EP2240619B1 - Creep resistant steel - Google Patents
Creep resistant steel Download PDFInfo
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- EP2240619B1 EP2240619B1 EP08717748.1A EP08717748A EP2240619B1 EP 2240619 B1 EP2240619 B1 EP 2240619B1 EP 08717748 A EP08717748 A EP 08717748A EP 2240619 B1 EP2240619 B1 EP 2240619B1
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- creep
- resistant steel
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- steel
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
Definitions
- the invention relates to steels based on 9-12% chromium, which are used for rotors in the power plant sector. It concerns the choice and the proportionate tuning of special alloying elements which allow the setting of an exceptionally good creep resistance at temperatures of 550 ° C and above in this material.
- the steel according to the invention should also have a high toughness after long-term aging, so that it can be used both in gas and steam turbines.
- Maragingitic-hardening steels based on 9-12% chromium are widely used materials in power plant technology. They were developed for use in steam power plants at operating temperatures above 600 ° C and steam pressures above 250 bar to increase the efficiency of power plants. Under these operating conditions, the creep resistance and the oxidation resistance of the material play a special role.
- chromium in the abovementioned range not only provides good resistance to atmospheric corrosion but also complete through-hardenability of thick-walled forgings, for example as monobloc rotors or as rotor disks in gas and steam turbines.
- Proven alloys of this type usually contain about 0.08 to 0.2% carbon, which in solution allows the setting of a hard martensitic structure.
- a good combination of heat resistance and ductility of martensitic steels is made possible by a tempering treatment in which the precipitation of carbon in the form of carbides with simultaneous recovery of the dislocation substructure forms a particle-stabilized subgrain structure.
- the tempering behavior and the resulting properties can be effectively influenced by the choice and proportionate tuning of specific carbide formers such as Mo, W, V, Nb and Ta.
- German steel X20CrMoV12.1 known under DIN.
- the contents of Cr, Mo, W were optimized taking into account N, Nb and / or B to improve creep and creep rupture strengths for 600 ° C applications.
- the carbides such as M 23 C 6 .
- the Ni contents were limited to values of less than 0.25% in these steels.
- the fracture toughness values are disadvantageous, which does not play a major role in steam turbine applications and can therefore be neglected, but must be avoided in gas turbine applications.
- EP 0 931 845 A1 a nickel-containing 12% chromium steel similar in structure to the German steel X12CrNiMo12, in which reduces the element molybdenum compared to the known steel X12 CrNiMo12, but an increased content of tungsten was alloyed.
- DE 198 32 430 A1 is a further optimization of the X12CrNiMo12 similar steel with the name M152 disclosed in which by the addition of rare earth elements, the embrittlement tendency in the temperature range between 425 and 500 ° C is limited.
- EP 0 866 145 A2 describes a new class of martensitic chromium steels with nitrogen contents in the range of 0.12 to 0.25% and in EP 1 158 067 A1 with nitrogen contents of 0.12 to 0.18%, wherein the weight ratio V / N is in the range between 3.5 and 4.2.
- the entire structure of the structure is controlled by the formation of special nitrides, in particular vanadium nitrides, which can be distributed in a variety of ways by forging, austenitizing, controlled cooling or annealing. While strength is achieved through the nitriding's curing effect, the aim is to achieve high ductility through the distribution and morphology of the nitrides, but above all by limiting grain coarsening during forging and during solution heat treatment.
- US2002020473 discloses a high-chromium, heat-resistant, ferritic steel having the following composition (in% by weight): 0.02 to 0.15% C, 0.05 to 1.5% Mn, ⁇ 0.03% P, ⁇ 0.015% S, 8 to 13% Cr, 1.5 to 4% W, 2 to 6% Co, 0.1 to 0.5% V, 0.01 to 0.15% Ta, 0.01 to 0.15% Nb, 0.001 to 0.2% Nd, ⁇ 0.02% N, 0.0005 to 0.02% B, 0.001 to 0.05 % Al, at least one of Ca ( ⁇ 0.02%), Y ( ⁇ 0.2%), La ( ⁇ 0.2%) and Hf ( ⁇ 0.2%), remainder Fe.
- composition in% by weight
- a heat resistant steel with good toughness properties is known for use as a turbine rotor, which has the following chemical composition (% by weight): 0.05-0.30 C, 0.20 or less Si, 0-1.0 Mn, 8-14 Cr, 0.5-3.0 Mo, 0.10-0.50 V, 1.5-5.0 Ni, 0.01-0.5 Nb, 0.01-0.08 N, 0.001-0.020 B, balance iron and unavoidable impurities. Boron microalloying results in precipitates at the grain boundaries and increases the time stability of the carbonitrides at high temperatures, but higher levels of B reduce the toughness of the steel. Disadvantages of this proposed composition are also the relatively high permitted Si values of 0.2%. Although Si serves advantageously as a deoxidizer at the time of melting, parts of it remain as oxides in the steel, which is disadvantageous in a reduced toughness.
- the invention has for its object to provide a 9-12% Cr steel, which is characterized over the prior art by increased creep strength at temperatures of 550 ° C and above and which improved resistance to embrittlement in long-term aging and a has relatively high toughness, so that it can be used especially in gas turbine, but also in steam turbine power plants. It should preferably find application for rotors of turbomachinery, so that the efficiency and the output can be increased over the known prior art.
- the core of the invention is a steel having the following chemical composition (in% by weight): 0.08 to 0.16 C, 9.0 to 12.0 Cr, 0.1 to 0.5 Mn, 2.3 to 3 Ni, 1.5 to 2.0 Mo, 0.1 to 0.4 V, 0.01 to 0.06 Nb, 0.02 to 0.08 N, 0.001 to 2 Ta, 0.001 to 0.5 La, 0.0001 to 1 Pd, 0.004 to 0.012 B, maximum 0.005 P, maximum 0.005 S, maximum 0.05 Si, maximum 0.005 Sn, balance iron and unavoidable impurities ,
- the steel according to the invention particularly preferably has the following chemical composition (in% by weight): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.007 B, 0.005 P, 0.005 S, 0.05 Si, 0.005 Sn, balance iron and unavoidable impurities.
- the advantage of the invention is that the inventive alloy compared to the known from the prior art alloys of similar composition, but without B addition or without La and Pd addition, with the same heat treatment improved creep properties at temperatures of 550 ° C and above, while also good toughness properties (elongation, impact work) and improved resistance to embrittlement during long-term aging can be achieved.
- a starting structure which is characterized by a tough matrix and the presence of heat-resistant nitrides, borides and carbides.
- the toughness of the base matrix is adjusted by the presence of substitution elements, preferably nickel.
- substitution elements preferably nickel.
- the contents of these substitution elements are determined to provide optimal unfolding of both martensite hardening and particle hardening by precipitation of special nitrides, e.g. As vanadium nitrides or niobium nitrides, to set the highest heat resistance possible.
- both hardening mechanisms lower the ductility. Characteristically, a minimum ductility is observed in the area of secondary hardening. This minimum ductility need not be caused exclusively by the actual precipitation hardening mechanism. A certain embrittlement contribution may also be provided by segregation of impurities to the grain boundaries or possibly also by near-order adjustments of dissolved alloy atoms.
- nickel contents above 2% by weight are expected to lower the Ac1 temperature (which is the temperature at which ferrite begins to convert to austenite during heating) to temperatures below 700 ° C. So if the strength is increased by lowering the tempering temperature below 700 ° C, then in the presence of increased nickel contents during tempering with a partial conversion of ferrite into austenite can be expected. This is associated with a certain ductility-promoting grain regeneration. However, it should be noted that the carbide precipitation above the Ac1 temperature is only incomplete, since the solubility of the austenite-stabilizing element carbon in austenite is greater than in the ferrite.
- the austenite which forms is not sufficiently stabilized, so that a larger volume fraction of the reformed austenite undergoes further martensitic transformation in the post-anneal cooling.
- a certain ductility contribution of nickel can come into solid solution as a substitution element. This can be explained electron-theoretically in such a way that the element nickel feeds additional, free electrons into the iron grid and thereby makes the iron alloys even more "metallic".
- Manganese is on the left side next to the element iron in the periodic system of elements. It is an electron-poorer element, so its action in solid solution should be distinctly different from that of nickel. Nonetheless, it is an austenite stabilizing element which greatly lowers the Ac1 temperature, but leaves no particularly positive but rather unfavorable effect on ductility.
- manganese is understood to be an impurity element which promotes temper embrittlement substantially. Therefore, the content of manganese is usually limited to very small amounts.
- a weight proportion of 9-12% chromium allows good through-hardenability of thick-walled components and ensures sufficient oxidation resistance up to a temperature of 550 ° C.
- a proportion by weight of less than 9% impairs the through-hardenability.
- Contents above 12% lead to the accelerated formation of hexagonal chromium nitrides during the tempering process, which, in addition to nitrogen, also cures vanadium, thus reducing the effectiveness of vanadium nitride curing.
- the optimum chromium content is 10.5 to 11.5%.
- the range to be specified should take into account the metallurgical possibilities in the range between 0.1 and 0.5% by weight, preferably between 0.1 and 0.25%, in particular at 0.2% for manganese and at max. 0.05% by weight for silicon.
- Nickel is used as an austenite stabilizing element to suppress delta ferrite. In addition, it is said to improve ductility as a dissolved element in the ferritic matrix.
- Nickel contents of 2.3 to about 3% by weight make sense. Nickel contents above 4% by weight increase the austenite stability such that after solution heat treatment and tempering an increased proportion of retained austenite or tempering austenite can be present in the tempered martensite.
- the nickel content is preferably 2.3 to 2.8, in particular 2.5% by weight.
- Molybdenum improves creep strength by solid solution hardening as a partially dissolved element and precipitation hardening during a long-term stress.
- An excessively high proportion of this element leads to embrittlement during long-term aging, which is due to the precipitation and coarsening of Laves phase (W, Mo) and Sigma phase (Mo).
- the range for Mo is 1.5 to 2% by weight, preferably 1.6 to 1.8% by weight, in particular 1.7% by weight.
- V / N ratio sometimes also increases the stability of the vanadium nitride over the chromium nitride.
- the specific content of nitrogen and vanadium nitrides depends on the optimum volume fraction of the vanadium nitrides, which are to remain as insoluble primary nitrides during the solution annealing. The greater the total content of vanadium and nitrogen, the greater is the proportion of vanadium nitrides, which no longer goes into solution and the greater the grain refining effect.
- the preferred content of nitrogen is in the range from 0.02 to 0.08% by weight, preferably 0.025 to 0.055% by weight, particularly preferably 0.04% by weight N, and that of vanadium is in the range between 0.1 and 0.4% by weight. , preferably 0.2 to 0.3% by weight, and especially at 0.25% by weight.
- Niobium is a strong nitride former that aids the grain refining effect. In order to keep the volume fraction of the primary nitrides small, their total proportion must be limited to 0.1% by weight. Niobium dissolves in vanadium nitride in small amounts and can thus improve the stability of the vanadium nitride. Niobium is added in the range between 0.01 and 0.06% by weight, preferably 0.02 to 0.04% by weight, and in particular at 0.03% by weight.
- Ta influences the creep resistance positively. Addition of 0.001 to 2% by weight of Ta has the effect, on the one hand, that due to the greater tendency of tantalum to form carbides as chromium, the precipitation of undesired chromium carbides at the grain boundaries and, on the other hand, the undesirable depletion of the mixed crystal in chromium are reduced.
- the preferred range for Ta is 0.005 to 0.1% by weight, in particular a Ta content of 0.01% by weight should be set.
- the carbon content should therefore be limited upwards to 0.16% by weight.
- Another disadvantage is the fact that carbon increases the hardening during welding.
- the preferred carbon content is in the range between 0.10 and 0.14% by weight, preferably 0.12% by weight.
- the boron content should be limited to 40 to 120 ppm.
- La 2 S 3 Lanthanum binds the sulfur in the steel through the formation of lanthanum sulfide La 2 S 3 .
- La 2 S 3 is much more stable than MnS 2 . It has a melting point of> 2100 ° C, while MnS 2 decomposes at high temperatures to release S.
- stable sulfide formers in steel such as La are much better than Mn.
- the grain size is advantageously reduced by the micro-alloying with La, which also has an advantageous effect if the material is tested non-destructively by ultrasonic methods.
- a grain size ASTM 6 was determined by the applicant, whereas for a 12% Cr steel microblasted with B and La, the grain size at the same austenitizing temperature only remains ASTM 7 was.
- the weldability of the 12% Cr steels is improved.
- the content of La should be 0.001 to 0.5% by weight, preferably 0.01 to 0.1% by weight, especially 0.05% by weight.
- Pd forms an ordered Fe-Pd L1 0 intermetallic phase with the iron of the steel, the ⁇ "phase.
- This stable ⁇ " phase increases the high temperature creep strength by stabilizing grain boundary precipitates such as M 23 C 6 and acts thus have a positive effect on the creep properties.
- palladium has the disadvantage of high costs.
- the Pd content of the proposed steel should be in the range of 0.0001 to 1, preferably 0.0005 to 0.01 wt%, with a content of 0.001 wt% being particularly suitable.
- the investigated inventive alloy L2 had the following chemical composition (in% by weight): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.0070 B, 0.05 Si, 0.005 P, 0.005 S, 0.005 Sn, balance iron and unavoidable impurities.
- the comparative alloy VL1 used was a prior art commercial steel of the type X12CrNiMoV11-2-2 having the following chemical composition (in% by weight): 0.10-0.14 C, 11.0-12.0 Cr, 0.25 Mn, 2.0-2.6 Ni, 1.3-1.8 Mo, 0.2-0.35 V, 0.02-0.05 N, 0.15 Si, 0.026 P and 0.015 S.
- Fig. 1 shows the creep properties for the two alloys VL1 and L2, ie the creep rupture strength and the 1% yield strength at 550 ° C.
- the mean times to break and to reach a 1% elongation are thus shown, depending on the voltage at 550 ° C.
- the alloy L2 according to the invention advantageously requires significantly longer times when the same voltage is applied until a 1% elongation is reached than the comparison alloy VL1. In the time to break (creep strength), this difference is even more evident, since the in Fig. 1 Alloy L2 samples with an arrow have not yet broken. In the case of the alloy L2 according to the invention, a clear shift to longer is here Recognize times, which is of particular advantage for the planned use as a gas turbine or steam turbine rotor.
- Fig. 3 the fracture toughnesses and impact energies at room temperature are compared for the two investigated alloys in the above-described heat treatment state (without aging). Despite the significantly better creep properties at high temperatures (see Fig. 1 and 2 ), the toughness of the alloy according to the invention scarcely deteriorates.
- the alloy according to the invention is distinguished on the one hand by a very good creep resistance at temperatures of 450 ° C., preferably 550 ° C., and above, and is thus superior to the conventional 12% Cr steels.
- This is mainly due to the influence of boron, tantalum and palladium, which are alloyed in the specified range. Boron, tantalum and palladium stabilize the M 23 C 6 precipitates, which play a significant strengthening role during creep, with Pd additionally forming a stable intermetallic phase with the iron, which also contributes to increasing creep resistance.
- the dislocation density is maintained until breakage, thus improving creep strength of the steel.
- a similar effect on increasing creep strength is found in Ta and Pd.
- the alloy of the present invention has improved resistance to embrittlement upon long-term aging and comparatively high toughness. This is due to the addition of lanthanum in the specified range, because both the grain size is reduced as well as stable lanthanum sulfide La 2 S 3 are formed.
- the inventive alloy is thus particularly advantageous for rotors in gas and steam turbines, which are exposed to high inlet temperatures of about 550 ° C, can be used advantageously.
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Description
Die Erfindung bezieht sich auf Stähle auf der Basis von 9-12 % Chrom, die für Rotoren im Kraftwerksbereich eingesetzt werden. Sie betrifft die Wahl und das mengenanteilsmässige Abstimmen spezieller Legierungselemente, welche die Einstellung einer aussergewöhnlich guten Kriechfestigkeit bei Temperaturen von 550 °C und darüber in diesem Material ermöglichen. Der erfindungsgemässe Stahl soll auch eine hohe Zähigkeit nach Langzeitalterung aufweisen, so dass er sowohl in Gas- als auch Dampfturbinen eingesetzt werden kann.The invention relates to steels based on 9-12% chromium, which are used for rotors in the power plant sector. It concerns the choice and the proportionate tuning of special alloying elements which allow the setting of an exceptionally good creep resistance at temperatures of 550 ° C and above in this material. The steel according to the invention should also have a high toughness after long-term aging, so that it can be used both in gas and steam turbines.
Martensitisch-härtbare Stähle auf der Basis von 9-12 % Chrom sind weitverbreitete Werkstoffe der Kraftwerkstechnik. Sie wurden entwickelt für eine Anwendung in Dampfkraftwerken bei Betriebstemperaturen oberhalb 600 °C und Dampfdrücken oberhalb 250 bar, um die Effizienz der Kraftwerke zu erhöhen. Unter diesen Betriebsbedingungen spielen die Kriechfestigkeit und der Oxidationswiderstand des Materials eine besondere Rolle.Maragingitic-hardening steels based on 9-12% chromium are widely used materials in power plant technology. They were developed for use in steam power plants at operating temperatures above 600 ° C and steam pressures above 250 bar to increase the efficiency of power plants. Under these operating conditions, the creep resistance and the oxidation resistance of the material play a special role.
Es ist bekannt, dass die Zugabe von Chrom im obengenannten Bereich nicht nur eine gute Beständigkeit gegen atmosphärische Korrosion, sondern auch die vollständige Durchhärtbarkeit von dickwandigen Schmiedestücken ermöglicht, so wie sie etwa als Monoblockrotoren oder als Rotorscheiben in Gas- und Dampfturbinen Anwendung finden. Bewährte Legierungen dieser Art enthalten gewöhnlich etwa 0.08 bis 0.2 % Kohlenstoff, welcher in Lösung die Einstellung einer harten martensitischen Struktur ermöglicht. Eine gute Kombination von Warmfestigkeit und Duktilität martensitischer Stähle wird durch eine Anlassbehandlung ermöglicht, in welcher sich durch die Ausscheidung von Kohlenstoff in Form von Karbiden unter gleichzeitiger Erholung der Versetzungssubstruktur eine teilchenstabilisierte Subkornstruktur bildet. Das Anlassverhalten und die hieraus resultierenden Eigenschaften können wirksam durch die Wahl und das mengenanteilsmässige Abstimmen spezieller Karbidbildner wie zum Beispiel Mo, W, V, Nb und Ta beeinflusst werden.It is known that the addition of chromium in the abovementioned range not only provides good resistance to atmospheric corrosion but also complete through-hardenability of thick-walled forgings, for example as monobloc rotors or as rotor disks in gas and steam turbines. Proven alloys of this type usually contain about 0.08 to 0.2% carbon, which in solution allows the setting of a hard martensitic structure. A good combination of heat resistance and ductility of martensitic steels is made possible by a tempering treatment in which the precipitation of carbon in the form of carbides with simultaneous recovery of the dislocation substructure forms a particle-stabilized subgrain structure. The tempering behavior and the resulting properties can be effectively influenced by the choice and proportionate tuning of specific carbide formers such as Mo, W, V, Nb and Ta.
Ein typischer Vertreter, welcher in Dampfkraftwerken, insbesondere als Rotorstahl breite Verwendung gefunden hat, ist der unter DIN bekannte deutsche Stahl X20CrMoV12.1.A typical representative who has found widespread use in steam power plants, in particular as rotor steel, is the German steel X20CrMoV12.1 known under DIN.
Es ist ferner bekannt, dass die Duktilität auf einem Festigkeitsniveau von 850 MPa durch das Zu legieren von Nickel deutlich verbessert werden kann. Solche Legierungen finden daher dort eine breite Verwendung, wo deutlich höhere Anforderungen an sowohl Festigkeit wie auch Duktilität gestellt werden, typischer Weise als Scheibenwerkstoffe für Gasturbinenrotoren. Ein typischer Vertreter derartiger Legierungen, welcher in der Gasturbinentechnik, insbesondere als Werkstoff für Rotorscheiben breite Verwendung gefunden hat, ist der unter DIN bekannte deutsche Stahl X12CrNiMo12. Tendenziell wird durch Nickel aber nachteilig die Warmfestigkeit bei hohen Temperaturen gesenkt. Dies wird mit einer reduzierten Karbidstabilität in nickelhaltigen Stählen in Beziehung gesetzt.It is also known that the ductility at a strength level of 850 MPa can be significantly improved by the alloying of nickel. Such alloys are therefore widely used where significantly higher demands are placed on both strength and ductility, typically as disk materials for gas turbine rotors. A typical representative of such alloys, which has found wide use in gas turbine technology, in particular as a material for rotor disks, is the German steel X12CrNiMo12 known under DIN. However, nickel tends to reduce hot strength at high temperatures. This is related to reduced carbide stability in nickel-containing steels.
In der vergangenen Zeit wurden verschiedene Anstrengungen unternommen, um spezielle Eigenschaften der bekannten 9-12% Cr-Stähle zu verbessern. So wird beispielsweise in der Veröffentlichung
In derartigen Legierungen wurden die Gehalte an Cr, Mo, W unter Berücksichtigung von N, Nb und/oder B optimiert, um die Kriech- und Zeitstandfestigkeiten für Anwendungen bei 600 °C zu verbessern. Durch Zugabe von Bor sollen die Karbide, wie beispielsweise M23C6, stabilisiert werden. Wegen der schädlichen Wirkung von Nickel auf die Langzeiteigenschaften, wurden bei diesen Stählen die Ni-Gehalte auf Werte kleiner 0.25 % beschränkt. Bei diesen Legierungen sind nachteilig die Bruchzähigkeitswerte tief, was zwar bei Dampfturbinenanwendungen keine grosse Rolle spielt und daher vernachlässigt werden kann, bei Gasturbinenanwendungen aber vermieden werden muss.In such alloys, the contents of Cr, Mo, W were optimized taking into account N, Nb and / or B to improve creep and creep rupture strengths for 600 ° C applications. By adding boron, the carbides, such as M 23 C 6 , are stabilized. Because of the harmful effect of nickel on the long-term properties, the Ni contents were limited to values of less than 0.25% in these steels. In the case of these alloys, the fracture toughness values are disadvantageous, which does not play a major role in steam turbine applications and can therefore be neglected, but must be avoided in gas turbine applications.
In späteren Veröffentlichungen (
Speziell für Gasturbinenanwendungen wurden Anstrengungen unternommen, um bei 9-12 % Cr-Stählen entweder die Zeitstandfestigkeiten im Bereich von 450 bis 500°C auf hohem Duktilitätsniveau zu verbessern oder die Versprödungsneigung bei Temperaturen zwischen 425 und 500 °C zu reduzieren. So beschreibt die europäische Patentanmeldung
Nachteilig ist, dass in keinem der obengenannten Entwicklungen die Festigkeit, insbesondere die Warmfestigkeit bei Temperaturen zwischen 300 und 600 °C, auf einem dem Stahl X12CrNiMo12 vergleichbar hohen Duktilitätsniveau verbessert werden konnte.The disadvantage is that in none of the abovementioned developments could the strength, in particular the heat resistance at temperatures between 300 and 600 ° C., be improved on a level of ductility comparable to the steel X12CrNiMo12.
Ein möglicher Ansatz zur Verbesserung der Warmfestigkeit bei gleichzeitig hoher Duktilität wurde mit der Entwicklung von Stählen mit erhöhten Stickstoffgehalten vorgeschlagen. In
Aus
Schliesslich werden in
Der Erfindung liegt die Aufgabe zugrunde, einen 9-12 % Cr-Stahl zu schaffen, welcher sich gegenüber dem bekannten Stand der Technik durch eine erhöhte Kriechfestigkeit bei Temperaturen von 550 °C und darüber auszeichnet und welcher eine verbesserte Beständigkeit gegenüber Versprödung bei Langzeitalterung und eine vergleichsweise hohe Zähigkeit aufweist, so dass er vor allem in Gasturbinen-, aber auch in Dampfturbinenkraftwerken eingesetzt werden kann. Er soll vorzugsweise für Rotoren von Turbomaschinen Anwendung finden, damit die Effizienz und der Ausstoss gegenüber dem bekannten Stand der Technik erhöht werden können.The invention has for its object to provide a 9-12% Cr steel, which is characterized over the prior art by increased creep strength at temperatures of 550 ° C and above and which improved resistance to embrittlement in long-term aging and a has relatively high toughness, so that it can be used especially in gas turbine, but also in steam turbine power plants. It should preferably find application for rotors of turbomachinery, so that the efficiency and the output can be increased over the known prior art.
Kern der Erfindung ist ein Stahl mit folgender chemischer Zusammensetzung (Angaben in Gew.- %): 0.08 bis 0.16 C, 9.0 bis 12.0 Cr, 0.1 bis 0.5 Mn, 2.3 bis 3 Ni, 1.5 bis 2.0 Mo, 0.1 bis 0.4 V, 0.01 bis 0.06 Nb, 0.02 bis 0.08 N, 0.001 bis 2 Ta, 0.001 bis 0.5 La, 0.0001 bis 1 Pd, 0.004 bis 0.012 B, maximal 0.005 P, maximal 0.005 S, maximal 0.05 Si, maximal 0.005 Sn, Rest Eisen und unvermeidbare Verunreinigungen.The core of the invention is a steel having the following chemical composition (in% by weight): 0.08 to 0.16 C, 9.0 to 12.0 Cr, 0.1 to 0.5 Mn, 2.3 to 3 Ni, 1.5 to 2.0 Mo, 0.1 to 0.4 V, 0.01 to 0.06 Nb, 0.02 to 0.08 N, 0.001 to 2 Ta, 0.001 to 0.5 La, 0.0001 to 1 Pd, 0.004 to 0.012 B, maximum 0.005 P, maximum 0.005 S, maximum 0.05 Si, maximum 0.005 Sn, balance iron and unavoidable impurities ,
Bevorzugte Bereiche für die einzelnen Legierungselemente der erfindungsgemässen Zusammensetzung sind in den Unteransprüchen enthalten, wobei besonders bevorzugt der Stahl erfindungsgemäss folgende chemische Zusammensetzung aufweist (Angaben in Gew.- %): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.007 B, 0.005 P, 0.005 S, 0.05 Si, 0.005 Sn, Rest Eisen und unvermeidbare Verunreinigungen.Preferred ranges for the individual alloying elements of the composition according to the invention are contained in the subclaims, wherein the steel according to the invention particularly preferably has the following chemical composition (in% by weight): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.007 B, 0.005 P, 0.005 S, 0.05 Si, 0.005 Sn, balance iron and unavoidable impurities.
Der Vorteil der Erfindung besteht darin, dass die erfindungsgemässe Legierung im Vergleich zu den aus dem Stand der Technik bekannten Legierungen ähnlicher Zusammensetzung, allerdings ohne B-Zusatz bzw. ohne La-und Pd-Zusatz, bei gleicher Wärmebehandlung verbesserte Kriecheigenschaften bei Temperaturen von 550 °C und darüber aufweist, wobei auch gute Zähigkeitseigenschaften (Dehnung, Schlagarbeit) und eine verbesserte Beständigkeit gegen Versprödung bei Langzeitalterung erzielt werden.The advantage of the invention is that the inventive alloy compared to the known from the prior art alloys of similar composition, but without B addition or without La and Pd addition, with the same heat treatment improved creep properties at temperatures of 550 ° C and above, while also good toughness properties (elongation, impact work) and improved resistance to embrittlement during long-term aging can be achieved.
Es wird ein Anlassgefüge eingestellt, das sich durch eine zähe Grundmatrix und durch die Anwesenheit warmfestigkeitsbringender Nitride, Boride und Karbide auszeichnet. Die Zähigkeit der Grundmatrix wird durch die Anwesenheit von Substitionselementen, vorzugsweise durch Nickel, eingestellt. Die Gehalte dieser Substitutionselemente sind so bestimmt, dass sie eine optimale Entfaltung von sowohl der Martensithärtung wie auch der Teilchenhärtung durch Ausscheidung von Sondernitriden, z. B. Vanadiumnitride oder Niob-Nitride, zur Einstellung höchster Warmfestigkeiten ermöglichen.It is set a starting structure, which is characterized by a tough matrix and the presence of heat-resistant nitrides, borides and carbides. The toughness of the base matrix is adjusted by the presence of substitution elements, preferably nickel. The contents of these substitution elements are determined to provide optimal unfolding of both martensite hardening and particle hardening by precipitation of special nitrides, e.g. As vanadium nitrides or niobium nitrides, to set the highest heat resistance possible.
Grundsätzlich senken beide Härtungsmechanismen die Duktilität. Charakteristischer Weise wird dabei im Bereich der Sekundärhärtung ein Duktilitätsminimum beobachtet. Dieses Duktilitätsminimum braucht nicht ausschliesslich durch den eigentlichen Ausscheidungshärtungsmechanismus hervorgerufen zu sein. Ein gewisser Versprödungsbeitrag kann auch durch Segregation von Verunreinigungen an die Korngrenzen oder möglicherweise auch durch Nahordnungseinstellungen von gelösten Legierungsatomen geliefert werden.Basically, both hardening mechanisms lower the ductility. Characteristically, a minimum ductility is observed in the area of secondary hardening. This minimum ductility need not be caused exclusively by the actual precipitation hardening mechanism. A certain embrittlement contribution may also be provided by segregation of impurities to the grain boundaries or possibly also by near-order adjustments of dissolved alloy atoms.
Eine Erhöhung der Anlasstemperatur über den Sekundärhärtungsbereich führt zur vollständigen Ausscheidung mit deutlichem Wachstum von Karbiden. Dadurch nimmt die Festigkeit ab und die Duktilität zu. Wesentlich ist, dass durch die gleichzeitige Erholung der Versetzungssubstruktur und der Teilchenvergröberung die Duktilität verstärkt zunimmt, so dass die Kombination aus Festigkeit und Duktilität insgesamt verbessert wird. Diese Verbesserung ist der Bildung einer teilchenstabilisierten Subkornstruktur zuzuschreiben. Dabei ist davon auszugehen, dass sowohl die Duktilität als auch die Festigkeit teilchenstabilisierter Subkornstrukturen durch Ungleichmässigkeiten in der Topologie der Teilchen-Subkornstruktur verringert wird. Ausscheidungen auf Subkorngrenzen sind einer beschleunigten Vergröberung unterworfen und neigen zur Koagulation mit benachbarten Ausscheidungen. Grobe und koagulierte Phasen erzeugen bruchauslösende Spannungsspitzen, welche die Duktilität senken. Vor allem aber wird durch die ungleichmässige Verteilung der Ausscheidungen auch der bei hohen Temperaturen wirksamste Härtungsmechanismus, nämlich die Teilchenhärtung, stark begrenzt.Increasing the tempering temperature over the secondary hardening area results in complete precipitation with significant growth of carbides. As a result, the strength decreases and the ductility increases. Importantly, the simultaneous recovery of dislocation substructure and particle coarsening increases ductility so as to improve the overall combination of strength and ductility. This improvement is attributable to the formation of a particle-stabilized subgrain structure. It can be assumed that both the ductility and the strength of particle-stabilized subgrain structures are reduced by unevenness in the topology of the particle sub-grain structure. Precipitose precipitates are subject to accelerated coarsening and tend to coagulate with adjacent precipitates. Coarse and coagulated phases generate fracture stress peaks, which reduce ductility. Above all, however, the non-uniform distribution of the precipitates also severely limits the hardening mechanism which is most effective at high temperatures, namely particle hardening.
Eine Massnahme zur Duktilitätssteigerung in konventionellen, martensitischhärtbaren Stählen ist das Zu legieren von Nickel. Die Ursachen hierzu sind jedoch nicht in allen Punkten bekannt und dürften stark vom Nickelgehalt abhängen. So können kleine Anteile von Nickel schon sehr dutktilitätsfördernd sein, wenn dadurch etwa die Bildung von Delta-Ferrit vollständig unterdrückt werden kann.One measure for increasing the ductility in conventional martensitic-hardening steels is the alloying of nickel. However, the reasons for this are not known in all respects and should depend heavily on the nickel content. Thus, small amounts of nickel can be very Ductititätsfördernd, if it can be completely suppressed, for example, the formation of delta ferrite.
Bei Nickelgehalten über 2 Gew.- % wird hingegen erwartet, dass durch Nickel die Ac1-Temperatur (das ist diejenige Temperatur, bei der sich während des Aufheizens Ferrit in Austenit umzuwandeln beginnt) auf Temperaturen unter 700 °C gesenkt wird. Soll also die Festigkeit durch ein Absenken der Anlasstemperatur unter 700 °C gesteigert werden, dann ist in Anwesenheit erhöhter Nickelgehalte beim Anlassen mit einer partiellen Umwandlung von Ferrit in Austenit zu rechnen. Dies ist mit einer gewissen duktilitätsfördernden Kornneubildung verbunden. Hingegen ist jedoch zu beachten, dass die Karbidausscheidung oberhalb der Ac1-Temperatur nur unvollständig abläuft, da die Löslichkeit des austenitstabilisierenden Elements Kohlenstoff im Austenit grösser ist als im Ferrit. Der sich bildende Austenit ist weiter nicht hinreichend stabilisiert, so dass ein grösserer Volumenanteil des rückgebildeten Austenits einer weiteren martensitischen Umwandlung bei der Rückabkühlung nach dem Anlassen unterworfen ist. Neben den beiden vorgenannten Wirkungsbeiträgen von Nickel zur Duktilitätssteigerung kann ein gewisser Duktilitätsbeitrag von Nickel in seiner Wirkung als Substitutionselement in fester Lösung kommen. Dies lässt sich elektronentheoretisch so erklären, dass das Element Nickel zusätzliche, freie Elektronen in das Eisengitter speist und dadurch die Eisenlegierungen noch "metallischer" macht.By contrast, nickel contents above 2% by weight are expected to lower the Ac1 temperature (which is the temperature at which ferrite begins to convert to austenite during heating) to temperatures below 700 ° C. So if the strength is increased by lowering the tempering temperature below 700 ° C, then in the presence of increased nickel contents during tempering with a partial conversion of ferrite into austenite can be expected. This is associated with a certain ductility-promoting grain regeneration. However, it should be noted that the carbide precipitation above the Ac1 temperature is only incomplete, since the solubility of the austenite-stabilizing element carbon in austenite is greater than in the ferrite. Furthermore, the austenite which forms is not sufficiently stabilized, so that a larger volume fraction of the reformed austenite undergoes further martensitic transformation in the post-anneal cooling. In addition to the two above-mentioned contributions of nickel to the ductility increase, a certain ductility contribution of nickel can come into solid solution as a substitution element. This can be explained electron-theoretically in such a way that the element nickel feeds additional, free electrons into the iron grid and thereby makes the iron alloys even more "metallic".
Grundsätzlich weisen konventionelle, martensitisch-härtbare Stähle, welche mit Nickel legiert sind, gegenüber nickelarmen Legierungen keine besonderen Warmfestigkeitsvorteile auf. Dies trifft zumindest für Prüftemperaturen oberhalb 500 °C zu und könnte bei erhöhten Nickelgehalten mit der oben erwähnten Reaustenitisierung beim Anlassen zusammenhängen. Es ist ferner bekannt, dass das Zu legieren von Nickel in derartige Stähle die Gefügeinstabilität unter langzeitigen Auslagerungsbedingungen bei erhöhten Temperaturen deutlich verschärft. Diese langzeitige Gefügeinstabilität wird dabei mit einer beschleunigten Vergröberung der Karbide in Beziehung gesetzt.Basically, conventional martensitic-hardenable steels which are alloyed with nickel have no particular advantages in heat resistance compared to nickel-poor alloys. This is true at least for test temperatures above 500 ° C and could be related to the above-mentioned reactivation on tempering at elevated nickel levels. It is also known that the alloying of nickel into such steels significantly aggravates the structural instability under long-term aging conditions at elevated temperatures. This long-term structural instability is related to an accelerated coarsening of the carbides.
Mangan liegt auf der linken Seite neben dem Element Eisen im periodischen System der Elemente. Es ist ein elektronenärmeres Element, womit seine Wirkung in fester Lösung deutlich verschieden sein sollte von Nickel. Nichtsdestoweniger ist es ein austenitstabilisierendes Element, welches die Ac1-Temperatur stark senkt, jedoch keine besonders positive, sondern eine eher ungünstige Wirkung auf die Duktilität hinterlässt. Auf der Seite der kohlenstoffhaltigen 12 % Chromstähle wird Mangan als ein Verunreinigungselement verstanden, welches die Anlassversprödung wesentlich fördert. Daher wird der Gehalt an Mangan gewöhnlich auf Kleinstmengen begrenzt.Manganese is on the left side next to the element iron in the periodic system of elements. It is an electron-poorer element, so its action in solid solution should be distinctly different from that of nickel. Nonetheless, it is an austenite stabilizing element which greatly lowers the Ac1 temperature, but leaves no particularly positive but rather unfavorable effect on ductility. On the carbonaceous 12% chromium steel side, manganese is understood to be an impurity element which promotes temper embrittlement substantially. Therefore, the content of manganese is usually limited to very small amounts.
Nachfolgend werden die bevorzugten Mengen in Gewichtsprozenten für jedes Element und die Gründe für die gewählten erfindungsgemässen Legierungsbereiche in ihrem Zusammenhang mit den hieraus resultierenden Möglichkeiten der Wärmebehandlungen aufgezeigt.The preferred amounts in weight percents for each element and the reasons for the selected alloying ranges according to the invention are shown below in connection with the heat treatment possibilities resulting therefrom.
Ein Gewichtsanteil von 9-12 % Chrom ermöglicht eine gute Durchhärtbarkeit dickwandiger Bauteile und stellt eine hinreichende Oxidationsbeständigkeit bis zu einer Temperatur von 550 °C sicher. Ein Gewichtsanteil unter 9 % beeinträchtigt die Durchvergütbarkeit. Gehalte oberhalb 12 % führen zur beschleunigten Bildung von hexagonalen Chromnitriden während des Anlassvorgangs, welche neben Stickstoff auch Vanadium abbinden, und damit die Wirksamkeit einer Aushärtung durch Vanadiumnitride verringern. Der optimale Chromgehalt liegt bei 10.5 bis 11.5 %.A weight proportion of 9-12% chromium allows good through-hardenability of thick-walled components and ensures sufficient oxidation resistance up to a temperature of 550 ° C. A proportion by weight of less than 9% impairs the through-hardenability. Contents above 12% lead to the accelerated formation of hexagonal chromium nitrides during the tempering process, which, in addition to nitrogen, also cures vanadium, thus reducing the effectiveness of vanadium nitride curing. The optimum chromium content is 10.5 to 11.5%.
Diese Elemente fördern die Anlassversprödung und müssen daher auf kleinste Gehalte begrenzt werden. Der zu spezifierende Bereich sollte unter Berücksichtigung der metallurgischen Möglichkeiten im Bereich zwischen 0.1 und 0.5 Gew. -%, vorzugsweise zwischen 0.1 und 0.25 %, insbesondere bei 0.2 % für Mangan und bei max. 0.05 % Gew.- % für Silizium liegen.These elements promote temper embrittlement and must therefore be limited to the smallest amounts. The range to be specified should take into account the metallurgical possibilities in the range between 0.1 and 0.5% by weight, preferably between 0.1 and 0.25%, in particular at 0.2% for manganese and at max. 0.05% by weight for silicon.
Nickel wird als austenitstabilisierendes Element zur Unterdrückung von Delta-Ferrit eingesetzt. Darüber hinaus soll es als ein gelöstes Element in der ferritischen Matrix die Duktilität verbessern. Nickelgehalte von 2.3 bis etwa 3 Gew.- % sind sinnvoll. Nickelgehalte oberhalb 4 Gew.- % verstärken die Austenitstabilität derart, dass nach dem Lösungsglühen und Anlassen ein erhöhter Anteil von Restaustenit beziehungsweise Anlassaustenit im vergüteten Martensit vorliegen kann. Vorzugsweise liegt der Nickelgehalt bei 2.3 bis 2.8, insbesondere 2.5 Gew.- %.Nickel is used as an austenite stabilizing element to suppress delta ferrite. In addition, it is said to improve ductility as a dissolved element in the ferritic matrix. Nickel contents of 2.3 to about 3% by weight make sense. Nickel contents above 4% by weight increase the austenite stability such that after solution heat treatment and tempering an increased proportion of retained austenite or tempering austenite can be present in the tempered martensite. The nickel content is preferably 2.3 to 2.8, in particular 2.5% by weight.
Molybdän verbessert die Kriechfestigkeit durch Mischkristallhärtung als partiell gelöstes Element und durch Ausscheidungshärtung während einer Langzeitbeanspruchung. Ein übermässig hoher Anteil dieses Elementes führt jedoch zu Versprödung während einer Langzeitauslagerung, welche durch die Ausscheidung und Vergröberung von Laves-Phase (W, Mo) und Sigma-Phase (Mo) gegeben ist. Der Bereich für Mo liegt bei 1.5 bis 2 Gew.- %, vorzugsweise bei 1.6 bis 1.8 Gew.- %, insbesondere bei 1.7 Gew.- %.Molybdenum improves creep strength by solid solution hardening as a partially dissolved element and precipitation hardening during a long-term stress. An excessively high proportion of this element, however, leads to embrittlement during long-term aging, which is due to the precipitation and coarsening of Laves phase (W, Mo) and Sigma phase (Mo). The range for Mo is 1.5 to 2% by weight, preferably 1.6 to 1.8% by weight, in particular 1.7% by weight.
Diese beiden Elemente zusammen kontrollieren massgeblich die Korngrössenausbildung und die Ausscheidungshärtung. Ein leicht überstöchiometrisches V/N-Verhältnis erhöht mitunter auch die Stabilität des Vanadiumnitrids gegenüber des Chromnitrids. Der konkrete Gehalt an Stickstoff und Vanadiumnitriden richtet sich nach dem optimalen Volumenanteil der Vanadiumnitride, welche während der Lösungsglühung als unlösliche Primärnitride zurückbleiben sollen. Je grösser der Gesamtanteil von Vanadium und Stickstoff ist, umso grösser ist derjenige Anteil der Vanadiumnitride, welcher nicht mehr in Lösung geht und umso grösser ist die Kornfeinungswirkung. Der positive Einfluss der Kornfeinung auf die Duktilität ist jedoch begrenzt, da mit zunehmendem Volumenanteil von Primärnitriden die Primärnitride selbst die Duktilität begrenzen. Der bevorzugte Gehalt an Stickstoff liegt im Bereich 0.02 bis 0.08 Gew.- %, vorzugsweise 0.025 bis 0.055 Gew.- %, besonders bevorzugt bei 0.04 Gew.- % N, und derjenige von Vanadium liegt im Bereich zwischen 0.1 und 0.4 Gew.- %, vorzugsweise 0.2 bis 0.3 Gew.- %,und insbesondere bei 0.25 Gew. - %.Together, these two elements significantly control grain size formation and precipitation hardening. A slightly more than stoichiometric V / N ratio sometimes also increases the stability of the vanadium nitride over the chromium nitride. The specific content of nitrogen and vanadium nitrides depends on the optimum volume fraction of the vanadium nitrides, which are to remain as insoluble primary nitrides during the solution annealing. The greater the total content of vanadium and nitrogen, the greater is the proportion of vanadium nitrides, which no longer goes into solution and the greater the grain refining effect. However, the positive effect of grain refining on ductility is limited because with increasing volume fraction of primary nitrides, the primary nitrides themselves limit ductility. The preferred content of nitrogen is in the range from 0.02 to 0.08% by weight, preferably 0.025 to 0.055% by weight, particularly preferably 0.04% by weight N, and that of vanadium is in the range between 0.1 and 0.4% by weight. , preferably 0.2 to 0.3% by weight, and especially at 0.25% by weight.
Niob ist ein starker Nitridbildner, welche die Kornfeinungswirkung unterstützen. Um den Volumenanteil der Primärnitride klein zu halten, muss ihr Gesamtanteil auf 0.1 Gew.- % begrenzt werden. Niob löst sich in kleinen Mengen im Vanadiumnitrid und kann damit die Stabilität des Vanadiumnitrids verbessern. Niob wird im Bereich zwischen 0.01 und 0.06 Gew.- %, vorzugsweise 0.02 bis 0.04 Gew.- %, und insbesondere mit 0.03 Gew. -% zulegiert.Niobium is a strong nitride former that aids the grain refining effect. In order to keep the volume fraction of the primary nitrides small, their total proportion must be limited to 0.1% by weight. Niobium dissolves in vanadium nitride in small amounts and can thus improve the stability of the vanadium nitride. Niobium is added in the range between 0.01 and 0.06% by weight, preferably 0.02 to 0.04% by weight, and in particular at 0.03% by weight.
Diese Elemente verstärken zusammen mit Silizium und Mangan die Anlassversprödung bei Langzeitauslagerungen im Bereich zwischen 350 und 500°C. Diese Elemente sollten daher auf maximal tolerierbare Anteile (0.005 Gew.- %) begrenzt werden.Together with silicon and manganese, these elements increase the embrittlement of long-term aging in the range between 350 and 500 ° C. These elements should therefore be limited to maximum tolerable levels (0.005 wt%).
Ta beeinflusst die Kriechfestigkeit positiv. Ein Zulegieren von 0.001 bis 2 Gew.- % Ta bewirkt, dass aufgrund der grösseren Neigung von Tantal zur Karbidbildung als Chrom einerseits die Ausscheidung von unerwünschten Chromkarbiden an den Korngrenzen, andererseits auch die unerwünschte Verarmung des Mischkristalls an Chrom verringert wird. Der bevorzugte Bereich für Ta liegt bei 0.005 bis 0.1 Gew.- %, insbesondere sollte ein Ta-Gehalt von 0.01 Gew.- % eingestellt werden.Ta influences the creep resistance positively. Addition of 0.001 to 2% by weight of Ta has the effect, on the one hand, that due to the greater tendency of tantalum to form carbides as chromium, the precipitation of undesired chromium carbides at the grain boundaries and, on the other hand, the undesirable depletion of the mixed crystal in chromium are reduced. The preferred range for Ta is 0.005 to 0.1% by weight, in particular a Ta content of 0.01% by weight should be set.
Kohlenstoff bildet beim Anlassen Chromkarbide, welche für eine verbesserte Kriechfestigkeit förderlich sind. Bei zu hohen Kohlenstoffgehalten führt der hieraus resultierende erhöhte Volumenanteil von Karbiden jedoch zu einer Duktilitätsminderung, welche insbesondere durch die Karbidvergröberung während einer Langzeitauslagerung zum Tragen kommt. Der Kohlenstoffgehalt sollte daher nach oben auf 0.16 Gew.- % begrenzt werden. Nachteilig ist auch die Tatsache, dass Kohlenstoff die Aufhärtung beim Schweissen verstärkt. Der bevorzugte Kohlenstoffgehalt liegt im Bereich zwischen 0.10 und 0.14 Gew.- %, vorzugsweise bei 0.12 Gew.- %.Carbon forms chromium carbides on tempering, which are conducive to improved creep resistance. At too high carbon contents, however, the resulting increased volume fraction of carbides leads to a ductility reduction, which comes into play in particular by the carbide coarsening during long-term storage. The carbon content should therefore be limited upwards to 0.16% by weight. Another disadvantage is the fact that carbon increases the hardening during welding. The preferred carbon content is in the range between 0.10 and 0.14% by weight, preferably 0.12% by weight.
Bor stabilisiert die M23C6-Ausscheidungen und verbessert somit die Kriechfestigkeit des Stahles, wobei aber die Bildung von Bornitriden auf Kosten der Vandiumkarbonitride verhindert werden muss. Ausserdem ist aber zu beachten, dass die Austenitisierungstemperatur erhöht werden muss, um homogenes Bor in der Matrix zu erhalten, was aber wiederum zu einer Erhöhung der Korngrösse und damit zu schlechteren Eigenschaften des Materials führt. Daher soll der Bor-Gehalt auf 40 bis 120 ppm begrenzt werden. Vorzugsweise ist ein B-Gehalt von 50 ppm bis 120 ppm, besonders bevorzugt von ca. 70 ppm, einzustellen.Boron stabilizes the M 23 C 6 precipitates and thus improves the creep resistance of the steel, but the formation of boron nitrides has to be prevented at the expense of the vandium carbonitrides. In addition, however, it should be noted that the austenitizing temperature must be increased in order to obtain homogeneous boron in the matrix, which in turn leads to an increase in the particle size and thus to poorer properties of the material. Therefore, the boron content should be limited to 40 to 120 ppm. Preferably, a B content of 50 ppm to 120 ppm, more preferably of about 70 ppm to adjust.
Lanthan bindet den Schwefel im Stahl durch die Bildung von Lanthansulfid La2S3. La2S3 ist wesentlich stabiler als MnS2. Es hat einen Schmelzpunkt von > 2100 °C, während sich MnS2 bei hohen Temperaturen unter Freisetzung von S zersetzt. Da aber aufgrund des Stahlherstellungsprozesses gewisse Gehalte an S einerseits notwendig sind und andererseits als Verunreinigungen auch nicht vermeidbar sind, und Schwefel die Versprödungsneigung des Materials nachteilig erhöht, sind stabile Sulfidbildner im Stahl wie La wesentlich besser als Mn. Ausserdem wird durch das Mikrolegieren mit La vorteilhaft die Korngrösse reduziert, was sich auch vorteilhaft dabei auswirkt, wenn das Material zerstörungsfrei durch Ultraschallverfahren geprüft wird. So wurde von der Anmelderin beispielsweise bei einem mit B dotierten 12% Cr-Stahl bei einer Austenitisierungstemperatur von 1100 °C eine Korngrösse ASTM 6 ermittelt, während bei einem mit B und La mikrolegierten 12 % Cr-Stahl die Korngrösse bei der gleichen Austenitisierungstemperatur nur noch ASTM 7 betrug. Hinzu kommt, dass wegen der sehr hohen Stabilität der Lanthansulfide und des positiven Effekts auf die Behinderung von interdentrischen Schweissrissen die Schweissbarkeit der 12% Cr-Stähle verbessert wird. Da Lanthan aber nachteilig auch Oxide bildet, sollte der Gehalt an La bei 0.001 bis 0.5 Gew.- %, vorzugsweise bei 0.01 bis 0.1 Gew.- %, insbesondere bei 0.05 Gew.- %, liegen.Lanthanum binds the sulfur in the steel through the formation of lanthanum sulfide La 2 S 3 . La 2 S 3 is much more stable than MnS 2 . It has a melting point of> 2100 ° C, while MnS 2 decomposes at high temperatures to release S. However, since certain contents of S are necessary on the one hand because of the steelmaking process and on the other hand as impurities are unavoidable, and sulfur adversely increases the embrittlement tendency of the material, stable sulfide formers in steel such as La are much better than Mn. In addition, the grain size is advantageously reduced by the micro-alloying with La, which also has an advantageous effect if the material is tested non-destructively by ultrasonic methods. For example, in the case of a 12% Cr steel doped with B at an austenitizing temperature of 1100 ° C., a grain size ASTM 6 was determined by the applicant, whereas for a 12% Cr steel microblasted with B and La, the grain size at the same austenitizing temperature only remains ASTM 7 was. In addition, because of the very high stability of the lanthanum sulfides and the positive effect on the obstruction of interdental weld cracks, the weldability of the 12% Cr steels is improved. However, since lanthanum also adversely forms oxides, the content of La should be 0.001 to 0.5% by weight, preferably 0.01 to 0.1% by weight, especially 0.05% by weight.
Pd bildet mit dem Eisen des Stahles eine geordnete intermetallische Fe-Pd L10 - Phase, die α"-Phase. Diese stabile α"-Phase erhöht die Zeitstandfestigkeit bei hohen Temperaturen durch Stabilisation der Korngrenzenausscheidungen, wie z.B. M23C6, und wirkt sich somit positiv auf die Kriecheigenschaften aus. Palladium hat allerdings den Nachteil hoher Kosten. Der Pd-Gehalt des vorgeschlagenen Stahles sollte im Bereich von 0.0001 bis 1, vorzugsweise von 0.0005 bis 0.01 Gew. -% liegen, wobei ein Gehalt von 0.001 Gew. -% besonders geeignet ist.Pd forms an ordered Fe-Pd L1 0 intermetallic phase with the iron of the steel, the α "phase. This stable α" phase increases the high temperature creep strength by stabilizing grain boundary precipitates such as M 23 C 6 and acts thus have a positive effect on the creep properties. However, palladium has the disadvantage of high costs. The Pd content of the proposed steel should be in the range of 0.0001 to 1, preferably 0.0005 to 0.01 wt%, with a content of 0.001 wt% being particularly suitable.
In der Zeichnung ist ein Ausführungsbeispiel der Erfindung dargestellt. Es zeigen:
- Fig. 1
- eine graphische Darstellung, bei welcher die Spannungen ausgewählter Legierungen (nach dem Stand der Technik VL1 bzw. entsprechend der vorliegenden Erfindung L2) bei einer Temperatur von 550 °C über der mittleren Zeit bis zum Bruch bzw. bis zur 1 % Dehnung des Materials aufgetragen sind;
- Fig. 2
- eine graphische Darstellung analog zu
Fig.1 , aber bei einer Temperatur von 450 °C; - Fig. 3
- eine graphische Darstellung, bei welcher die Bruchzähigkeit (linkes Teilbild) und die Schlagenergie (rechtes Teilbild) für die beiden Legierungen VL1 und L2 bei Raumtemperatur im wärmebehandelten Zustand (ohne Auslagerung) gegenübergestellt sind und
- Fig. 4
- eine graphische Darstellung analog zu
Fig. 3 , bei welcher aber die Proben nach der Wärmebehandlung zusätzlich 3000 Stunden bei 480 °C ausgelagert wurden.
- Fig. 1
- a graph in which the voltages of selected alloys (according to the prior art VL1 and according to the present invention L2) at a temperature from 550 ° C over the mean time to break or to 1% elongation of the material, respectively;
- Fig. 2
- a graphic representation analogous to
Fig.1 but at a temperature of 450 ° C; - Fig. 3
- a graph in which the fracture toughness (left partial image) and the impact energy (right partial image) for the two alloys VL1 and L2 are compared at room temperature in the heat treated state (without outsourcing) and
- Fig. 4
- a graphic representation analogous to
Fig. 3 , in which, however, the samples after the heat treatment were additionally stored for 3,000 hours at 480 ° C.
Nachfolgend wird die Erfindung anhand eines Ausführungsbeispieles und der
Die untersuchte erfindungsgemässe Legierung L2 wies folgende chemische Zusammensetzung (Angaben in Gew.- %) auf: 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.0070 B, 0.05 Si, 0.005 P, 0.005 S, 0.005 Sn, Rest Eisen und unvermeidbare Verunreinigungen.The investigated inventive alloy L2 had the following chemical composition (in% by weight): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.0070 B, 0.05 Si, 0.005 P, 0.005 S, 0.005 Sn, balance iron and unavoidable impurities.
Als Vergleichslegierung VL1 wurde ein aus dem Stand der Technik bekannter kommerzieller Stahl des Typs X12CrNiMoV11-2-2 verwendet mit folgender chemischer Zusammensetzung (Angaben in Gew.- %): 0.10-0.14 C, 11.0-12.0 Cr, 0.25 Mn, 2.0-2.6 Ni, 1.3-1.8 Mo, 0.2-0.35 V, 0.02-0.05 N, 0.15 Si, 0.026 P und 0.015 S.The comparative alloy VL1 used was a prior art commercial steel of the type X12CrNiMoV11-2-2 having the following chemical composition (in% by weight): 0.10-0.14 C, 11.0-12.0 Cr, 0.25 Mn, 2.0-2.6 Ni, 1.3-1.8 Mo, 0.2-0.35 V, 0.02-0.05 N, 0.15 Si, 0.026 P and 0.015 S.
Beide Legierungen haben somit eine vergleichbare Zusammensetzung mit dem Unterschied, dass die erfindungsgemässe Legierung L2 zusätzlich mit Nb, B, sowie La und Pd mikrolegiert ist und Ta enthält.Both alloys thus have a comparable composition with the difference that the inventive alloy L2 is additionally microalloyed with Nb, B, as well as La and Pd and contains Ta.
Die erfindungsgemässe Legierung L2 und die Vergleichslegierung VL1 wurden den folgenden Wärmebehandlungsprozessen unterzogen:
- 1. Normalisierung bei 1100 °C / 3h / Ventilatorluft-Abkühlung auf Raumtemperatur
- 2. Anlassbehandlung bei 640 °C / 5h / Luft-Abkühlung auf Raumtemperatur
- 1. Normalization at 1100 ° C / 3h / fan air cooling to room temperature
- 2. Tempering treatment at 640 ° C / 5h / air cooling to room temperature
Aus den derartig behandelten Werkstoffen wurden Proben zur Ermittlung der mechanischen Eigenschaften hergestellt. Es wurden Langzeitauslagerung bei 450 °C, 480 °C bzw. 550 °C unter bestimmten mechanischen Belastungen durchgeführt, sowie die Schlagenergie und die Bruchzähigkeit bei Raumtemperatur ermittelt. Die Ergebnisse sind in den
Es zeigt sich, dass bei der genannten Temperatur die erfindungsgemässe Legierung L2 vorteilhaft wesentlich längere Zeiten bei Einwirkung der gleichen Spannung bis zum Erreichen einer 1 %igen Dehnung benötigt als die Vergleichslegierung VL1. Bei der Zeit bis zum Bruch (Zeitstandfestigkeit) ist dieser Unterschied noch deutlicher zu sehen, da die in
In
In
Den Einfluss einer Langzeitauslagerung bei einer Temperatur von 480 °C zeigt
Diese sehr gute Eigenschaftskombination (sehr hohe Kriechfestigkeit bei Temperaturen von 450 °C und wesentlich darüber, gute Zähigkeitseigenschaften nach Langzeitauslagerung bei hohen Temperaturen) wird im Vergleich zum Stand der Technik erreicht durch die Kombination der Legierungselemente B, Ta, La und Pd in den angegebenen Bereichen.This very good combination of properties (very high creep resistance at temperatures of 450 ° C. and significantly higher, good toughness properties after long-term aging at high temperatures) is achieved in comparison to the prior art by the combination of the alloying elements B, Ta, La and Pd in the specified ranges ,
Zusammenfassend ist zu sagen, dass sich die erfindungsgemässe Legierung einerseits durch eine sehr gute Kriechfestigkeit bei Temperaturen von 450 °C, vorzugsweise 550 °C, und darüber auszeichnet und damit den konventionellen 12%Cr-Stählen überlegen ist. Dies ist vorwiegend auf den Einfluss von Bor, Tantal und Palladium zurückzuführen, welche im angegebenen Bereich zulegiert werden. Bor, Tantal und Palladium stabilisieren die M23C6-Ausscheidungen, welche eine wesentliche verfestigende Rolle während des Kriechens spielen, wobei Pd zusätzlich eine stabile intermetallische Phase mit dem Eisen bildet, was auch zur Erhöhung der Kriechfestigkeit beiträgt. Zusätzlich wird die Versetzungsdichte bis zum Bruch erhalten und somit Kriechfestigkeit des Stahles verbessert. Einen ähnlichen Effekt auf die Erhöhung der Kriechfestigkeit haben Ta und Pd. Andererseits weist die erfindungsgemässe Legierung eine verbesserte Beständigkeit gegenüber Versprödung bei Langzeitalterung und eine vergleichsweise hohe Zähigkeit auf. Dies ist zurückzuführen auf die Zugabe von Lanthan im angegebenen Bereich, weil dadurch die sowohl Korngrösse reduziert wird als auch stabile Lanthansulfide La2S3 gebildet werden.In summary, it should be said that the alloy according to the invention is distinguished on the one hand by a very good creep resistance at temperatures of 450 ° C., preferably 550 ° C., and above, and is thus superior to the conventional 12% Cr steels. This is mainly due to the influence of boron, tantalum and palladium, which are alloyed in the specified range. Boron, tantalum and palladium stabilize the M 23 C 6 precipitates, which play a significant strengthening role during creep, with Pd additionally forming a stable intermetallic phase with the iron, which also contributes to increasing creep resistance. In addition, the dislocation density is maintained until breakage, thus improving creep strength of the steel. A similar effect on increasing creep strength is found in Ta and Pd. On the other hand, the alloy of the present invention has improved resistance to embrittlement upon long-term aging and comparatively high toughness. This is due to the addition of lanthanum in the specified range, because both the grain size is reduced as well as stable lanthanum sulfide La 2 S 3 are formed.
Die erfindungsgemässe Legierung ist somit besonders für Rotoren in Gas- und Dampfturbinen, welche hohen Eintrittstemperaturen von über 550 °C ausgesetzt sind, vorteilhaft einsetzbar.The inventive alloy is thus particularly advantageous for rotors in gas and steam turbines, which are exposed to high inlet temperatures of about 550 ° C, can be used advantageously.
Selbstverständlich ist die Erfindung nicht auf das beschriebene Ausführungsbeispiel beschränkt.Of course, the invention is not limited to the embodiment described.
Claims (27)
- Creep-resistant steel, characterized by the following chemical composition (given in % by weight): 0.08 to 0.16 C, 9.0 to 12.0 Cr, 0.1 to 0.5 Mn, 2.3 to 3 Ni, 1.5 to 2.0 Mo, 0.1 to 0.4 V, 0.01 to 0.06 Nb, 0.02 to 0.08 N, 0.001 to 2 Ta, 0.001 to 0.5 La, 0.0001 to 1 Pd, 0.004 to 0.012 B, maximum 0.005 P, maximum 0.005 S, maximum 0.05 Si, maximum 0.005 Sn, and the remainder iron and unavoidable impurities.
- Creep-resistant steel according to claim 1, characterized by 2.3 to 2.8% Ni.
- Creep-resistant steel according to claim 2, characterized by 2.5% Ni.
- Creep-resistant steel according to claim 1, characterized by 10 to 12% Cr.
- Creep-resistant steel according to claim 4, characterized by 10.5 to 11.5% Cr.
- Creep-resistant steel according to claim 1, characterized by 0.10 to 0.14% C.
- Creep-resistant steel according to claim 6, characterized by 0.12% C.
- Creep-resistant steel according to claim 1, characterized by 0.10 to 0.25% Mn.
- Creep-resistant steel according to claim 8, characterized by 0.20% Mn.
- Creep-resistant steel according to claim 1, characterized by 1.6 to 1.8% Mo.
- Creep-resistant steel according to claim 10, characterized by 1.7% Mo.
- Creep-resistant steel according to claim 1, characterized by 0.2 to 0.3% V.
- Creep-resistant steel according to claim 12, characterized by 0.25% V.
- Creep-resistant steel according to claim 1, characterized by 0.02 to 0.04% Nb.
- Creep-resistant steel according to claim 14, characterized by 0.03% Nb.
- Creep-resistant steel according to claim 1, characterized by 0.025 to 0.055% N.
- Creep-resistant steel according to claim 16, characterized by 0.04% N.
- Creep-resistant steel according to claim 1, characterized by 0.005 to 0.012% B.
- Creep-resistant steel according to claim 18, characterized by 0.007% B.
- Creep-resistant steel according to claim 1, characterized by 0.005 to 0.1% Ta.
- Creep-resistant steel according to claim 20, characterized by 0.01% Ta.
- Creep-resistant steel according to claim 1, characterized by 0.01 to 0.1% La.
- Creep-resistant steel according to claim 22, characterized by 0.05% La.
- Creep-resistant steel according to claim 1, characterized by 0.0001 to 1% Pd.
- Creep-resistant steel according to claim 24, characterized by 0.0005 to 0.01% Pd.
- Creep-resistant steel according to claim 25, characterized by 0.001% Pd.
- Creep-resistant steel according to any of claims 1 to 26, characterized in that it is used for rotors of thermal turbomachines.
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CH5062007 | 2007-03-29 | ||
PCT/EP2008/053004 WO2008119638A1 (en) | 2007-03-29 | 2008-03-13 | Creep resistant steel |
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JP5578893B2 (en) * | 2010-03-12 | 2014-08-27 | 株式会社日立製作所 | Member having sliding portion of steam turbine |
CH704427A1 (en) * | 2011-01-20 | 2012-07-31 | Alstom Technology Ltd | Welding additive material. |
JP5608280B1 (en) * | 2013-10-21 | 2014-10-15 | 大同工業株式会社 | Chain bearing, its manufacturing method, and chain using the same |
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JPS6024353A (en) * | 1983-07-20 | 1985-02-07 | Japan Steel Works Ltd:The | Heat-resistant 12% cr steel |
JPS63171856A (en) * | 1987-01-09 | 1988-07-15 | Hitachi Ltd | Heat-resisting steel and gas turbine using same |
US5310431A (en) * | 1992-10-07 | 1994-05-10 | Robert F. Buck | Creep resistant, precipitation-dispersion-strengthened, martensitic stainless steel and method thereof |
DE4440632A1 (en) * | 1994-11-14 | 1996-05-15 | Bayer Ag | Method and device for conveying hot, aggressive media |
DE19712020A1 (en) * | 1997-03-21 | 1998-09-24 | Abb Research Ltd | Fully martensitic steel alloy |
JPH10265909A (en) | 1997-03-25 | 1998-10-06 | Toshiba Corp | Heat resistant steel with high toughness, turbine rotor, and their production |
US5820817A (en) | 1997-07-28 | 1998-10-13 | General Electric Company | Steel alloy |
US5906791A (en) * | 1997-07-28 | 1999-05-25 | General Electric Company | Steel alloys |
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JP3982069B2 (en) * | 1998-07-08 | 2007-09-26 | 住友金属工業株式会社 | High Cr ferritic heat resistant steel |
JP4221518B2 (en) * | 1998-08-31 | 2009-02-12 | 独立行政法人物質・材料研究機構 | Ferritic heat resistant steel |
DE10025808A1 (en) * | 2000-05-24 | 2001-11-29 | Alstom Power Nv | Martensitic hardenable tempering steel with improved heat resistance and ductility |
KR100532877B1 (en) * | 2002-04-17 | 2005-12-01 | 스미토모 긴조쿠 고교 가부시키가이샤 | Austenitic stainless steel excellent in high temperature strength and corrosion resistance, heat resistant pressurized parts, and the manufacturing method thereof |
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EP2240619B1 (en) | 2007-03-29 | 2017-01-25 | General Electric Technology GmbH | Creep resistant steel |
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