EP0752481B1 - Alliage de nickel malléable - Google Patents

Alliage de nickel malléable Download PDF

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Publication number
EP0752481B1
EP0752481B1 EP96106945A EP96106945A EP0752481B1 EP 0752481 B1 EP0752481 B1 EP 0752481B1 EP 96106945 A EP96106945 A EP 96106945A EP 96106945 A EP96106945 A EP 96106945A EP 0752481 B1 EP0752481 B1 EP 0752481B1
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EP
European Patent Office
Prior art keywords
max
carbon
alloy
alloys
content
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
EP96106945A
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German (de)
English (en)
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EP0752481A1 (fr
Inventor
Ulrich Dr.-Ing. Brill
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Krupp VDM GmbH
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Krupp VDM GmbH
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Publication of EP0752481A1 publication Critical patent/EP0752481A1/fr
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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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • 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 a kneadable nickel alloy for Items with high resistance to isothermal and cyclic high temperature oxidation, high Heat resistance and creep rupture strength at temperatures up to 1200 ° C.
  • Objects such as furnace components, firing racks, Beam pipes, furnace rollers, furnace muffles, support and Fasteners in kilns for ceramic Products, catalyst foils and diesel glow plugs are not only used at very high temperatures for example, isothermally loaded above 1000 ° C, but must also be subjected to cyclical temperature loads Heating and cooling have grown. You have to therefore due to scale resistance not only with isothermal, but also with cyclic oxidation, as well as through distinguish sufficient heat and creep rupture strength. (All the following% figures are mass%)
  • An austenitic is for the first time from US Pat. No. 3,607,243 Alloy made famous with contents up to 0.1% Carbon, 58 - 63% nickel, 21 - 25% chromium, 1 - 1.7% Aluminum, and optionally up to 0.5% silicon, up to 1.0% Manganese, up to 0.6% titanium, up to 0.006% boron, up to 0.1% magnesium, up to 0.05% calcium, balance iron, where the phosphorus content is below 0.030%, the Sulfur content should be below 0.015%, which is a good one Resistance especially against cyclic oxidation Has temperatures up to 1093 ° C.
  • the Heat resistance values are given as follows: 80 MPa for 982 ° C, 45 MPa for 1093 ° C and 23 MPa for 1149 ° C.
  • the creep rupture strength is 32 MPa after 1000 hours for 871 ° C, 16 MPa for 982 ° C and 7 MPa for 1093 ° C.
  • This material has proven itself particularly in application in the temperature range above 1000 ° C. This is based on the formation of a protective chromium oxide-aluminum oxide layer and especially on the low The tendency of the oxide layer to flake off when the temperature changes.
  • the material has become one important alloy developed in industrial furnace construction. Typical applications are jet pipes for gas and oil-fired ovens and transport rollers in roller hearth ovens for firing ceramic products. Furthermore is the material for parts in exhaust gas detoxification systems and petrochemical plants.
  • the material known from US Pat. No. 3,607,243 is nitrogen in amounts of 0 , 04 to 0.1% is added and at the same time a titanium content of 0.2 to 1.0% is mandatory.
  • the chrome contents are 19-28% and the aluminum contents 0.75-2.0% with nickel contents of 55-65%.
  • the carbon content should not exceed 0.1% in order to avoid the formation of carbides, in particular of the M 23 C 6 type, since these adversely affect the microstructure of the structure and affect the properties of the alloy at very high temperatures.
  • EP 0 508 058 A1 discloses the alloying of Carbon levels from 0.12 to 0.30% in connection with the stable carbide formers titanium (0.01 to 1.0%), niobium (0.01 to 1.0%) and zirconium (0.01 to 0.20%) into one Nickel alloy with 23 - 30% chromium, 8 - 11% iron, 1.8 - 2.4% aluminum, 0.01 - 0.15% yttrium, 0.001 - 0.015% magnesium, 0.001 - 0.010% calcium, at maximum contents of 0.030% for nitrogen, 0.50% for Silicon, 0.25% for manganese, 0.020% for phosphorus and 0.010% for sulfur. To ensure one sufficient resistance to oxidation at temperatures above 1100 ° C, chrome contents of at least 23% required.
  • the hot and creep rupture strengths achieved with this material exceed the 1% yield strengths (R p1.0 / 10 4 ) and creep rupture strengths (R m / 10 4 ) as well as the thermal strengths (R m ) and yield strengths (4 p1.0 ) in the temperature range of 850 - 1200 ° C. Nevertheless, there are applications in which the strengths achieved are not yet sufficient. In particular, these are cassettes and firing racks, in which the material cross-section must be made very thin for economic reasons, and linings of combustion chambers of gas turbines, in which a significant improvement in efficiency can only be achieved at significantly higher wall or operating temperatures.
  • the task is solved by an austenitic carbide-strengthened nickel-chromium-iron wrought alloy, consisting of 0.20 to 0.40% carbon with a quantity of carbon that can be precipitated
  • C * C total - (C solved + C born Ti + C born + C born Zr ) from 0.083% to 0.300%, 25 to 30.0% Chrome, 8 to 11.0% Iron, more than 2.4 to 3.0%
  • Aluminum 0.01 to 0.15% Yttrium, 0.01 to 0.20% Titanium, 0.01 to 0.20% Niobium, 0.01 to 0.10% Zirconium, 0.001 to 0.015%
  • Magnesium 0.001 to 0.010% Calcium, ⁇ 0.036% Nitrogen, Max. 0.50% Silicon, Max. 0.25% Manganese, Max. 0.020% Phosphorus, Max. 0.010% Sulfur,
  • the carbide-strengthened wrought nickel-chromium-iron alloy according to the invention not only has defined carbon contents from 0.20 to 0.40%, but also specifies with C * 0,0 0.083% carbon a specification for the remaining carbon which can be eliminated .
  • C * 0,0 0.083%
  • the Cr 23 C 6 carbides observed up to that point were no longer excreted, but rather primarily eliminated Cr 7 C 3 carbides were observed. Their amount increases with increasing C * content.
  • the Cr 7 C 3 carbides excreted between the liquidus and solidus temperatures have a strength-increasing effect comparable to that of titanium, niobium and zirconium carbides.
  • chrome contents of at least 25.0% required. This limit shouldn't either are undercut because the chrome content decreases Amount of dissolved and therefore not excreted Carbon increases.
  • the upper limit shouldn't be 30% exceed to problems with the hot forming of the Avoid alloy.
  • Aluminum brings about an increase in the heat resistance, in particular in the temperature range from 600 to 800 ° C, which the material passes through in use both during heating and cooling, due to the precipitation of the phase Ni 3 Al ( ⁇ '-phase). Since the elimination of this phase is associated with a drop in toughness, it is necessary to limit the aluminum content.
  • the determination of the elongation at break in the temperature range from room temperature to 1200 ° C. showed no significant reduction in the elongation at break in the temperature range from 600 to 800 ° C., so that the aluminum content could be set at more than 2.4 to 3.0%.
  • the silicon content should be kept as low as possible to the formation of low melting phases avoid. So the silicon content should be less than or equal 0.50%, which is technically no problem today is manageable.
  • the manganese content should not exceed 0.25%, to have negative effects on the resistance to oxidation to avoid the material.
  • Additions of magnesium and calcium are used for improvement the hot formability and also have an improving effect the oxidation resistance.
  • the Upper limits of 0.015% for magnesium and 0.010% for Calcium should not be exceeded as above levels of magnesium and Calcium the appearance of low melting phases favor and so again the hot formability worsen.
  • the iron content of the alloy according to the invention is in the range of 8 up to 11% around ferrochrome and cheap when melting the alloy To be able to use ferronickel instead of more expensive pure nickel and chrome metal.
  • Table 1 contains analyzes of six of the prior art Alloys A, B, C, D, G, H and three of the invention Alloys E, J, K.
  • Table 2 shows the levels of precipitated Cr 23 C 6 and Cr 7 C 3 carbide calculated for alloys A - K.
  • All examined alloys are in a very narrow scatter band of max. ⁇ 0.040 g / m 2 h and therefore allow the statement that the alloys E, J and K according to the invention are not subject to any limited oxidation resistance compared to the prior art, despite their high content of carbon which can be precipitated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Heat Treatment Of Steel (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Chemically Coating (AREA)
  • Materials For Medical Uses (AREA)
  • Heat Treatment Of Articles (AREA)
  • Contacts (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Forging (AREA)

Claims (1)

  1. Alliage de nickel pétrissable, durci par carbures, austénitique, composé de (en % en poids)
    0,20 à 0,40 % de carbone
    avec une quantité de carbone précipitable C* = Ctotal - (Cdissous + Ccombiné Ti + Ccombiné Nb + Ccombiné Zr) de 0,083 % à 0,300 %, 25 à 30,0 % de chrome 8 à 11,0 % de fer plus de 2,4 à 3,0 % d'aluminium 0,01 à 0,15 % d'yttrium 0,01 à 0,20 % de titane 0,01 à 0,20 % de niobium 0,01 à 0,10 % de zirconium 0,001 à 0,015 % de magnésium 0,001 à 0,010 % de calcium ≤ 0,036 % d'azote max. 0,50 % de silicium max. 0,25 % de manganèse max. 0,020 % de phosphore max. 0,010 % de soufre,
    le reste étant du nickel, des impuretés inévitables résultant de l'élaboration, y compris.
EP96106945A 1995-07-04 1996-05-03 Alliage de nickel malléable Expired - Lifetime EP0752481B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19524234 1995-07-04
DE19524234A DE19524234C1 (de) 1995-07-04 1995-07-04 Knetbare Nickellegierung

Publications (2)

Publication Number Publication Date
EP0752481A1 EP0752481A1 (fr) 1997-01-08
EP0752481B1 true EP0752481B1 (fr) 2001-08-01

Family

ID=7765913

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96106945A Expired - Lifetime EP0752481B1 (fr) 1995-07-04 1996-05-03 Alliage de nickel malléable

Country Status (11)

Country Link
US (1) US5755897A (fr)
EP (1) EP0752481B1 (fr)
JP (1) JP3106157B2 (fr)
KR (1) KR970006528A (fr)
CN (1) CN1053226C (fr)
AT (1) ATE203780T1 (fr)
CA (1) CA2179214C (fr)
DE (2) DE19524234C1 (fr)
IL (1) IL118594A (fr)
TW (1) TW366365B (fr)
ZA (1) ZA965615B (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990026510A (ko) * 1997-09-25 1999-04-15 윤종용 외장형 히트 싱크를 구비하는 수직실장형 반도체 패키지 모듈
DE19753539C2 (de) * 1997-12-03 2000-06-21 Krupp Vdm Gmbh Hochwarmfeste, oxidationsbeständige knetbare Nickellegierung
US5997809A (en) * 1998-12-08 1999-12-07 Inco Alloys International, Inc. Alloys for high temperature service in aggressive environments
GB2361933A (en) * 2000-05-06 2001-11-07 British Nuclear Fuels Plc Melting crucible made from a nickel-based alloy
DE102006053917B4 (de) * 2005-11-16 2019-08-14 Ngk Spark Plug Co., Ltd. Für Verbrennungsmotoren benutzte Zündkerze
JP5201708B2 (ja) * 2006-04-14 2013-06-05 三菱マテリアル株式会社 Ｎｉ基耐熱合金溶接用ワイヤー
US7823556B2 (en) * 2006-06-19 2010-11-02 Federal-Mogul World Wide, Inc. Electrode for an ignition device
DE102008051014A1 (de) * 2008-10-13 2010-04-22 Schmidt + Clemens Gmbh + Co. Kg Nickel-Chrom-Legierung
DE102012002514B4 (de) * 2011-02-23 2014-07-24 VDM Metals GmbH Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit
DE102014001329B4 (de) * 2014-02-04 2016-04-28 VDM Metals GmbH Verwendung einer aushärtenden Nickel-Chrom-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
DE102014001330B4 (de) 2014-02-04 2016-05-12 VDM Metals GmbH Aushärtende Nickel-Chrom-Kobalt-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
CN104451267A (zh) * 2014-11-22 2015-03-25 湘潭高耐合金制造有限公司 一种镍钇合金火花塞电极材料及其制备方法
KR102504107B1 (ko) 2015-10-27 2023-02-27 삼성전자주식회사 멀티미디어 인터페이스 커넥터와 이를 구비한 전자 기기
IT202100000086A1 (it) * 2021-01-05 2022-07-05 Danieli Off Mecc Apparato per il riscaldo di prodotti siderurgici

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607243A (en) * 1970-01-26 1971-09-21 Int Nickel Co Corrosion resistant nickel-chromium-iron alloy
US4312682A (en) * 1979-12-21 1982-01-26 Cabot Corporation Method of heat treating nickel-base alloys for use as ceramic kiln hardware and product
US4439248A (en) * 1982-02-02 1984-03-27 Cabot Corporation Method of heat treating NICRALY alloys for use as ceramic kiln and furnace hardware
US4784830A (en) * 1986-07-03 1988-11-15 Inco Alloys International, Inc. High nickel chromium alloy
US4882125A (en) * 1988-04-22 1989-11-21 Inco Alloys International, Inc. Sulfidation/oxidation resistant alloys
DE4111821C1 (fr) * 1991-04-11 1991-11-28 Vdm Nickel-Technologie Ag, 5980 Werdohl, De
FR2675818B1 (fr) * 1991-04-25 1993-07-16 Saint Gobain Isover Alliage pour centrifugeur de fibres de verre.
DE4130140C1 (fr) * 1991-09-11 1992-11-19 Krupp-Vdm Ag, 5980 Werdohl, De
DE4130139C1 (fr) * 1991-09-11 1992-08-06 Krupp-Vdm Ag, 5980 Werdohl, De
ES2073873T3 (es) * 1991-12-20 1995-08-16 Inco Alloys Ltd Aleacion de ni-cr con alta resistencia a la temperatura.
KR940014865A (ko) * 1992-12-11 1994-07-19 에드워드 에이. 스틴 고온 저항성 니켈-크롬 합금
EP0611938A1 (fr) * 1993-02-10 1994-08-24 Robert Thomas Metall- und Elektrowerke Râtelier de caisson pour articles de poterie

Also Published As

Publication number Publication date
DE59607396D1 (de) 2001-09-06
JP3106157B2 (ja) 2000-11-06
EP0752481A1 (fr) 1997-01-08
CA2179214A1 (fr) 1997-01-05
CN1053226C (zh) 2000-06-07
US5755897A (en) 1998-05-26
ATE203780T1 (de) 2001-08-15
IL118594A0 (en) 1996-10-16
IL118594A (en) 2000-06-01
TW366365B (en) 1999-08-11
DE19524234C1 (de) 1997-08-28
CN1147560A (zh) 1997-04-16
KR970006528A (ko) 1997-02-21
JPH0925530A (ja) 1997-01-28
ZA965615B (en) 1997-01-27
CA2179214C (fr) 2000-08-01

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