EP0508058A1 - Austenitic alloy nickel-chromium-iron - Google Patents
Austenitic alloy nickel-chromium-iron Download PDFInfo
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- EP0508058A1 EP0508058A1 EP92102228A EP92102228A EP0508058A1 EP 0508058 A1 EP0508058 A1 EP 0508058A1 EP 92102228 A EP92102228 A EP 92102228A EP 92102228 A EP92102228 A EP 92102228A EP 0508058 A1 EP0508058 A1 EP 0508058A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
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- the invention relates to an austenitic nickel-chromium-iron alloy and its use as a material for objects with high resistance to isothermal and cyclic high-temperature oxidation, high heat resistance and creep rupture strength at temperatures above 1100 to 1200 ° C.
- Objects such as furnace components, radiant tubes, furnace rollers, furnace muffles and support systems in furnaces for ceramic products are not only isothermally stressed at very high temperatures above 1000 ° C, but must also be able to withstand cyclical temperature stresses when heating up and cooling the furnaces or radiant tubes. They must therefore be characterized by scaling resistance not only in the case of isothermal, but also in the case of cyclic oxidation, and by sufficient heat resistance and creep resistance.
- An austenitic alloy is known for the first time from US Pat. No. 3,607,243 with contents of (data in% by weight) 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, the rest iron, the Phosphorus content less than 0.030%, the sulfur content should be less than 0.015%, which is particularly resistant to cyclic oxidation at temperatures up to 2000 ° F (1093 ° C).
- the heat resistance values are given as follows: 80 MPa for 1800 ° F, 45 MPa for 2000 ° F and 23 MPa for 2100 ° F.
- the creep rupture strength after 1000 hours is 32 MPa for 1600 ° F, 16 MPa for 1800 ° F and 7 MPa for 2000 ° F.
- the material NiCr23Fe with material no. 2.4851 and the UNS designation N 06601 introduced into industrial application. This material has proven itself particularly when used in the temperature range above 1000 ° C. This is based on the formation of a protective chromium oxide-aluminum oxide layer, but in particular on the overall low tendency of the oxide layer to flake off under alternating temperatures.
- the material has developed into an important material in industrial furnace construction. Typical applications are jet pipes for gas-fired furnaces and transport rollers in roller hearth furnaces for ceramic products. The material is also suitable for parts in exhaust gas detoxification plants and petrochemical plants.
- the material known from US Pat. No. 3,607,243 contains nitrogen in amounts of 0.04 to 0.1 wt .-% added and at the same time a titanium content of 0.2 to 1.0 wt .-% 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% by weight in order to avoid the formation of carbides, in particular of the M23C6 type, since these adversely affect the microstructure of the structure and affect the properties of the alloy at very high temperatures.
- the resistance to oxidation (expressed by the so-called cyclical mass change (g / m2 ⁇ h) in air at high test temperatures, for example 2000 ° F, as described in US Pat. No. 4,784,830) is not the only decisive factor for the service life of highly heat-resistant objects, but also the heat resistance and the creep rupture strength at the respective application temperatures.
- the contents are: carbon 0.15 to 0.25% chrome 24 to 26% aluminum 2.1 to 2.4% yttrium 0.05 to 0.12% titanium 0.40 to 0.60% niobium 0.40 to 0.60% Zircon 0.01 to 0.10% nitrogen max 0.010% with unchanged content ranges of the remaining alloy elements.
- the nickel-chromium-iron alloy according to the invention has a departure from the previous state of the art, which only permits carbon contents up to a maximum of 0.10% by weight, since it was believed that only with these low carbon contents did the required oxidation resistance at temperatures up to 1200 ° C. to be able to guarantee carbon contents of 0.12 to 0.30% by weight.
- carbon contents of this order of magnitude in combination with the additives also provided according to the invention not only increase the heat resistance and the creep rupture strength, but also improve the oxidation resistance, Since the nitrogen content in the alloy according to the invention is kept as low as possible, the present carbon contents of 0.12 to 0.30% by weight in connection with the stable carbide formers titanium, niobium and zircon essentially form carbides of these elements, which also occur at temperatures up to 1200 ° C are thermally stable. The formation of chromium carbides, so of the type Cr23C6, is largely prevented.
- Chromium contents of at least 23% by weight are required to ensure adequate resistance to oxidation at temperatures above 1100 ° C.
- the upper limit should not exceed 30% by weight in order to avoid problems with the hot deformation of the alloy.
- Aluminum especially in the temperature range from 600 to 800 ° C, which the material passes through in use both during heating and cooling, increases the heat resistance by eliminating the phase Ni3Al (so-called ⁇ 'phase). Since the elimination of this phase is associated with a decrease in toughness, it is necessary to limit the aluminum content to 1.8 to 2.4% by weight.
- the silicon content should be kept as low as possible in order to avoid the formation of low-melting phases.
- the manganese content should not exceed 0.25% by weight in order to avoid negative effects on the oxidation resistance of the material.
- magnesium and calcium serve to improve the hot formability and also improve the oxidation resistance.
- the upper limits of 0.015% by weight (magnesium) and 0.010% by weight (calcium) should not are exceeded, since magnesium and calcium contents above these limit values promote the occurrence of low-melting phases and thus in turn impair the hot formability.
- the iron contents of the alloy according to the invention are in the range from 8 to 11% by weight. They are necessary in order to be able to use inexpensive ferrochrome and ferronickel when melting the alloy.
- Table 1 contains the analyzes of two alloys A and B covered by the invention and an alloy C according to the prior art, as can be found in US Pat. No. 4,784,830.
- the alloy A according to the invention in the entire temperature range of interest from 850 to 1200 ° C. is at significantly higher values than the alloy C according to the prior art, both in terms of the heat resistance Rm and at the 1% yield strength Rp.
- alloy B according to the invention Even better values are achieved by alloy B according to the invention, the alloy composition of which lies within the alloy variant given by claim 2. With this alloy variant, both the heat resistance and the yield point can be almost doubled up to temperatures of 1000 ° C.
- the creep behavior of alloy A according to the invention is compared with that of alloy C according to the prior art.
- the creep rupture strength and the 1% yield stress limit were determined in conventional creep rupture tests (see DE book “Material Science Steel", Volume 1, Springer-Verlag Berlin, 1984, pages 384 to 396 and DIN 50118).
- the creep rupture strength (MPa) is a measure of the ability of a material not to be destroyed under the influence of an acting load.
- the 1% yield stress limit which specifies the stress (in MPa) at a given loading time at which a 1% elongation is reached, characterizes the functional failure of the material under a specific long-term loading for the respective temperature.
- Alloy A according to the invention is clearly superior over the entire temperature range both in terms of creep rupture strength and in the 1% tensile yield strength of alloy C according to the prior art.
- the strength gain of alloy A according to the invention is more than 25% at all temperatures compared to alloy C.
- the behavior of the alloy A according to the invention can be better assessed than the behavior of the alloy C corresponding to the prior art, which cuts the abscissa (transition to loss of mass) already at approx. 1000 ° C., while the alloy A only at approx. 1050 ° C has a zero crossing.
- the objects mentioned can be easily manufactured from the material according to the invention, since it is not only readily thermoformable, but also for cold processing operations - such as Cold rolling to thin dimensions, folding, deep drawing, flanging - has the necessary forming capacity.
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Abstract
Description
Die Erfindung betrifft eine austenitische Nickel-Chrom-Eisen-Legierung und ihre Verwendung als Werkstoff für Gegenstände mit hoher Beständigkeit gegenüber isothermer und zyklischer Hochtemperaturoxidation, hoher Warmfestigkeit und Zeitstandfestigkeit bei Temperaturen oberhalb von 1100 bis 1200 °C.The invention relates to an austenitic nickel-chromium-iron alloy and its use as a material for objects with high resistance to isothermal and cyclic high-temperature oxidation, high heat resistance and creep rupture strength at temperatures above 1100 to 1200 ° C.
Gegenstände, wie Ofenbauteile, Strahlrohre, Ofenrollen, Ofenmuffeln und Stützsysteme in Brennöfen für keramische Erzeugnisse werden im Einsatz nicht nur bei sehr hohen Temperaturen oberhalb 1000 °C isotherm belastet, sondern müssen auch zyklischen Temperaturbelastungen beim Aufheizen und Abkühlen der Öfen oder Strahlrohre gewachsen sein.
Sie müssen sich daher durch Zunderbeständigkeit nicht nur bei isothermer, sondern auch bei zyklischer Oxidation, sowie durch eine ausreichende Warmfestigkeit und Zeitstandfestigkeit auszeichnen.Objects such as furnace components, radiant tubes, furnace rollers, furnace muffles and support systems in furnaces for ceramic products are not only isothermally stressed at very high temperatures above 1000 ° C, but must also be able to withstand cyclical temperature stresses when heating up and cooling the furnaces or radiant tubes.
They must therefore be characterized by scaling resistance not only in the case of isothermal, but also in the case of cyclic oxidation, and by sufficient heat resistance and creep resistance.
Aus der US-PS 3 607 243 ist erstmals eine austenitische Legierung bekannt geworden mit Gehalten von (Angaben in Gew.-%) bis 0,1 % Kohlenstoff, 58 - 63 % Nickel, 21 - 25 % Chrom, 1 - 1,7 % Aluminium, sowie wahlweise bis 0,5 % Silizium, bis 1,0 % Mangan, bis 0,6 % Titan, bis 0,006 % Bor, bis 0,1 % Magnesium, bis 0,05 % Calcium, Rest Eisen, wobei der Phosphorgehalt unter 0,030 %, der Schwefelgehalt unter 0,015 % liegen soll, die eine gute Beständigkeit insbesondere gegen zyklische Oxidation bei Temperaturen bis 2000 °F (1093 °C) aufweist.
Die Warmfestigkeitswerte werden wie folgt angegeben: 80 MPa für 1800 °F, 45 MPa für 2000 °F und 23 MPa für 2100 °F.An austenitic alloy is known for the first time from US Pat. No. 3,607,243 with contents of (data in% by weight) 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, the rest iron, the Phosphorus content less than 0.030%, the sulfur content should be less than 0.015%, which is particularly resistant to cyclic oxidation at temperatures up to 2000 ° F (1093 ° C).
The heat resistance values are given as follows: 80 MPa for 1800 ° F, 45 MPa for 2000 ° F and 23 MPa for 2100 ° F.
Die Zeitstandfestigkeit beträgt nach 1000 Stunden 32 MPa für 1600 °F, 16 MPa für 1800 °F und 7 MPa für 2000 °F.
Davon ausgehend hat sich der innerhalb dieser Legierungsgrenzen liegende Werkstoff NiCr23Fe mit der Werkstoff-Nr. 2.4851 und der UNS-Bezeichnung N 06601 in die industrielle Anwendung eingeführt.
Dieser Werkstoff bewährt sich vor allem bei der Anwendung im Temperaturbereich oberhalb von 1000 °C. Dies beruht auf der Bildung einer schützenden Chromoxid-Aluminiumoxidschicht, insbesondere jedoch auf der insgesamt geringen Neigung der Oxidschicht zum Abplatzen bei Temperatur-Wechselbelastung. Der Werkstoff hat sich so zu einem wichtigen Werkstoff im industriellen Ofenbau entwickelt. Typische Anwendungen sind Strahlrohre für gasbeheizte Öfen und Transportrollen in Rollenherdöfen für keramische Erzeugnisse. Darüberhinaus ist der Werkstoff auch für Teile in Abgasentgiftungsanlagen und petrochemischen Anlagen geeignet.
Um die für die Anwendung dieses Werkstoffs maßgebenden Eigenschaften noch weiter - für Anwendungstemperaturen oberhalb von 1100 bis 1200 °C - zu steigern, wird gemäß der US-PS 4 784 830 dem aus der, US-PS 3 607 243 bekannten Werkstoff Stickstoff in Mengen von 0,04 bis 0,1 Gew.-% zugesetzt und gleichzeitig zwingend ein Titangehalt von 0,2 bis 1,0 Gew.-% gefordert. Vorteilhafterweise soll auch der Siliziumgehalt oberhalb von 0,25 Gew.-% liegen und mit dem Titangehalt so korreliert sein, daß sich ein Verhältnis Si:Ti = 0,85 bis 3,0 ergibt. Die Chromgehalte betragen 19 - 28 % und die Aluminiumgehalte 0,75 - 2,0 % bei Nickelgehalten von 55 - 65 %.
Mit diesen Maßnahmen wird eine Verbesserung der Oxidationsbeständigkeit bei Anwendungstemperaturen bis 1200 °C erzielt, wodurch die Lebensdauer von z.B. Ofenrollen auf 12 Monate und mehr gegenüber 2 Monaten bei Ofenrollen, gefertigt aus dem Werkstoff gemäß US-PS 3 607 243, gesteigert werden konnte. Diese Verbesserung der Lebensdauer von Ofenbauteilen beruht vor allem auf einer Stabilisierung des Mikrogefüges durch Titannitride bei Temperaturen von 1200 °C.The creep rupture strength after 1000 hours is 32 MPa for 1600 ° F, 16 MPa for 1800 ° F and 7 MPa for 2000 ° F.
Based on this, the material NiCr23Fe with material no. 2.4851 and the UNS designation N 06601 introduced into industrial application.
This material has proven itself particularly when used in the temperature range above 1000 ° C. This is based on the formation of a protective chromium oxide-aluminum oxide layer, but in particular on the overall low tendency of the oxide layer to flake off under alternating temperatures. The material has developed into an important material in industrial furnace construction. Typical applications are jet pipes for gas-fired furnaces and transport rollers in roller hearth furnaces for ceramic products. The material is also suitable for parts in exhaust gas detoxification plants and petrochemical plants.
In order to further increase the properties which are decisive for the use of this material - for application temperatures above 1100 to 1200 ° C. - according to US Pat. No. 4,784,830, the material known from US Pat. No. 3,607,243 contains nitrogen in amounts of 0.04 to 0.1 wt .-% added and at the same time a titanium content of 0.2 to 1.0 wt .-% mandatory. Advantageously, the silicon content should also be above 0.25% by weight and be correlated with the titanium content in such a way that a Si: Ti ratio = 0.85 to 3.0 results. The chrome contents are 19-28% and the aluminum contents 0.75-2.0% with nickel contents of 55-65%.
With these measures, an improvement in the oxidation resistance is achieved at application temperatures up to 1200 ° C., whereby the service life of, for example, oven rolls can be increased to 12 months and more compared to 2 months for oven rolls made from the material according to US Pat. No. 3,607,243. This improvement in the lifespan of furnace components is primarily due to the stabilization of the microstructure by titanium nitride at temperatures of 1200 ° C.
Der Kohlenstoffgehalt soll ebenso, wie in der US-PS 3 607 243 beschrieben, 0,1 Gew.-% nicht überschreiten, um eine Ausbildung von Karbiden, insbesondere vom Typ M₂₃C₆, zu vermeiden, da diese sich nachteilig auf die Mikrostruktur des Gefüges und auf die Eigenschaften der Legierung bei sehr hohen Temperaturen auswirken.The carbon content, as described in US Pat. No. 3,607,243, should not exceed 0.1% by weight in order to avoid the formation of carbides, in particular of the M₂₃C₆ type, since these adversely affect the microstructure of the structure and affect the properties of the alloy at very high temperatures.
Für die Lebensdauer von hochhitzebeständigen Gegenständen ist jedoch nicht allein die Oxidationsbeständigkeit (ausgedrückt durch die sogenannte zyklische Massenänderung (g/m²·h) in Luft bei hohen Testtemperaturen, z.B. 2000 °F, wie in der US-PS 4 784 830 beschrieben) maßgebend, sondern auch die Warmfestigkeit und die Zeitstandfestigkeit bei den jeweiligen Anwendungstemperaturen.However, the resistance to oxidation (expressed by the so-called cyclical mass change (g / m² · h) in air at high test temperatures, for example 2000 ° F, as described in US Pat. No. 4,784,830) is not the only decisive factor for the service life of highly heat-resistant objects, but also the heat resistance and the creep rupture strength at the respective application temperatures.
Es ist Aufgabe der Erfindung, Nickel-Chrom-Eisen-Legierungen der eingangs genannten Art so auszugestalten, daß bei ausreichender Oxidationsbeständigkeit die Werte für die Warmfestigkeit und die Zeitstandfestigkeit verbessert sind, wodurch die Lebensdauer von aus solchen Legierungen gefertigten Gegenständen bedeutend erhöht wird.It is an object of the invention to design nickel-chromium-iron alloys of the type mentioned at the outset such that, with sufficient oxidation resistance, the values for the heat resistance and the creep rupture strength are improved, as a result of which the service life of objects made from such alloys is significantly increased.
Gelöst wird diese Aufgabe durch eine
Austenitische Nickel-Chrom-Eisen-Legierung,
bestehend aus (Angaben in Gewichtsprozent) :
einschließlich unvermeidbarer erschmelzungsbedingter Verunreinigungen.This task is solved by a
Austenitic nickel-chromium-iron alloy,
consisting of (data in percent by weight):
including unavoidable melt-related contaminants.
Nach einer bevorzugten Legierungsvariante betragen die Gehalte an
bei unveränderten Gehaltsbereichen der restlichen Legierungselemente.According to a preferred alloy variant, the contents are:
with unchanged content ranges of the remaining alloy elements.
Die erfindungsgemäße Nickel-Chrom-Eisen-Legierung weist in Abkehr vom bisherigen Stand der Technik, der Kohlenstoffgehalte nur bis maximal 0,10 Gew.-% zuläßt, da man glaubte, nur mit diesen geringen Kohlenstoffgehalten die geforderte Oxidationsbeständigkeit bei Temperaturen bis 1200 °C gewährleisten zu können, Kohlenstoffgehalte von 0,12 bis 0,30 Gew.-% auf.
In überraschender Weise bewirken Kohlenstoffgehalte in dieser Größenordnung in Verbindung mit den erfindungsgemäß weiterhin vorgesehenen Zusätzen, insbesondere an Yttrium und Zirkon, nicht nur eine Steigerung der Warmfestigkeit und der Zeitstandfestigkeit, sondern verbessern auch noch die Oxidationsbeständigkeit,
Da bei der erfindungsgemäßen Legierung der Stickstoffgehalt möglichst niedrig gehalten wird, entstehen bei den vorliegenden Kohlenstoffgehalten von 0,12 bis 0,30 Gew.-% in Verbindung mit den stabilen Karbidbildnern Titan, Niob und Zirkon im wesentlichen Karbide dieser Elemente, die auch bei Temperaturen bis zu 1200 °C thermisch stabil sind.Die Bildung von Chromkarbiden, so vom Typ Cr₂₃C₆, wird dadurch weitgehend unterbunden. Dies führt dazu, daß erstens durch die Bildung der im Vergleich zu Chromkarbiden thermisch stabileren Titan-, Niob- und Zirkonkarbide die Warmfestigkeit und die Zeitstandfestigkeit nachhaltig verbessert wird, zweitens mehr Chrom zur Bildung einer schützenden Chromoxid-Schicht zur Verfügung steht und damit die Oxidationsbeständigkeit bei gleichzeitiger Zugabe von Yttrium und Zirkon verbessert wird.The nickel-chromium-iron alloy according to the invention has a departure from the previous state of the art, which only permits carbon contents up to a maximum of 0.10% by weight, since it was believed that only with these low carbon contents did the required oxidation resistance at temperatures up to 1200 ° C. to be able to guarantee carbon contents of 0.12 to 0.30% by weight.
Surprisingly, carbon contents of this order of magnitude in combination with the additives also provided according to the invention, in particular yttrium and zirconium, not only increase the heat resistance and the creep rupture strength, but also improve the oxidation resistance,
Since the nitrogen content in the alloy according to the invention is kept as low as possible, the present carbon contents of 0.12 to 0.30% by weight in connection with the stable carbide formers titanium, niobium and zircon essentially form carbides of these elements, which also occur at temperatures up to 1200 ° C are thermally stable. The formation of chromium carbides, so of the type Cr₂₃C₆, is largely prevented. This leads to the fact that, firstly, the formation of titanium, niobium and zirconium carbides, which are more thermally stable than chromium carbides, sustainably improves the heat resistance and creep rupture strength, secondly, more chromium is available to form a protective chromium oxide layer and thus the oxidation resistance simultaneous addition of yttrium and zircon is improved.
Zur Sicherstellung einer ausreichenden Oxidationsbeständigkeit bei Temperaturen von oberhalb 1100 °C sind Chrom-Gehalte von mindestens 23 Gew.-% erforderlich. Die obere Grenze sollte 30 Gew.-% nicht überschreiten, um Probleme bei der Warmverformung der Legierung zu vermeiden.Chromium contents of at least 23% by weight are required to ensure adequate resistance to oxidation at temperatures above 1100 ° C. The upper limit should not exceed 30% by weight in order to avoid problems with the hot deformation of the alloy.
Aluminium bewirkt, besonders im Temperaturbereich von 600 bis 800 °C, den der Werkstoff im Einsatz sowohl beim Aufheizen als auch beim Abkühlen durchläuft, eine Steigerung der Warmfestigkeit durch Ausscheidung der Phase Ni₃Al (sog. γ' - Phase). Da die Ausscheidung dieser Phase gleichzeitig mit einem Abfall der Zähigkeit verbunden ist, ist es notwendig, die Gehalte an Aluminium auf 1,8 bis 2,4 Gew.-% zu begrenzen.Aluminum, especially in the temperature range from 600 to 800 ° C, which the material passes through in use both during heating and cooling, increases the heat resistance by eliminating the phase Ni₃Al (so-called γ 'phase). Since the elimination of this phase is associated with a decrease in toughness, it is necessary to limit the aluminum content to 1.8 to 2.4% by weight.
Der Silizium-Gehalt sollte möglichst niedrig gehalten werden, um die Bildung von niedrig schmelzenden Phasen zu vermeiden.
Der Mangan-Gehalt sollte 0,25 Gew.-% nicht überschreiten, um negative Auswirkungen auf die Oxidationsbeständigkeit des Werkstoffes zu vermeiden.The silicon content should be kept as low as possible in order to avoid the formation of low-melting phases.
The manganese content should not exceed 0.25% by weight in order to avoid negative effects on the oxidation resistance of the material.
Zusätze von Magnesium und Calcium dienen der Verbesserung der Warmumformbarkeit und wirken sich auch verbessernd auf die Oxidationsbeständigkeit aus. Hierbei sollten die Obergrenzen von 0,015 Gew.-% (Magnesium) und 0,010 Gew.-% (Calcium) jedoch nicht überschritten werden, da oberhalb dieser Grenzwerte liegende Gehalte an Magnesium und Calcium das Auftreten niedrig schmelzender Phasen begünstigen und so wiederum die Warmumformbarkeit verschlechtern.Additions of magnesium and calcium serve to improve the hot formability and also improve the oxidation resistance. However, the upper limits of 0.015% by weight (magnesium) and 0.010% by weight (calcium) should not are exceeded, since magnesium and calcium contents above these limit values promote the occurrence of low-melting phases and thus in turn impair the hot formability.
Die Eisen-Gehalte der erfindungsgemäßen Legierung liegen im Bereich von 8 bis 11 Gew.-%. Sie sind dadurch bedingt, um beim Erschmelzen der Legierung preiswertes Ferrochrom und Ferronickel einsetzen zu können.The iron contents of the alloy according to the invention are in the range from 8 to 11% by weight. They are necessary in order to be able to use inexpensive ferrochrome and ferronickel when melting the alloy.
Im folgenden werden die mit der erfindungsgemäßen Legierung erzielten Vorteile näher erläutert. Tabelle 1 enthält die Analysen von zwei unter die Erfindung fallenden Legierungen A und B sowie einer Legierung C entsprechend dem Stand der Technik, wie er der US-PS 4 784 830 entnommen werden kann.
Die Werkstoffeigenschaften dieser Legierungen sind Gegenstand der Figuren 1 bis 5.The material properties of these alloys are the subject of FIGS. 1 to 5.
Im einzelnen zeigen
- Fig. 1
- für die Legierungen A, B und C
die Warmfestigkeit Rm (MPa) in Abhängigkeit von der Temperatur (°C) - Fig. 2
- für die Legierungen A, B und C
die 1 %-Streckgrenze Rp (MPa) in Abhängigkeit von der Temperatur (°C) - Fig. 3
- für die Legierungen A und C
die 1 %-Zeitdehngrenze Rp 1,0/10000 (MPa) nach einer Zeit von 10000 Stunden in Abhängigkeit von der Temperatur (°C) - Fig. 4
- für die Legierungen A und C
die Zeitstandfestigkeit Rm/10000 (MPa) nach einer Zeit von 10000 Stunden in Abhängigkeit von der Temperatur (°C) - Fig. 5
- für die Legierungen A und C
die zyklische Oxidationsbeständigkeit in Luft (spezifische Masseänderung in g/m²·h) in Abhängigkeit von der Temperatur (°C).
- Fig. 1
- for alloys A, B and C
the heat resistance Rm (MPa) depending on the temperature (° C) - Fig. 2
- for alloys A, B and C
the 1% yield strength Rp (MPa) depending on the temperature (° C) - Fig. 3
- for alloys A and C.
the 1% yield strength Rp 1.0 / 10000 (MPa) after a period of 10000 hours depending on the temperature (° C) - Fig. 4
- for alloys A and C.
the creep rupture strength Rm / 10000 (MPa) after a time of 10000 hours depending on the temperature (° C) - Fig. 5
- for alloys A and C.
the cyclic oxidation resistance in air (specific mass change in g / m² · h) depending on the temperature (° C).
Die in Fig. 1 für die Warmfestigkeit und in Fig. 2 für die 1 %-Streckgrenze in Abhängigkeit der Temperatur aufgetragenen Werte sind wichtige Kenngrößen, inwieweit der Werkstoff bei einer bestimmten Temperatur belastet werden kann.The values plotted in FIG. 1 for the heat resistance and in FIG. 2 for the 1% yield strength as a function of the temperature are important parameters to what extent the material can be loaded at a certain temperature.
Es ist zu erkennen, daß die erfindungsgemäße Legierung A im gesamten interessierenden Temperaturbereich von 850 bis 1200 °C bei deutlich höheren Werten als die Legierung C nach dem Stand der Technik liegt, sowohl bei der Warmfestigkeit Rm als auch bei der 1 %-Streckgrenze Rp.It can be seen that the alloy A according to the invention in the entire temperature range of interest from 850 to 1200 ° C. is at significantly higher values than the alloy C according to the prior art, both in terms of the heat resistance Rm and at the 1% yield strength Rp.
Noch bessere Werte werden von der erfindungsgemäßen Legierung B erreicht, deren Legierungszusammensetzung innerhalb der durch Anspruch 2 gegebenen Legierungsvariante liegt. Durch diese Legierungsvariante können bis zu Temperaturen von 1000 °C sowohl die Warmfestigkeit als auch die Streckgrenze fast verdoppelt werden.Even better values are achieved by alloy B according to the invention, the alloy composition of which lies within the alloy variant given by
In den Figuren Fig. 3 und Fig. 4 ist das Zeitstandverhalten der erfindungsgemäßen Legierung A mit dem der Legierung C gemäß dem Stand der Technik verglichen.
Die Zeitstandfestigkeit und die 1 %-Zeitdehngrenze wurden in üblichen Zeitstandversuchen ermittelt (siehe dazu DE-Buch "Werkstoffkunde Stahl", Band 1, Springer-Verlag Berlin, 1984, Seiten 384 bis 396 und DIN 50118).
Die Zeitstandfestigkeit (MPa) gilt als ein Maß für die Fähigkeit eines Werkstoffes, unter dem Einfluß einer wirkenden Last nicht zerstört zu werden. Die 1 %-Zeitdehngrenze, die bei einer vorgegebenen Belastungszeit die Spannung (in MPa) angibt, bei der eine 1 %-Dehnung erreicht wird, charakterisiert das funktionelle Versagen des Werkstoffes bei einer bestimmten Langzeitbelastung für die jeweilige Temperatur. 3 and 4 , the creep behavior of alloy A according to the invention is compared with that of alloy C according to the prior art.
The creep rupture strength and the 1% yield stress limit were determined in conventional creep rupture tests (see DE book "Material Science Steel",
The creep rupture strength (MPa) is a measure of the ability of a material not to be destroyed under the influence of an acting load. The 1% yield stress limit, which specifies the stress (in MPa) at a given loading time at which a 1% elongation is reached, characterizes the functional failure of the material under a specific long-term loading for the respective temperature.
Die erfindungsgemäße Legierung A ist sowohl in der Zeitstandfestigkeit als auch in der 1 %-Zeitdehngrenze der Legierung C entsprechend dem Stand der Technik über den gesamten Temperaturbereich deutlich überlegen. Der Festigkeitsgewinn der erfindungsgemäßen Legierung A beträgt im Vergleich zur Legierung C bei jeder Temperatur mehr als 25 %.Alloy A according to the invention is clearly superior over the entire temperature range both in terms of creep rupture strength and in the 1% tensile yield strength of alloy C according to the prior art. The strength gain of alloy A according to the invention is more than 25% at all temperatures compared to alloy C.
In Fig. 5 wird die an Luft ermittelte zyklische Oxidationsbeständigkeit der Legierungen A und C mit Hilfe der Darstellung der spezifischen Massenänderung über der Temperatur verglichen.
Gewünscht werden in der Regel Massenzunahmen (+), da Massenabnahmen (-) häufig ein Anzeichen für stark abplatzenden Zunder sind.In FIG. 5 , the cyclic oxidation resistance of alloys A and C determined in air is compared with the aid of the representation of the specific change in mass over temperature.
Mass increases (+) are usually desired, since mass decreases (-) are often a sign of severely flaking scale.
Aus diesem Grunde ist das Verhalten der erfindungsgemäßen Legierung A besser zu bewerten als das dem Stand der Technik entsprechende Verhalten der Legierung C, die die Abzisse (Übergang zum Massenverlust) schon bei ca. 1000 °C schneidet, während die Legierung A erst bei ca. 1050 °C einen Nulldurchgang aufweist.For this reason, the behavior of the alloy A according to the invention can be better assessed than the behavior of the alloy C corresponding to the prior art, which cuts the abscissa (transition to loss of mass) already at approx. 1000 ° C., while the alloy A only at approx. 1050 ° C has a zero crossing.
Die erfindungsgemäße Nickel-Chrom-Eisen-Legierung ist wegen ihrer guten Eigenschaften bei hohen Temperaturen ein bevorzugter Werkstoff für Gegenstände, die im praktischen Betrieb bezogen auf eine Temperatur von 1100 °C und eine Belastungsdauer von 10000 Stunden eine Zeitstandfestigkeit (Rm/10000) von mindestens 5 MPa bei einer 1 %-Zeitdehngrenze (Rp1,0/10000) von mindestens 2 MPa und hohe Oxidationsbeständigkeit aufweisen müssen,
wie z. B.
- Strahlrohre zum Beheizen von Öfen
- Ofenrollen für das Glühen von metallischem oder keramischem Gut
- Muffeln für Blankglühöfen, z.B. für Öfen für das Blankglühen von Edelstählen
- Rohre für die Sauerstofferhitzung bei der Produktion von Titandioxid (TiO₂)
- Ethylencrackrohre
- Ofengestelle und Tragekreuze für stationäre Glühungen
- Isolierungen für Auspuffkrümmer
- Katalysatorfolien für die Abgasreinigung, insbesondere bei thermisch hochbelasteten Klein-Benzinmotoren, wie Motoren für Kettensägen, Heckenscheren und Rasenmäher.
such as B.
- Radiant tubes for heating ovens
- Oven rolls for the annealing of metallic or ceramic material
- Muffle for bright annealing furnaces, eg for furnaces for bright annealing stainless steel
- Tubes for oxygen heating in the production of titanium dioxide (TiO₂)
- Ethylene cracking pipes
- Furnace frames and crosses for stationary annealing
- Exhaust manifold insulation
- Catalyst foils for exhaust gas purification, especially for small gasoline engines with high thermal loads, such as engines for chainsaws, hedge trimmers and lawnmowers.
Die genannten Gegenstände lassen sich aus dem erfindungsgemäßen Werkstoff leicht fertigen, da er nicht nur gut warmverformbar ist, sondern auch das für Kaltverarbeitungsvorgänge - wie z.B. Kaltwalzen auf dünne Abmessungen, Abkanten, Tiefziehen, Bördeln - nötige Umformvermögen besitzt.The objects mentioned can be easily manufactured from the material according to the invention, since it is not only readily thermoformable, but also for cold processing operations - such as Cold rolling to thin dimensions, folding, deep drawing, flanging - has the necessary forming capacity.
Claims (3)
bestehend aus (Angaben in Gewichtsprozent) :
consisting of (data in percent by weight):
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4111821 | 1991-04-11 | ||
| DE4111821A DE4111821C1 (en) | 1991-04-11 | 1991-04-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0508058A1 true EP0508058A1 (en) | 1992-10-14 |
| EP0508058B1 EP0508058B1 (en) | 1995-08-16 |
Family
ID=6429356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92102228A Expired - Lifetime EP0508058B1 (en) | 1991-04-11 | 1992-02-11 | Austenitic alloy nickel-chromium-iron |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5980821A (en) |
| EP (1) | EP0508058B1 (en) |
| JP (1) | JP3066996B2 (en) |
| AT (1) | ATE126548T1 (en) |
| AU (1) | AU653801B2 (en) |
| CA (1) | CA2065464C (en) |
| DE (2) | DE4111821C1 (en) |
| ES (1) | ES2079705T3 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0549286A1 (en) * | 1991-12-20 | 1993-06-30 | Inco Alloys Limited | High temperature resistant Ni-Cr alloy |
| EP0752481A1 (en) * | 1995-07-04 | 1997-01-08 | Krupp VDM GmbH | Malleable nickel alloy |
| WO1999028515A1 (en) * | 1997-12-03 | 1999-06-10 | Krupp Vdm Gmbh | High temperature oxidation resistant ductile nickel alloy |
| DE102012002514A1 (en) | 2011-02-23 | 2012-08-23 | Thyssenkrupp Vdm Gmbh | Nickel-chromium-iron-aluminum alloy with good processability |
| DE102012011161A1 (en) | 2012-06-05 | 2013-12-05 | Outokumpu Vdm Gmbh | Nickel-chromium-aluminum alloy with good processability, creep resistance and corrosion resistance |
| WO2014023274A1 (en) | 2012-08-10 | 2014-02-13 | Outokumpu Vdm Gmbh | Usage of a nickel-chromium-iron-aluminium alloy with good workability |
| US9650698B2 (en) | 2012-06-05 | 2017-05-16 | Vdm Metals International Gmbh | Nickel-chromium alloy having good processability, creep resistance and corrosion resistance |
| DE102018107248A1 (en) | 2018-03-27 | 2019-10-02 | Vdm Metals International Gmbh | USE OF NICKEL CHROME IRON ALUMINUM ALLOY |
| WO2020126053A1 (en) * | 2018-12-21 | 2020-06-25 | Sandvik Intellectual Property Ab | New use of a nickel-based alloy |
| US10870908B2 (en) | 2014-02-04 | 2020-12-22 | Vdm Metals International Gmbh | Hardening nickel-chromium-iron-titanium-aluminium alloy with good wear resistance, creep strength, corrosion resistance and processability |
| WO2021110217A1 (en) | 2019-12-06 | 2021-06-10 | Vdm Metals International Gmbh | Nickel-chromium-iron-aluminum alloy having good processability, creep resistance and corrosion resistance, and use thereof |
| US11098389B2 (en) | 2014-02-04 | 2021-08-24 | Vdm Metals International Gmbh | Hardened nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and workability |
| DE102022105658A1 (en) | 2022-03-10 | 2023-09-14 | Vdm Metals International Gmbh | Process for producing a component from the semi-finished product of a nickel-chromium-aluminum alloy |
| DE102022105659A1 (en) | 2022-03-10 | 2023-09-14 | Vdm Metals International Gmbh | Process for producing a welded component from a nickel-chromium-aluminum alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US7074350B2 (en) * | 2001-03-23 | 2006-07-11 | Citizen Watch Co., Ltd. | Brazing filler metal |
| US6488783B1 (en) * | 2001-03-30 | 2002-12-03 | Babcock & Wilcox Canada, Ltd. | High temperature gaseous oxidation for passivation of austenitic alloys |
| JP3998983B2 (en) | 2002-01-17 | 2007-10-31 | 松下電器産業株式会社 | Unicast-multicast converter and video surveillance system |
| DE10302989B4 (en) * | 2003-01-25 | 2005-03-03 | Schmidt + Clemens Gmbh & Co. Kg | Use of a heat and corrosion resistant nickel-chromium steel alloy |
| EP1610081A1 (en) * | 2004-06-25 | 2005-12-28 | Haldor Topsoe A/S | Heat exchange process and heat exchanger |
| US8597438B2 (en) | 2007-10-05 | 2013-12-03 | Sandvik Intellectual Property Ab | Use and method of producing a dispersion strengthened steel as material in a roller for a roller hearth furnace |
| US8506883B2 (en) * | 2007-12-12 | 2013-08-13 | Haynes International, Inc. | Weldable oxidation resistant nickel-iron-chromium-aluminum alloy |
| US9551051B2 (en) | 2007-12-12 | 2017-01-24 | Haynes International, Inc. | Weldable oxidation resistant nickel-iron-chromium aluminum alloy |
| JP5857894B2 (en) * | 2012-07-05 | 2016-02-10 | 新日鐵住金株式会社 | Austenitic heat-resistant alloy |
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| JPH0660369B2 (en) * | 1988-04-11 | 1994-08-10 | 新日本製鐵株式会社 | Cr-Ni type stainless steel that is less likely to crack during the casting process or the subsequent hot rolling process |
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- 1991-04-11 DE DE4111821A patent/DE4111821C1/de not_active Expired - Fee Related
-
1992
- 1992-02-11 ES ES92102228T patent/ES2079705T3/en not_active Expired - Lifetime
- 1992-02-11 DE DE59203257T patent/DE59203257D1/en not_active Expired - Lifetime
- 1992-02-11 EP EP92102228A patent/EP0508058B1/en not_active Expired - Lifetime
- 1992-02-11 AT AT92102228T patent/ATE126548T1/en active
- 1992-04-02 US US07/862,486 patent/US5980821A/en not_active Expired - Lifetime
- 1992-04-07 CA CA002065464A patent/CA2065464C/en not_active Expired - Lifetime
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| GB810366A (en) * | 1957-09-25 | 1959-03-11 | Mond Nickel Co Ltd | Improvements relating to heat-resisting alloys |
| US3607243A (en) * | 1970-01-26 | 1971-09-21 | Int Nickel Co | Corrosion resistant nickel-chromium-iron alloy |
| EP0251295A2 (en) * | 1986-07-03 | 1988-01-07 | Inco Alloys International, Inc. | High nickel chromium alloy |
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Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0549286A1 (en) * | 1991-12-20 | 1993-06-30 | Inco Alloys Limited | High temperature resistant Ni-Cr alloy |
| EP0752481A1 (en) * | 1995-07-04 | 1997-01-08 | Krupp VDM GmbH | Malleable nickel alloy |
| JPH0925530A (en) * | 1995-07-04 | 1997-01-28 | Krupp Vdm Gmbh | Forgeable nickel alloy |
| US5755897A (en) * | 1995-07-04 | 1998-05-26 | Krupp Vdm Gmbh | Forgeable nickel alloy |
| CN1053226C (en) * | 1995-07-04 | 2000-06-07 | 克鲁普德国联合金属制造有限公司 | Forgeable nickel alloy |
| WO1999028515A1 (en) * | 1997-12-03 | 1999-06-10 | Krupp Vdm Gmbh | High temperature oxidation resistant ductile nickel alloy |
| DE102012002514A1 (en) | 2011-02-23 | 2012-08-23 | Thyssenkrupp Vdm Gmbh | Nickel-chromium-iron-aluminum alloy with good processability |
| WO2012113373A1 (en) | 2011-02-23 | 2012-08-30 | Thyssenkrupp Vdm Gmbh | Nickel-chromium-iron-aluminum alloy having good processability |
| US9476110B2 (en) | 2011-02-23 | 2016-10-25 | Vdm Metals International Gmbh | Nickel—chromium—iron—aluminum alloy having good processability |
| CN103443312A (en) * | 2011-02-23 | 2013-12-11 | 奥托昆普德国联合金属制造有限公司 | Nickel-chromium-iron-aluminum alloy having good processability |
| CN103443312B (en) * | 2011-02-23 | 2015-07-08 | 奥托昆普德国联合金属制造有限公司 | Nickel-chromium-iron-aluminum alloy having good processability |
| DE102012002514B4 (en) * | 2011-02-23 | 2014-07-24 | VDM Metals GmbH | Nickel-chromium-iron-aluminum alloy with good processability |
| DE102012013437B3 (en) * | 2011-02-23 | 2014-07-24 | VDM Metals GmbH | Use of a nickel-chromium-iron-aluminum alloy with good processability |
| DE102012011161A1 (en) | 2012-06-05 | 2013-12-05 | Outokumpu Vdm Gmbh | Nickel-chromium-aluminum alloy with good processability, creep resistance and corrosion resistance |
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| US9650698B2 (en) | 2012-06-05 | 2017-05-16 | Vdm Metals International Gmbh | Nickel-chromium alloy having good processability, creep resistance and corrosion resistance |
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| WO2013182177A1 (en) | 2012-06-05 | 2013-12-12 | Outokumpu Vdm Gmbh | Nickel-chromium-aluminum alloy having good processability, creep resistance and corrosion resistance |
| DE102012015828B4 (en) * | 2012-08-10 | 2014-09-18 | VDM Metals GmbH | Use of a nickel-chromium-iron-aluminum alloy with good processability |
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| US11098389B2 (en) | 2014-02-04 | 2021-08-24 | Vdm Metals International Gmbh | Hardened nickel-chromium-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and workability |
| US11162160B2 (en) | 2018-03-27 | 2021-11-02 | Vdm Metals International Gmbh | Use of a nickel-chromium-iron-aluminum alloy |
| DE102018107248A1 (en) | 2018-03-27 | 2019-10-02 | Vdm Metals International Gmbh | USE OF NICKEL CHROME IRON ALUMINUM ALLOY |
| WO2019185082A1 (en) | 2018-03-27 | 2019-10-03 | Vdm Metals International Gmbh | Use of a nickel-chromium-iron-aluminium alloy |
| WO2020126053A1 (en) * | 2018-12-21 | 2020-06-25 | Sandvik Intellectual Property Ab | New use of a nickel-based alloy |
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| DE102022105658A1 (en) | 2022-03-10 | 2023-09-14 | Vdm Metals International Gmbh | Process for producing a component from the semi-finished product of a nickel-chromium-aluminum alloy |
| DE102022105659A1 (en) | 2022-03-10 | 2023-09-14 | Vdm Metals International Gmbh | Process for producing a welded component from a nickel-chromium-aluminum alloy |
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2065464A1 (en) | 1992-10-12 |
| JPH07216483A (en) | 1995-08-15 |
| DE59203257D1 (en) | 1995-09-21 |
| ES2079705T3 (en) | 1996-01-16 |
| US5980821A (en) | 1999-11-09 |
| CA2065464C (en) | 2002-03-26 |
| JP3066996B2 (en) | 2000-07-17 |
| AU653801B2 (en) | 1994-10-13 |
| EP0508058B1 (en) | 1995-08-16 |
| AU1478792A (en) | 1992-10-15 |
| ATE126548T1 (en) | 1995-09-15 |
| DE4111821C1 (en) | 1991-11-28 |
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