EP1501953B1 - Alliage nickel-chrome-fonte resistant a la chaleur et a la corrosion - Google Patents

Alliage nickel-chrome-fonte resistant a la chaleur et a la corrosion Download PDF

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Publication number
EP1501953B1
EP1501953B1 EP04704238A EP04704238A EP1501953B1 EP 1501953 B1 EP1501953 B1 EP 1501953B1 EP 04704238 A EP04704238 A EP 04704238A EP 04704238 A EP04704238 A EP 04704238A EP 1501953 B1 EP1501953 B1 EP 1501953B1
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Prior art keywords
nickel
chromium
alloy
aluminum
chromium alloy
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Expired - Lifetime
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EP04704238A
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German (de)
English (en)
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EP1501953A1 (fr
EP1501953B8 (fr
Inventor
Rolf Kirchheiner
Dietlinde Jakobi
Petra Becker
Ricky Durham
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Schmidt and Clemens GmbH and Co KG
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Schmidt and Clemens GmbH and Co KG
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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
    • C22C19/051—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%
    • 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
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W

Definitions

  • High-temperature processes for example in petroleum chemistry, require materials that are not only heat-resistant, but also sufficiently resistant to corrosion and, in particular, that are subject to the stresses of hot product and combustion gases.
  • the coils of cracking and reforming furnaces outside of highly oxidizing combustion gases with a temperature up to 1100 ° C and more applied, while in the Inhern of cracking tubes at temperatures up to 1100 ° C a strong carburizing and in the interior of reformer tubes at temperatures up to 900 ° C and high pressure a weak carburizing and different oxidizing atmosphere prevails.
  • the contact with the hot combustion gases also leads to a nitriding of the pipe material and the formation of a scale layer, which is associated with an increase in the pipe outside diameter by a few percent and a reduction in the wall thickness by up to 10%.
  • the carburizing atmosphere in the tube interior causes carbon diffuses into the pipe material and it comes there at temperatures above 900 ° C for the formation of carbides such as M 23 C 6 and with increasing carburization to the emergence of the carbon-rich carbide M 7 C 3 .
  • carbides such as M 23 C 6
  • M 7 C 3 the carbon-rich carbide
  • the consequence of this is internal stress due to the increase in volume associated with carbide formation or conversion as well as a decrease in strength and toughness of the pipe material.
  • graphite or split carbon can be produced and, in conjunction with internal stresses, cracking can occur, through which carbon is increasingly introduced into the pipe material.
  • High-temperature processes therefore require materials with high creep rupture strength, microstructural stability and carburization and oxidation resistance. These requirements are met, within limits, by alloys containing, in addition to iron, 20 to 35% nickel, 20 to 25% chromium and for improving carburization resistance up to 1.5% silicon, for example the nickel-chromium steel alloy 35Ni25Cr-1, which is suitable for centrifugally cast tubes. 5Si, which is resistant to oxidation and carburization even at temperatures of 1100 ° C. The high nickel content reduces the rate of diffusion and the solubility of the carbon and thus increases the carburization resistance.
  • the alloys form at elevated temperatures under oxidizing conditions a cover layer of Cr 2 O 3 , which acts as a barrier against penetration of oxygen and carbon into the underlying tube material.
  • a cover layer of Cr 2 O 3 acts as a barrier against penetration of oxygen and carbon into the underlying tube material.
  • the Cr 2 O 3 becomes volatile, so that the protective effect of the cover layer is rapidly lost.
  • a series of high-heat, oxidation and carburization resistant nickel-base alloys are known, including the alloy 6125 Gt / alloy 603 GT with 62% nickel, 25% chromium, 0.22% carbon, 2.8% aluminum, 0.2% titanium and 9% iron, as well as 0.1% yttrium and 0.1% Zr a further development of the also described largely matching alloy 6025HT / alloy 602 CA, but with 0.18% carbon and only 2.3% aluminum, but 9.5% iron.
  • the alloy 602 CA also includes an alloy comprising 25% chromium, 9.5% iron, 2.2% aluminum, 0.18% carbon, 0.15% titanium, 0.06% zirconium and 0.08% Yttrium, rest nickel described.
  • the invention pursues the objective of damaging the mechanism of damage: carburizing - reducing the creep strength - to curb internal oxidation with the further consequence of increased carburization and oxidation, and to provide a cast alloy that can be used even at extremely high operating temperatures in carburizing and / or still has an adequate life span in an oxidizing atmosphere.
  • the invention achieves this with the aid of a nickel-chromium casting alloy with specific contents of carbon, aluminum and yttrium.
  • the invention consists in using a casting alloy up to 0.8% carbon up to 0.2% silicon up to 0.2% manganese 15 up to 40% chrome 0.5 up to 13% iron 1.5 up to 7% aluminum 0.1 up to 2.5% niobium up to 1.5% titanium 0.01 up to 0.4% zirconium up to 0.06% nitrogen until 12 % cobalt until 5 % molybdenum until 6 % tungsten 0.01 up to 0.1% Yttrium, rest nickel and usual impurities.
  • the total content of the alloy of nickel, chromium and aluminum should be 80 to 90%.
  • the alloy individually or side by side, contains at most 0.7% carbon, up to 30% chromium, up to 12% iron, 2.2 to 6% aluminum, 0.1 to 2.0% niobium, 0.01 to 1.0% Titanium, up to 0.15% zirconium and - for high creep resistance - up to 10% cobalt, at least 3% molybdenum and up to 5% tungsten, for example 4 to 8% cobalt, up to 4% molybdenum and 2 to 4% tungsten, if it is does not primarily depend on the high oxidation resistance. Depending on the stress in the individual case, therefore, the contents of cobalt, molybdenum and tungsten must be selected within the content limits according to the invention.
  • Particularly suitable is an alloy with at most 0.7% carbon, at most 0.2, more preferably at most 0.1% silicon, up to 0.2% manganese, 18 to 30% chromium, 0.5 to 12% iron, 2, 2 to 5% aluminum, 0.4 to 1.6% niobium, 0.01 to 0.6% titanium, 0.01 to 0.15% zirconium, at most 0.06% nitrogen, at most 10% cobalt and at most 5 % Tungsten.
  • Optimum results can be achieved if the chromium content is not more than 26.5%, the iron content is not more than 11%, the aluminum content is 3 to 6%, the titanium content is more than 0.15%, the zirconium content is more than 0.05% Cobalt content at least 0.2%, the tungsten content above 0.05% and the yttrium content is 0.019 to 0.089%.
  • the high creep strength of the alloy according to the invention for example a service life of 2000 hours at a load of 4 to 6 MPa and a temperature of 1200 ° C, guarantees the maintenance of a closed and firmly adhering oxidic barrier layer in the form of a high aluminum content of the alloy self-supplementing or renewable, against carburization and oxidation effective Al 2 O 3 layer.
  • This layer consists, as investigations have shown, of ⁇ -Al 2 O 3 and contains at best selective mixed oxides which do not change the character of the ⁇ -Al 2 O 3 layer; this assumes at higher temperatures, especially above 1050 ° C in view of the rapidly decreasing at these temperatures resistance of the Cr 2 O 3 layer of conventional materials increasingly the protection of the alloy according to the invention against carburization and oxidation.
  • On the Al 2 O 3 barrier layer can - at least partially - still a cover layer of nickel oxide (NiO) and mixed oxides (Ni (Cr, Al) 2 O 4 ) are located, their nature and extent
  • NiO nickel oxide
  • Ni (Cr, Al) 2 O 4 ) mixed oxides
  • the structure of the alloy according to the invention above 4% aluminum inevitably contains ⁇ '-phase, which acts as a solidifying agent at low and medium temperatures, but also reduces the toughness or elongation at break. In individual cases, it may therefore be necessary to draw a compromise between toughness and oxidation / carburization resistance based on the intended use.
  • the barrier layer according to the invention from ⁇ -Al 2 O 3, the stable Al 2 O 3 modification, is stable at all oxygen concentrations.
  • the table contains, as an example of two not falling under the invention wrought alloys with a comparatively low carbon content and very fine-grained microstructure of a particle size ⁇ 10 ⁇ m the comparison alloy 5 and 7, while all other trial alloys are cast alloys.
  • Yttrium is a strong oxide former, whose effect in the alloy according to the invention is that the conditions of formation and the adhesion of the ⁇ -Al 2 O 3 layer improve significantly.
  • the aluminum content of the alloy according to the invention has an important role to play in that aluminum leads to the formation of a ⁇ '-precipitation phase which causes a considerable increase in tensile strength.
  • the yield strength and the tensile strength of the three alloys 13, 19, 20 to 900 ° C. according to the invention are considerably above the strength values of the four comparative alloys.
  • the elongation at break of the alloys according to the invention essentially corresponds to that of the comparative alloys; It increases sharply above about 900 ° C, as is apparent from the diagram of Fig. 3, while the strength reaches the level of the comparative alloys (Fig. 1, 2). This is explained by the fact that from about 900 ° C, the ⁇ '-phase goes into solution and above about 1000 ° C is completely dissolved.
  • the creep behavior of inventive alloys with different contents of aluminum is shown in the Larson-Miller diagram of FIG. 4.
  • the graph of FIG. 13 shows that the contents of the alloy according to the invention should be matched to one another in such a way that the condition 9 % al ⁇ % Cr is satisfied.
  • the straight line in the diagram of Fig. 13 separates the region of the alloys with a sufficiently protective ⁇ -alumina layer above the straight line from the range of alloys with mixed oxide impaired carburization or catalytic coking.
  • Fig. 14 illustrates the superiority of the steel alloy according to the invention with reference to six embodiments 21 to 26 compared to the conventional comparative alloys 1, 3, 4 6 and 7.
  • the compositions of the experimental alloys 21 to 26 are shown in the table.
  • the graph of FIG. 15 shows that alloy 19 with an average aluminum content of 3.3% increases the reduction in service life with increasing load, while alloy 20 with its high aluminum content of 4.8% strengthens for all load cases results in a strong, but approximately equal reduction in the relative service life. From the diagram for 1200 ° C, a reduction in the service life with an increase in the aluminum content of 2.4% (Alloy 13) to 3.3% (Alloy 19) for all three load cases, a decrease in the relative life to about two-thirds. A further increase of the aluminum content to 4.8% (alloy 20) again shows a load-dependent reduction in the relative service life.
  • the two diagrams show that with increasing aluminum content, the service life before breakage in the creep test decreases. Furthermore, with increasing temperature and increasing duration of use or with decreasing stress, the negative influence of the aluminum on the creep life decreases.
  • the high aluminum alloys are particularly suitable for long-term use at temperatures for which no cast or centrifugally cast materials could be used so far.
  • cast alloy according to the invention is particularly suitable as a material for furnace parts, blasting furnaces for heating ovens, rollers for annealing, parts of strand and strip casting plants, hoods and muffles for annealing, parts of large diesel engines, containers for catalysts and for cracking and reformer tubes.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Mold Materials And Core Materials (AREA)
  • Catalysts (AREA)
  • Laminated Bodies (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Powder Metallurgy (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Ceramic Products (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Exhaust Silencers (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Supercharger (AREA)
  • Soft Magnetic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Claims (7)

  1. Utilisation d'un alliage nickel-chrome avec
    jusqu'à 0,8 % de carbone
    jusqu'à 0,2 % de silicium
    jusqu'à 0,2 % de manganèse
    de 15 à 40 % de chrome
    de 0,5 à 13 % de fer
    de 1,5 à 7 % d'aluminium
    de 0,1 à 2,5 % de niobium
    jusqu'à 1,5 % de titane
    de 0,01 à 0,4 % de zirconium
    jusqu'à 0,06 % d'azote
    jusqu'à 12 % de cobalt
    jusqu'à 5 % de molybdène
    jusqu'à 6 % de tungstène
    de 0,019 à 0,089 % d'yttrium,
    le reste étant du nickel et des impuretés usuelles
    comme matériau pour la fabrication de pièces moulées.
  2. Utilisation d'un alliage nickel-chrome selon la revendication 1 avec au maximum 0,7 % de carbone, jusqu'à 0,2 % de manganèse, de 18 à 30 % de chrome, de 0,5 à 12 % de fer, de 2,2 à 5 % d'aluminium, de 0,4 à 1,6 % de niobium, de 0,01 à 0,6 % de titane, de 0,01 à 0,15 % de zirconium, au maximum 0,06 % d'azote, au maximum 10 % de cobalt, au moins 3 % de molybdène, et au maximum 5 % de tungstène individuellement ou en juxtaposition les uns à côté des autres pour le but selon la revendication 1.
  3. Utilisation d'un alliage nickel-chrome selon la revendication 1 ou 2 comprenant au maximum 0,7 % de carbone, au maximum 0,1 % de silicium, jusqu'à 0,2 % de manganèse, de 18 à 30 % de chrome, de 0,5 à 12 % de fer, de 2,2 à 5 % d'aluminium, de 0,4 à 1,6 % de niobium, de 0,01 à 0,6 % de titane, de 0,01 à 0,15 % de zirconium, au maximum 0,06 % d'azote, au maximum 10 % de cobalt, jusqu'à 4 % de molybdène et au maximum 5 % de tungstène, pour le but selon la revendication 1.
  4. Utilisation d'un alliage nickel-chrome selon l'une quelconque des revendications 1 à 3 avec au maximum 26,5 % de chrome, au maximum 11 % de fer, de 3 à 6 % d'aluminium, plus de 0,15 % de titane, plus de 0,05 % de zirconium, au moins 0,2 % de cobalt, jusqu'à 4 % de molybdène et plus de 0,05 % de tungstène séparément ou en juxtaposition les uns à côté des autres pour le but selon la revendication 1.
  5. Utilisation d'un alliage nickel-chrome selon l'une quelconque des revendications 1 à 4, dont les teneurs en aluminium et en chrome satisfont à la condition 9 % d ′ ⁢ Al ≥ % de Cr
    Figure imgb0007
    pour le but selon la revendication 1.
  6. Utilisation d'un alliage nickel-chrome selon l'une quelconque des revendications 1 à 5, dans laquelle la teneur totale en nickel, en chrome et en aluminium va de 80 à 90 %, pour le but selon la revendication 1.
  7. Utilisation d'un alliage nickel-chrome selon l'une quelconque des revendications 1 à 6 comme matériau pour la fabrication de pièces de four, de tuyaux pour le chauffage de fours, de rouleaux pour fours à incandescence, de pièces de dispositifs moulées en forme de feuillets ou de boudins, de capots et de moufles pour fours à incandescence, de pièces de grands moteurs diesels, de corps moulés pour remplissages de catalyseurs ainsi que de tuyaux de dispositifs de craquage et de reformage.
EP04704238A 2003-01-25 2004-01-22 Alliage nickel-chrome-fonte resistant a la chaleur et a la corrosion Expired - Lifetime EP1501953B8 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10302989A DE10302989B4 (de) 2003-01-25 2003-01-25 Verwendung einer Hitze- und korrosionsbeständigen Nickel-Chrom-Stahllegierung
DE10302989 2003-01-25
PCT/EP2004/000504 WO2004067788A1 (fr) 2003-01-25 2004-01-22 Alliage nickel-chrome-fonte resistant a la chaleur et a la corrosion

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EP1501953A1 EP1501953A1 (fr) 2005-02-02
EP1501953B1 true EP1501953B1 (fr) 2007-05-23
EP1501953B8 EP1501953B8 (fr) 2008-01-23

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US (3) US20050129567A1 (fr)
EP (1) EP1501953B8 (fr)
JP (1) JP4607092B2 (fr)
KR (1) KR20050092452A (fr)
CN (1) CN100351412C (fr)
AT (1) ATE362997T1 (fr)
AU (1) AU2004207921A1 (fr)
BR (1) BRPI0406570B1 (fr)
CA (1) CA2513830C (fr)
DE (2) DE10302989B4 (fr)
EA (1) EA008522B1 (fr)
EG (1) EG23864A (fr)
ES (1) ES2287692T3 (fr)
HR (1) HRP20050728A2 (fr)
IL (1) IL169579A0 (fr)
MA (1) MA27650A1 (fr)
MX (1) MXPA05007806A (fr)
NO (1) NO20053617L (fr)
NZ (1) NZ541874A (fr)
PL (1) PL377496A1 (fr)
PT (1) PT1501953E (fr)
RS (1) RS20050552A (fr)
TR (1) TR200502892T1 (fr)
UA (1) UA80319C2 (fr)
WO (1) WO2004067788A1 (fr)
ZA (1) ZA200505714B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019034845A1 (fr) 2017-08-15 2019-02-21 Paralloy Limited Alliage résistant à l'oxydation

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CN104862535A (zh) * 2015-05-15 2015-08-26 新奥科技发展有限公司 一种镍基合金及其制备方法和应用
CN105463288B (zh) * 2016-01-27 2017-10-17 大连理工大学 高强高塑耐氯离子腐蚀的铸造合金及其制备方法
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JP7131318B2 (ja) * 2018-11-14 2022-09-06 日本製鉄株式会社 オーステナイト系ステンレス鋼
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CA2513830C (fr) 2010-12-14
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PT1501953E (pt) 2007-08-17
MXPA05007806A (es) 2006-04-27
UA80319C2 (en) 2007-09-10
ATE362997T1 (de) 2007-06-15
JP4607092B2 (ja) 2011-01-05
KR20050092452A (ko) 2005-09-21
NO20053617D0 (no) 2005-07-26
WO2004067788A1 (fr) 2004-08-12
EP1501953A1 (fr) 2005-02-02
US10724121B2 (en) 2020-07-28
NO20053617L (no) 2005-10-06
RS20050552A (sr) 2007-09-21
ZA200505714B (en) 2006-04-26
US20090016926A1 (en) 2009-01-15
TR200502892T2 (tr) 2005-09-21
EG23864A (en) 2007-11-19
AU2004207921A1 (en) 2004-08-12
DE502004003863D1 (de) 2007-07-05
JP2006516680A (ja) 2006-07-06
NZ541874A (en) 2008-03-28
ES2287692T3 (es) 2007-12-16
DE10302989B4 (de) 2005-03-03
HK1075679A1 (zh) 2005-12-23
CA2513830A1 (fr) 2004-08-12
US10041152B2 (en) 2018-08-07
CN1742106A (zh) 2006-03-01
US20050129567A1 (en) 2005-06-16
IL169579A0 (en) 2007-07-04
BRPI0406570A (pt) 2005-12-20
CN100351412C (zh) 2007-11-28
TR200502892T1 (tr) 2008-02-21
HRP20050728A2 (en) 2005-12-31
MA27650A1 (fr) 2005-12-01
EA200501178A1 (ru) 2005-12-29
PL377496A1 (pl) 2006-02-06
BRPI0406570B1 (pt) 2016-05-17
EP1501953B8 (fr) 2008-01-23
DE10302989A1 (de) 2004-08-05

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