1
EP0251295B1 EP87109408A EP87109408A EP0251295B1 EP 0251295 B1 EP0251295 B1 EP 0251295B1 EP 87109408 A EP87109408 A EP 87109408A EP 87109408 A EP87109408 A EP 87109408A EP 0251295 B1 EP0251295 B1 EP 0251295B1
Authority
EP
European Patent Office
Prior art keywords
alloy
nitrogen
alloy according
chromium
titanium
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
EP87109408A
Other languages
English (en)
French (fr)
Other versions
EP0251295A2 (de
EP0251295A3 (en
Inventor
Pasupathy Ganesan
Gaylord Smith
Curtis Steven Tassen
Jack Milton Wheeler
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.)
Huntington Alloys Corp
Original Assignee
Inco Alloys International 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 Inco Alloys International Inc filed Critical Inco Alloys International Inc
Publication of EP0251295A2 publication Critical patent/EP0251295A2/de
Publication of EP0251295A3 publication Critical patent/EP0251295A3/en
Application granted granted Critical
Publication of EP0251295B1 publication Critical patent/EP0251295B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W

Definitions

  • the subject invention is directed to a high nickel-chromium-iron alloy, and more particularly to a Ni-Cr-Fe alloy of special chemistry and micro-structure such that it is capable of affording a desired combination of properties at elevated temperatures upwards of 2000°F (1093°C) under oxidizing conditions.
  • rollers have been produced from electric-arc furnace melted, argon-oxygen decarburized (AOD) refined ingots.
  • the composition used differed somewhat from the above, a typical composition being approximately 0.03%C, 0.3% Si, 0.3% Mn, 22.5% Cr, 0.4% Ti, 0.02% Nb, 1.27% Al, 60.8% Ni, 0.08% Co, 0.29% Mo. 0.015% N, less than 0.001% 02, balance iron and impurities.
  • At 2050°F (1121°C) rollers lasted some 12 months and at times longer. However, at 2130°F (1165°C) such rollers manifested failure in 2 months or less.
  • the alloy contemplated herein contains 19 to 28% chromium, 55 to 65% nickel, 0.75 to 2% aluminum, 0.2 to 1% titanium, from 0.1 to 1% silicon, up to 1% each of molybdenum, manganese and niobium, up to 0.1% carbon, from 0.035 to 0.1% (e.g. 0.04 to 0.08%) nitrogen and up to 0.01% or even 0.1% boron, up to 0.1% calcium and up to 0.1% magnesium, the balance, apart from impurities, being iron.
  • a preferred alloy contains 21 to 25% Cr, 58 to 63% Ni, 1 to 2% Al, 0.3 to 0.7% Ti, 0.1 to 0.6% Si and optionally 0.1 to 0.8% Mo, up to 0.6% Mn, up to 0.4% Nb, 0.02 to 0.1% c, 0.04 to 0.08% N, with iron being the balance.
  • Nickel contributes to workability and fabricability as well as imparting strength and other benefits.
  • Aluminum and chromium confer oxidation resistance but if present to the excess lend to undesirable microstructural phases such as sigma. Little is gained with chromium levels much above 28% or aluminum levels exceeding 2%.
  • a level of about 0.1 to 0.5% Cr23C6 aids strength to about 2057°F (1125°C). Silicon and molybdenum stabilize the carbide phase. In this regard the presence of 0.1 to 0.6% silicon with or without 0.1 to 0.8% molybdenum is advantageous.
  • Titanium acts as a malleabilizer as well as serving to form the grain boundary pinning titanium nitride phase. Niobium will further stabilize the nitride phase and from 0.05 to 0.4% is beneficial.
  • Manganese is preferably held to low levels, preferably not about 0.6%, since higher percentages detract from oxidation resistance. Up to 0.006% boron may be present to aid malleability. Calcium and/or magnesium in amounts, say up to 0.05 or 0.1%, are useful for deoxidation and malleabilization.
  • Iron comprises essentially the balance of the alloy composition. This allows for the use of standard ferroalloys in melting thus reducing cost.
  • sulphur and phosphorus present as impurities should be maintained at low levels, e.g., up to 0.015% sulphur and up to 0.02 or 0.03% phosphorus. Copper can be present as an impurity.
  • the alloy is electric-arc furnace melted, AOD refined and electroslag remelted (ESR) for (a) uniform distribution of the nitrides (b) better nitrogen content control, and (c) to maximize yield.
  • ESR electroslag remelted
  • the nitrogen can be added to the AOD refined melt by means of a nitrogen blow just prior to pouring the ingot to be ESR melted.
  • the alloy is, as a practical matter, non age-hardenable or substantially non age-hardenable, and is comprised essentially of a stable austenitic matrix virtually free of detrimental quantities of subversive phases. For example, upon heating for prolonged periods, say 300 hours, at temperatures circa 1100°F (593°C) to 1400°F (760°C) metallographic analysis did not reveal the presence of the sigma phase.
  • Alloys A through C are low nitrogen compositions with varying carbon content. Although increasing carbon content progressively inhibited grain growth, it was ineffective in controlling grain size for long periods of time above about 1100°C (2010°F). Increasing the nitrogen level resulted in several beneficial attributes, as shown by the titanium-containing Alloy 2 of the invention. The uniform dispersion of nitride resulted in stabilization of the grain size and longer stress rupture lives at elevated temperature. The oxidation resistance of alloys within the invention was also improved (surprisingly) as measured by the reduction of the denuded zone beneath the surface scale. The nitrogen levels of Alloys D and E were also beneficial in comparison with A, B and C, but it is deemed that Alloy D would not perform as well as Alloys E and 2 over prolonged periods, as is indicated by the data in Table II.
  • Alloys A and B were fabricated into 26.9 mm diameter (1.06 in) x 2438.4mm (96 in.) rollers using 2.0 mm (0.08 in.) gauge sheets and then field tested in an actual furnace operating at 1165°C (2130°F). Both alloys failed by stress rupture in a short time. Alloy C was hot worked into a solid bar 26.9 mm (1.06 in.) diameter and in field operation for 6 days. The average grain size was 300 ⁇ m. after exposure, with grains as large as 1500 ⁇ m. The stress rupture life of an alloy similar to alloy A at 1177°C (2150°F) and 6.89 MPa (1 Ksi) was 308 hours.
  • Alloys E and 2 were fabricated similarly and exposed to the same thermal conditions as alloys A through C. (Alloys D, E and 2 are intermediate carbon content compositions with increasing nitrogen levels). The beneficial effect of increasing nitrogen content on grain size stability is demonstrated by the data in Table II. Rollers were fabricated from Alloy 2 (and also D) as described for Alloys A and B and are currently in field service without incident. Alloy E was fabricated into a solid roller as described for Alloy C. This alloy (1) was tested in field service at 1165°C (2130°F) for 8 days and then metallographically evaluated for grain size. The grain size was 300 ⁇ m after exposure and 50 ⁇ m prior to exposure.
  • the subject invention provide nickel chromium alloys which afford a combination of desirable metallurgical properties including (1) good oxidation resistance at elevated temperatures (2) high stress-rupture lives at such temperatures, and (3) a relatively stable microstructure.
  • the alloys are characterized by (4) a substantially uniform distribution of titanium nitrides (TiN) throughout the grains and grain boundaries.
  • TiN titanium nitrides
  • the nitrides are stable in the microstructure up to near the melting point provided at least 0.04% nitrogen is present. A nitrogen level down to 0.035% might be satisfactory in certain instances.
  • the grain size not exceed about 380 ⁇ m, preferably being not more than, 300 ⁇ m the size of the grains being uniform outwardly to the alloy surface.
  • the alloy of the present invention has been described in connection with the behavior of rollers in furnaces for frit production, the alloy is also deemed useful for heating elements, ignition tubes, radiant tubes, combustor components, burners, heat exchangers, furnace fixtures, mufflers, belts, etc.
  • the metal and ceramic process industries, chemical manufactures and the petroleum and petrochemical processing industries are illustrative of industries in which the alloy of the invention is deemed particularly useful.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)

Claims (8)

  1. Hochlegierte Nickel-Chrom-Legierung, gekennzeichnet durch (a) eine verbesserte Oxidationsbeständigkeit bei erhöhten Temperaturen, (b) gute Zeitstandfestigkeit bei derartigen Temperaturen und (c) eingestellte Korngröße, bestehend aus 55 bis 65% Nickel, 19 bis 28% Chrom, 0,75 bis 2% Aluminium, 0,2 bis 1% Titan, 0,035 bis 0,1% Stickstoff, bis 0,1% Kohlenstoff, 0,1 bis 1% Silizium, jeweils bis 1% Molybdän, Mangan und Niob sowie bis 0,1% Bor, bis 0,1% Kalzium und bis 0,1% Magnesium, Rest abgesehen von Verunreinigungen Eisen.
  2. Legierung nach Anspruch 1 mit 58 bis 63% Nickel, 21 bis 25% Chrom, 1 bis 2% Aluminium, 0,3 bis 0,7% Titan, 0,1 bis 0,6% Silizium und fakultativ 0,1 bis 0,8% Molybdän, bis 0,6% Mangan, bis 0,4% Niob, 0,02 bis 0,1% Kohlenstoff und 0,04 bis 0,08% Stickstoff.
  3. Legierung nach Anspruch 1 oder 2 mit Molybdän.
  4. Legierung nach Anspruch 1, mit 61,17% Nickel, 23,89% Chrom, 1,51% Aluminium, 0,37% Titan, 0,08% Stickstoff, 0,04% Kohlenstoff, 0,32% Silizium, 0,23% Molybdän und 0,29% Mangan, Rest Eisen abgesehen von Verunreinigungen.
  5. Legierung nach einem der Ansprüche 1 bis 4 mit Kalzium und/oder Magnesium.
  6. Gekneteter Gegenstand oder geknetetes Teil aus einer Legierung nach den Ansprüchen 1 bis 5 mit verhältnismäßig stabilem Mikrogefüge und im wesentlichen gleichmäßig über die Gefügekörner und Korngrenzen verteilten Titannitriden sowie einer mittleren Korngröße von höchstens etwa 380 um.
  7. Verwendung einer Legierung nach einem der Ansprüche 1 bis 5 als Werkstoff für Gegenstände und Teile mit guter Oxidationsbeständigkeit und zeitstandfestigkeit bei langfristiger Beanspruchung über 1093°C.
  8. Ofenrolle aus einer Legierung nach einem der Ansprüche 1 bis 5.
EP87109408A 1986-07-03 1987-06-30 Nickellegierung mit hohem Chromgehalt Expired - Lifetime EP0251295B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88162386A 1986-07-03 1986-07-03
US881623 1986-07-03

Publications (3)

Publication Number Publication Date
EP0251295A2 EP0251295A2 (de) 1988-01-07
EP0251295A3 EP0251295A3 (en) 1989-03-01
EP0251295B1 true EP0251295B1 (de) 1992-01-22

Family

ID=25378853

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87109408A Expired - Lifetime EP0251295B1 (de) 1986-07-03 1987-06-30 Nickellegierung mit hohem Chromgehalt

Country Status (6)

Country Link
EP (1) EP0251295B1 (de)
JP (1) JPS6326321A (de)
KR (1) KR880001836A (de)
AU (1) AU7505687A (de)
BR (1) BR8703367A (de)
CA (1) CA1304608C (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4787945A (en) * 1987-12-21 1988-11-29 Inco Alloys International, Inc. High nickel chromium alloy
DE4111821C1 (de) * 1991-04-11 1991-11-28 Vdm Nickel-Technologie Ag, 5980 Werdohl, De
ATE123819T1 (de) * 1991-12-20 1995-06-15 Inco Alloys Ltd Gegen hohe temperatur beständige ni-cr-legierung.
JP2904066B2 (ja) * 1995-08-31 1999-06-14 松下電器産業株式会社 温度センサ及びその製造方法
AT408665B (de) * 2000-09-14 2002-02-25 Boehler Edelstahl Gmbh & Co Kg Nickelbasislegierung für die hochtemperaturtechnik
FR2833019B1 (fr) * 2001-11-30 2004-09-10 Imphy Ugine Precision Alliage ferromagnetique pour la cuisson par induction
JP3814822B2 (ja) * 2002-03-08 2006-08-30 三菱マテリアル株式会社 高温熱交換器用フィンおよびチューブ
SE529003E (sv) * 2005-07-01 2011-06-27 Sandvik Intellectual Property Ni-Cr-Fe-legering för högtemperaturanvändning
PL2198065T3 (pl) 2007-10-05 2018-08-31 Sandvik Intellectual Property Ab Stal umocniona dyspersyjnie jako materiał w rolce dla pieca z trzonem samotokowym
DE102012002514B4 (de) * 2011-02-23 2014-07-24 VDM Metals GmbH Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit
DE102012015828B4 (de) * 2012-08-10 2014-09-18 VDM Metals GmbH Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3146136A (en) * 1961-01-24 1964-08-25 Rolls Royce Method of heat treating nickel base alloys
US3607243A (en) * 1970-01-26 1971-09-21 Int Nickel Co Corrosion resistant nickel-chromium-iron alloy
SU464648A1 (de) * 1973-10-02 1975-03-25

Also Published As

Publication number Publication date
CA1304608C (en) 1992-07-07
EP0251295A2 (de) 1988-01-07
AU7505687A (en) 1988-01-07
BR8703367A (pt) 1988-03-15
KR880001836A (ko) 1988-04-27
EP0251295A3 (en) 1989-03-01
JPS6326321A (ja) 1988-02-03

Similar Documents

Publication Publication Date Title
EP0381121A1 (de) Hochfester hitzebeständiger Stahl mit verbesserter Bearbeitbarkeit
EP0251295B1 (de) Nickellegierung mit hohem Chromgehalt
EP0295030B1 (de) Nickel-Chrom-Legierung
EP0544836B1 (de) Legierung mit niedrigem wärmeausdehnungskoeffizient und daraus hergestellter gegenstand
US4460542A (en) Iron-bearing nickel-chromium-aluminum-yttrium alloy
EP0075416B1 (de) Wärmebehandlung von Legierungen mit definierter Ausdehnung
US4006011A (en) Controlled expansion alloy
JPH02267240A (ja) 耐熱合金
EP0628088B2 (de) Nickel-molybdän-legierungen
EP0322156B1 (de) Nickellegierung mit hohem Chromgehalt
EP0076574B1 (de) Wärmebehandlung von Legierungen mit definierter Ausdehnung
US6610119B2 (en) Nickel-molybdenum alloys
US20010013383A1 (en) Trinickel aluminide-base heat-resistant alloy
JPH05113106A (ja) 高純度耐熱鋼および高純度耐熱鋼からなる高低圧一体型タービンロータの製造方法
EP0668366A1 (de) Kriechbeständige Eisen-Chrom-Aluminium-Legierung und Gegenstand daraus
JPH07252608A (ja) 熱間加工性フェライト系ステンレス鋼合金
JPH0931600A (ja) 高温用蒸気タービンロータ材
JPS6293353A (ja) オ−ステナイト系耐熱合金
JPH08291355A (ja) Ｃｒ基耐熱合金
JPH0459369B2 (de)
JPS6376851A (ja) 熱処理ポツト用Ｆｅ基耐熱合金
JPH07103436B2 (ja) 耐浸炭性にすぐれる耐熱合金
JPS61159556A (ja) 耐熱鋳造合金
JPH09235644A (ja) 耐熱鋳造合金
JPS6151625B2 (de)

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

Kind code of ref document: A2

Designated state(s): AT CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19890706

17Q First examination report despatched

Effective date: 19901227

RBV Designated contracting states (corrected)

Designated state(s): GB

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

REG Reference to a national code

Ref country code: DE

Ref legal event code: 8566

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): GB

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: GB

Payment date: 19960521

Year of fee payment: 10

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

Ref country code: GB

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

Effective date: 19970630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970630