EP0386730B1 - Alliage de nickel-chrome-fer - Google Patents

Alliage de nickel-chrome-fer Download PDF

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Publication number
EP0386730B1
EP0386730B1 EP90104349A EP90104349A EP0386730B1 EP 0386730 B1 EP0386730 B1 EP 0386730B1 EP 90104349 A EP90104349 A EP 90104349A EP 90104349 A EP90104349 A EP 90104349A EP 0386730 B1 EP0386730 B1 EP 0386730B1
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EP
European Patent Office
Prior art keywords
alloy
nicr
chromium
nickel
zirconium
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
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EP90104349A
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German (de)
English (en)
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EP0386730A1 (fr
Inventor
Ulrich Dr. Brill
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Krupp VDM GmbH
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Krupp VDM GmbH
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Publication date
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Priority to AT90104349T priority Critical patent/ATE89872T1/de
Publication of EP0386730A1 publication Critical patent/EP0386730A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing 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 invention relates to a thermoformable, austenitic Ni-Cr-Fe alloy with very good oxidation resistance and heat resistance.
  • Alloys of this type are used for the production of wires and strips for heating conductor resistors, for the production of support systems in furnaces and for other furnace components and increasingly also for nuclear reactors.
  • an alloy of the following composition has become known from DE-PS 30 37 209: up to 15% of one or more of the elements Mo, Rh, Hf, W, Ta and Nb up to 0.5% of one or more of the elements C, B, Mg, Zr and Ca. up to 1% Si, up to 2% Mn, up to 20% Co, up to 5% Ti, up to 30% Fe, balance Ni.
  • the main issue was a well-adhering aluminum oxide layer, which is expediently produced by pre-oxidation in an oxygen-containing atmosphere at above 1093 ° C.
  • an aluminum content of 2.5 to 8% has a strong effect on this alloy ⁇ '-excretion preferably in the temperature range of 600 to 800 ° C. This is associated with a sharp decrease in the ductility of the material, which can lead to material damage, particularly in furnaces that often pass through this temperature range during heating and cooling.
  • aluminum contents of 2.5 to 8% and chromium contents of 8 to 25% are not sufficient to only form aluminum oxide in NiCrAl alloys. Rather, the formation of aluminum oxide, chromium oxide, mixed oxides and internal oxidation occurs, a process that leads to a poorer protective effect than the pure chromium oxide, especially in the case of thermal-cyclical stress.
  • the alloy can also contain Ti, Al and Y.
  • zirconium on the resistance to oxidation is neutralized if zirconium is present as a stable carbide to improve the hot formability.
  • the positive influence of zirconium on the hot processing properties can be reversed if coarsely dispersed zirconium carbides are formed due to the non-coordinated addition of zirconium and carbon.
  • an alloy from DIN 17 742 (material no. 2.4867) is included known in the form of wires and tapes for the production of heating conductors and electrical resistors is suitable and is generally manufactured and offered with the following composition:
  • This heating conductor alloy is known under the short name NiCr 60 15. Under thermal cycling (according to FIG. 1b, see below) it has service life values that lie between those of the pure Ni-Cr alloy NiCr 80 20 on the one hand and those of the iron-based material NiCr 30 20 on the other hand (see FIG. 2). In addition, despite the higher melting point, the NiCr 60 15 alloy has a lower maximum operating temperature than the pure Ni-Cr alloy and does not have sufficient heat resistance for certain applications.
  • the maximum operating temperature which is usually limited to approx. 1200 ° C., can be increased by approx. 50 ° C. if the alloy elements are used there according to the prior art Form of mixed metal added lanthanides replaced by yttrium.
  • FIG. 1a shows, in a highly simplified manner, a device for checking the service life of a horizontally arranged, helically wound heating conductor (1) which is clamped at the end in a holder (2) and connected to a voltage source (3).
  • the heating conductor consisted of a 50 mm long coil with 12 turns and an inner diameter of 3 mm. The wire diameter was 0.4 mm.
  • the heating conductor was switched on and off in alternation of two minutes, whereby the maximum temperature reached during the heating phase was measured without contact using a radiation pyrometer and regulated to a constant value by changing the applied voltage.
  • Fig. 1b shows - also greatly simplified - a device for testing the life of a vertically hanging heating conductor wire (4) of one meter in length, which is clamped at its upper end in a holder (5), loaded with a variable weight (6) and with a voltage source (7) is connected.
  • FIG. 3 the service life of the material according to the invention determined with a device according to FIG. 1a at a maximum temperature set at 1150 ° C. is below the same conditions measured lifetime of the unmodified material "NiCr 60 15 old" compared.
  • the service life was increased from 2900 cycles to 4100 cycles, which means an improvement of over 40%.
  • the service life (number of cycles) was determined at temperatures of 1150, 1200 and 1250 ° C.
  • Table 1 shows that the modified alloy is significantly better at all temperatures. The differences are + 56.8% at 1150 ° C, + 33.9% at 1200 ° C and + 66.2% at 1250 ° C. It cannot yet be said whether the relative improvement in service life is actually temperature-dependent or only existed for the samples examined. With a correspondingly high number of samples, it will probably be found that the improvement on average is approximately the same at all temperatures, a value of at least 30% being expected.
  • modified alloy at 1200 or 1250 ° C still has 65 or 34% of the life of the base alloy at 1150 ° C is important in practice, which represents a considerable safety reserve, especially with regard to short-term exceeding of the operating temperatures is very desirable in most fields of application.
  • a high level of heat resistance is generally required for heating conductor windings, and thus for free-hanging The sagging of the windings can be avoided.
  • the heat resistance is based above all on solid-solution strengthening of the basic nickel structure by Cr and Fe and hardening by carbides.
  • Ti and Zr and N were alloyed, so that the modified alloy contains nitrides and carbonitrides in addition to the carbides.
  • the modified material showed a significantly longer service life.
  • Two complete heating elements such as those used for tumble dryers, were charged with 227 volts in 30-second cycles, with which a maximum temperature of 1150 ° C is achieved with a new heating element.
  • the comparative alloy "NiCr 60 15 old" only withstood around 130,000 cycles
  • the alloy “NiCr 60 15 new” according to the invention has so far endured more than 380,000 cycles in the test that has not yet ended. This almost triples the service life, which speaks for the considerable economic importance of the alloy according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Resistance Heating (AREA)
  • Heat Treatment Of Steel (AREA)
  • Contacts (AREA)
  • Dental Preparations (AREA)
  • Soft Magnetic Materials (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Materials For Medical Uses (AREA)
  • Laminated Bodies (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • High-Tension Arc-Extinguishing Switches Without Spraying Means (AREA)

Claims (3)

  1. Alliage austénitique de nickel-chrome-fer déformable à chaud avec de très bonnes résistance à l'oxydation et stabilité à chaud,
    caractérisé par
    Figure imgb0020
     avec la condition de valeur que la teneur en azote est réglée selon la formule % de N = (0,15 à 0,30) x % de Zr + (0,30 à 0,60) x % de Ti
    Figure imgb0021
  2. Alliage de nickel-chrome-fer selon la revendication 1, cependant avec
    Figure imgb0022
    Figure imgb0023
     avec la condition de valeur que la teneur en azote est réglée selon la formule % de N = (0,15 à 0,30) x % de Zr + (0,30 à 0,60) x % de Ti
    Figure imgb0024
  3. Alliage de nickel-chrome-fer selon la revendication 1 et 2, cependant avec
    Figure imgb0025
     avec la condition de valeur que la teneur en azote est réglée selon la formule % de N = (0,15 à 0,25) x % de Zr + (0,30 à 0,45) x % de Ti
    Figure imgb0026
EP90104349A 1989-03-09 1990-03-07 Alliage de nickel-chrome-fer Expired - Lifetime EP0386730B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90104349T ATE89872T1 (de) 1989-03-09 1990-03-07 Nickel-chrom-eisen-legierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3907564 1989-03-09
DE3907564A DE3907564A1 (de) 1989-03-09 1989-03-09 Nickel-chrom-eisen-legierung

Publications (2)

Publication Number Publication Date
EP0386730A1 EP0386730A1 (fr) 1990-09-12
EP0386730B1 true EP0386730B1 (fr) 1993-05-26

Family

ID=6375882

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90104349A Expired - Lifetime EP0386730B1 (fr) 1989-03-09 1990-03-07 Alliage de nickel-chrome-fer

Country Status (14)

Country Link
US (1) US4997623A (fr)
EP (1) EP0386730B1 (fr)
JP (1) JPH0689427B2 (fr)
KR (1) KR900014619A (fr)
AT (1) ATE89872T1 (fr)
AU (1) AU617242B2 (fr)
BR (1) BR9001105A (fr)
CA (1) CA2011152A1 (fr)
DD (1) DD292479A5 (fr)
DE (2) DE3907564A1 (fr)
ES (1) ES2042102T3 (fr)
IE (1) IE62547B1 (fr)
MX (1) MX172020B (fr)
ZA (1) ZA901579B (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2521579B2 (ja) * 1990-12-21 1996-08-07 新日本製鐵株式会社 Ｖ、Ｎａ、Ｓ、Ｃｌの存在する燃焼環境において耐食性を有する合金および複層鋼管
US5330590A (en) * 1993-05-26 1994-07-19 The United States Of America, As Represented By The Administrator Of The National Aeronautics & Space Administration High temperature creep and oxidation resistant chromium silicide matrix alloy containing molybdenum
DE4422521C1 (de) * 1994-06-28 1995-10-05 Krupp Vdm Gmbh Hochtemperatur-Knetlegierung
DK172987B1 (da) * 1994-12-13 1999-11-01 Man B & W Diesel As Cylinderelement, nikkelbaseret pålægningslegering og anvendelse af legeringen
US5851318A (en) * 1995-06-09 1998-12-22 Krupp Vdm Gmbh High temperature forgeable alloy
SE527319C2 (sv) 2003-10-02 2006-02-07 Sandvik Intellectual Property Legering för högtemperaturanvändning
SE529003E (sv) 2005-07-01 2011-10-11 Sandvik Intellectual Property Ni-Cr-Fe-legering för högtemperaturanvändning
DE102007005605B4 (de) 2007-01-31 2010-02-04 Thyssenkrupp Vdm Gmbh Eisen-Nickel-Chrom-Silizium-Legierung
DE102007029400B4 (de) * 2007-06-26 2014-05-15 Outokumpu Vdm Gmbh Eisen-Nickel-Chrom-Silizium-Legierung
CN103153102B (zh) 2010-09-29 2015-04-08 霍丁斯瑞典有限公司 适于保护头部的安全气囊
DK177487B1 (en) * 2012-07-06 2013-07-15 Man Diesel & Turbo Deutschland An exhaust valve spindle for an exhaust valve in an internal combustion engine
CN111411265B (zh) * 2020-03-21 2021-11-26 交大材料科技(江苏)研究院有限公司 一种镍基合金超薄板材
CN112080749B (zh) * 2020-09-09 2022-01-11 北京首钢吉泰安新材料有限公司 一种镍铬合金丝的表面处理方法和装置

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Publication number Priority date Publication date Assignee Title
US2581420A (en) * 1949-09-23 1952-01-08 Driver Harris Co Alloys
JPS5631345B2 (fr) * 1972-01-27 1981-07-21
JPS5111013A (ja) * 1974-07-19 1976-01-28 Nippon Steel Corp Tainetsunitsukerugokinno seizoho
US4400211A (en) * 1981-06-10 1983-08-23 Sumitomo Metal Industries, Ltd. Alloy for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking
US4400210A (en) * 1981-06-10 1983-08-23 Sumitomo Metal Industries, Ltd. Alloy for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking
US4421571A (en) * 1981-07-03 1983-12-20 Sumitomo Metal Industries, Ltd. Process for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking
US4626408A (en) * 1984-09-20 1986-12-02 Nippon Yakin Kogyo Kabushiki Kaisha Ni-based alloy excellent in intergranular corrosion resistance, stress corrosion cracking resistance and hot workability
JPS6179742A (ja) * 1984-09-26 1986-04-23 Mitsubishi Heavy Ind Ltd 耐熱合金
JPS61130464A (ja) * 1984-11-30 1986-06-18 Nippon Steel Corp 高耐食性高強度ドリルカラ−用非磁性鋼
EP0235075B1 (fr) * 1986-01-20 1992-05-06 Mitsubishi Jukogyo Kabushiki Kaisha Alliage à base de nickel et procédé pour sa fabrication

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
D.J.Baxter et al., "Werkstoffe und Korrosion", Nr. 35, 1984; Seiten 266-272# *
J.E.Antill et al., "The Journal of the Iron and Steel Institute", November 1967; Seiten 1136-1142# *
M.H.Lagrange et al., "Corrosion Science",Band 24, Nr. 7, 1984; Seiten 613-627# *

Also Published As

Publication number Publication date
ES2042102T3 (es) 1993-12-01
DD292479A5 (de) 1991-08-01
DE3907564A1 (de) 1990-09-13
ZA901579B (en) 1991-01-30
AU617242B2 (en) 1991-11-21
US4997623A (en) 1991-03-05
ATE89872T1 (de) 1993-06-15
IE900835L (en) 1990-09-09
IE62547B1 (en) 1995-02-08
KR900014619A (ko) 1990-10-24
JPH0320433A (ja) 1991-01-29
AU5117390A (en) 1990-09-20
DE59001527D1 (de) 1993-07-01
MX172020B (es) 1993-11-29
JPH0689427B2 (ja) 1994-11-09
BR9001105A (pt) 1991-03-05
CA2011152A1 (fr) 1990-09-09
EP0386730A1 (fr) 1990-09-12

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