EP2227572A1 - Austenitic heat-resistant nickel-base alloy - Google Patents

Austenitic heat-resistant nickel-base alloy

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Publication number
EP2227572A1
EP2227572A1 EP08865541A EP08865541A EP2227572A1 EP 2227572 A1 EP2227572 A1 EP 2227572A1 EP 08865541 A EP08865541 A EP 08865541A EP 08865541 A EP08865541 A EP 08865541A EP 2227572 A1 EP2227572 A1 EP 2227572A1
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Prior art keywords
alloy
max
alloy according
mass
sum
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EP08865541A
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German (de)
French (fr)
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EP2227572B1 (en
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Jutta KLÖWER
Bernd De Boer
Dietmar Schlager
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VDM Metals GmbH
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ThyssenKrupp VDM GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%

Definitions

  • the invention relates to an austenitic heat-resistant nickel-based alloy.
  • Alloy 81 with (in% by mass) 0.05% C, 30% Cr, 66% Ni, 0.9% Al and 1.8% Ti was used.
  • these alloys are used as valve base materials, wherein the valve seat section is additionally coated with an abrasion-resistant material, as described for example in EP-B 0521821.
  • This document gives the chemical composition (in mass%) of the base material as follows: 0.04 - 0.10% C 1 ⁇ 1, 0% Si, ⁇ 0.2% Cu, ⁇ 1, 0% Fe, ⁇ 1, 9% Mn, 18-21% Cr, 1, 8-2.7% Ti, 1, 0-1, 8% Al, ⁇ 2.0% Co, ⁇ 0.3% Mo, B, Zr, Rest of nickel.
  • a variant of this alloy is also mentioned among other things with 29 - 31% Cr.
  • 6,039,919 which describe an alloy of the following composition (in% by mass) for intake and exhaust valves of diesel engines, relate to this: ⁇ 0.1% C, ⁇ 1.0% Si , ⁇ 0.1% Mn, ⁇ 25 - ⁇ 32.2% Cr, ⁇ 3% Ti,> 1 - ⁇ 2% Al, balance Ni. But even this alloy does not provide sufficient hot corrosion resistance. In addition, in the future, more powerful engines, such as marine diesel engines, are operated at temperatures up to about 850 ° C, which also makes higher demands on the valve material, especially since the service life is to be maintained and no additional maintenance is desired.
  • DE-C 101 23 566 discloses an austenitic heat-resistant nickel-based alloy which has the following composition (in% by mass): 0.03-0.1% C, max. 0.005% S, max. 0.05% N, 25-35% Cr, max. 0.2% Mn, max. 0.1% Si, max. 0.2% Mo, 2 - 3% Ti, 0.02 - 1, 1% Nb, max. 0.1% Cu, max. 1% Fe, max. 0.08% P, 0.9-1.3% AI, max. 0.01% Mg, 0.02 - 0.1% Zr, max. 0.2% Co, the sum of Al + Ti + Nb being> 3.5%, the remainder being Ni and production-related conditions.
  • the alloy is characterized by additions of (in% by mass) 0.001-0.005% B, 0.01-0.04% Hf, and 0.01-0.04% Y.
  • the invention has for its object, up to a temperature of 850 ° C hot corrosion resistant material with mechanical properties which are not inferior to those of Alloy 80 A.
  • Remaining Ni and production-related admixtures where the sum of Ti + Al is between 3.3 and 4.3%, the sum of C + (10 x B) is between 0.05 and 0.2%, the sum of Hf + Zr is between 0.05 and 0.15% and the ratio Ti / Al> 3.
  • the material of the invention as a valve material is generally applicable and can be used in particular for future generations of marine diesel engines in the temperature range up to 850 ° C.
  • Table 1 shows an example of the chemical composition of two inventive examples E1 and E2.
  • two typical analyzes of the commercial alloys Alloy 80 A and Alloy 81 are listed.
  • the analyzes of the alloys E1 and E2 were obtained from a series of laboratory melts, which were melted in 10 kg blocks in the vacuum induction furnace, then hot rolled and solution heat treated at 1180 ° C for two hours in air with subsequent water quenching. The hardening of the alloys took place by two further annealing:
  • the alloys differed in the content of the elements discussed below, so that the evaluation of their mechanical properties and their behavior in the corrosive medium led to the analysis according to the invention.
  • the atmosphere was air with an SO 2 content of 0.5%.
  • the samples were swapped out at both 750 ° C and 850 ° C for 20 hours, 100 hours and 400 hours, respectively.
  • the ash was renewed after 100 hours, 200 hours and 300 hours to maintain the corrosiveness.
  • the depth of the internal corrosion could be reliably measured.
  • the Cr content must be as high as possible from the corrosion point of view. Metallurgically, however, 32% is a sensible upper limit. This shows the clear difference between the alloy variants with about 30% Cr and those with 20% Cr. The corrosion attack in the first mentioned alloys is at best only half as large.
  • the samples tested in the valve with a Cr content of 30% show a cobblestone-like appearance on macro photographs, which is reflected in the micrographs as a wavy sample surface, which is indicative of only moderate corrosion erosion. In contrast, the poorer samples already show strong even flaking.
  • Ti, Al A TkAI ratio of> 3 results in better corrosion resistance than lower Ti: Al ratios. This is attributed to the formation of a Ti-rich seam between the outer oxide layer and the region of internal sulfidation at high Ti contents.
  • Aluminum and titanium have a positive effect on the heat resistance due to the formation of ⁇ '-phase.
  • the sum of the elements Al + Ti should advantageously be between 3.5 and 4.3%. Too high a total content of these elements makes the thermoforming of the material difficult.
  • Si Silicon has been found to have no positive effect on corrosion properties and should be no more than 0.5%, better less than 0.1%.
  • Nb The niobium-alloyed samples basically have the thinnest corrosion layer, but this has no effect on the material loss itself Protective corrosion layer acts against the progression of the corrosion attack, the Nb content should be limited to a maximum of 0.5%. Furthermore, the Nb influences the material strength due to its high solubility in the ⁇ '-phase. At lower Nb levels below 0.5%, the Ti and Al content need not be adjusted.
  • B, C The addition of boron at levels of 0.002 - 0.01% improves corrosion resistance by reducing the internal sulfidation, which preferably proceeds along the grain boundaries, and thus reducing overall corrosion attack.
  • Carbon preferably forms Cr carbides at the grain boundaries.
  • Boron forms borides, which contribute to the stabilization of the grain boundaries and thus to long-term stability.
  • the forming Cr carbides lead to a Cr depletion in the vicinity of the grain boundaries, which is why at a high C content, the corrosion accelerated progresses.
  • carbides and borides must not overburden the grain boundaries, as they then hard precipitates greatly reduce the ductility of the material.
  • the sum of C + (10 x B) should not exceed 0.1%.
  • said sum is about 0.08%.
  • Hf Hafnium is often added to improve the high temperature oxidation resistance and obviously also influences the durability of the samples in vanadium ash and SO 2 atmosphere positively. Furthermore, Hf also changes the grain boundary properties under carbide or carbosulfide formation. Too high an HF content should be avoided, as otherwise the hot forming is no longer guaranteed. This results in a favorable concentration range between 0.02 and 0.08%, preferably 0.05%. The effect of Hf on the grain boundaries is comparable to the effect of Zr, which is why the empirical formula Hf + Zr ⁇ 0.10% advantageously results.
  • Zr Zirconium forms carbosulfides, which have a positive effect on the long-term strength and also contribute to the hot corrosion resistance by the binding of sulfur. It turned out that a Zr content between 0.01 and 0.05%. The aim is to have a Zr content in the range of 0.02%.
  • Co is an element that in principle increases the resistance to sulfur-containing media. On the other hand, it is also very expensive, which is why the co-alloying of Co is dispensed with. Due to admixtures in the feedstocks, however, the Co content can reach up to 2% without incurring increased costs.
  • the element iron occurs i.a. as an accompaniment element. Reducing the iron content to well below 1% increases the costs, since higher-quality starting materials would have to be selected. With a Fe content limited to 3%, you do not have to expect a significant deterioration of the corrosion resistance and not too high costs of the starting materials. However, an Fe content below 1% should be sought.
  • Mn The conditions mentioned for Fe also apply to Mn, whereby the Mn content can be reduced to less than 1% without much effort.
  • the alloy can be prepared by the usual methods of a melt operation, advantageously a melting in a vacuum with subsequent remelting in the electroslag process is useful.
  • a melting in a vacuum with subsequent remelting in the electroslag process is useful.
  • the formability for the production of rods for further processing to valves, such as marine diesel valves, is given.
  • the alloy according to the invention is also particularly suitable for the production of valves for large diesel engines in general, that is, for example, for such large diesel engines that are used in stationary facilities for power generation.

Abstract

Austenitic heat-resistant nickel-base alloy comprising (in % by mass) 0.03-0.1% of C, 28-32% of Cr, 0.01-≤ 0.5% of Mn, 0.01-≤ 0.3% of Si, 0.01-≤ 1.0% of Mo, 2.5-3.2% of Ti, 0.01-≤ 0.5% of Nb, 0.01-≤ 0.5% of Cu, 0.05-≤ 2.0% of Fe, 0.7-1.0% of Al, 0.001-≤ 0.03% of Mg, 0.01-≤ 1.0% of Co, 0.01-0.10% of Hf, 0.01-0.10% of Zr, 0.002-0.02% of B, 0.001-0.01% of N, max. 0.01% of S, max. 0.005% of Pb, max. 0.0005% of Bi, max. 0.01% of Ag, balance Ni and minor components due to the production method, where the sum of Ti + Al is from 3.3 to 4.3%, the sum of C + (10 × B) is from 0.05 to 0.2%, the sum of Hf + Zr is from 0.05 to 0.15% and the Ti/Al ratio is > 3.

Description

Austenitische warmfeste Nickel-Basis-Legierung Austenitic heat-resistant nickel-based alloy
Die Erfindung betrifft eine austenitische warmfeste Nickel-Basis-Legierung.The invention relates to an austenitic heat-resistant nickel-based alloy.
Das Institute of Marine Engineers mit den „Proceedings" Diesel Engine Combustion Chamber Materials for Heavy Fuel Operation, 1990, vermittelt eine Zusammenfassung bezüglich des damaligen Stands der Technik und der in den vorangegangenen Jahren durchgeführten intensiven Forschungs- und Entwicklungsarbeiten auf dem Gebiet der Ventilwerkstoffe. Etabliert hat sich danach für diese Anwendung hauptsächlich Alloy 80 A mit (in Masse-%) 0,08 % C, 19,5 % Cr, 75 % Ni, 1 ,4 % AI sowie 2,4 % Ti.The Institute of Marine Engineers, with the "Proceedings" Diesel Engine Combustion Chamber Materials for Heavy Fuel Operation, 1990, provides a summary of the state of the art and the extensive research and development efforts in the field of valve materials made in previous years After that, for this application, it was mainly Alloy 80 A with (in mass%) 0.08% C, 19.5% Cr, 75% Ni, 1.4% Al and 2.4% Ti.
Vereinzelt wurde auch Alloy 81 mit (in Masse-%) 0,05 % C, 30 % Cr, 66 % Ni, 0,9 % AI sowie 1 ,8 % Ti genutzt. Fallweise werden diese Legierungen als Ventilgrundmaterialien eingesetzt, wobei die Ventilsitzpartie zusätzlich mit einem abriebfesten Material beschichtet wird, wie es beispielsweise in der EP-B 0521821 beschrieben ist. Diese Druckschrift gibt die chemische Zusammensetzung (in Masse %) für das Grundmaterial wie folgt an: 0,04 - 0,10 % C1 ≤ 1 ,0 % Si, < 0,2 % Cu, < 1 ,0 % Fe, < 1 ,9 % Mn, 18 - 21 % Cr, 1 ,8 - 2,7 % Ti, 1 ,0 - 1 ,8 % AI, < 2,0 % Co, < 0,3 % Mo, B, Zr, Rest Nickel. Ferner ist eine Variante dieser Legierung unter anderem auch mit 29 - 31 % Cr angeführt.Occasionally, Alloy 81 with (in% by mass) 0.05% C, 30% Cr, 66% Ni, 0.9% Al and 1.8% Ti was used. Occasionally, these alloys are used as valve base materials, wherein the valve seat section is additionally coated with an abrasion-resistant material, as described for example in EP-B 0521821. This document gives the chemical composition (in mass%) of the base material as follows: 0.04 - 0.10% C 1 ≤ 1, 0% Si, <0.2% Cu, <1, 0% Fe, < 1, 9% Mn, 18-21% Cr, 1, 8-2.7% Ti, 1, 0-1, 8% Al, <2.0% Co, <0.3% Mo, B, Zr, Rest of nickel. Furthermore, a variant of this alloy is also mentioned among other things with 29 - 31% Cr.
Bei den gegenwärtigen Einsatztemperaturen von unter 750° C zeichnete sich Alloy 80 A durch eine höhere Lebensdauer in LCF-Versuchen und eine bessere Abriebfestigkeit aus, während Alloy 81 wegen seiner besseren Korrosionsbeständigkeit unter den Bedingungen, wie sie zum Beispiel in Schiffsdieselmotoren anzutreffen sind, geprüft wurde. Jede dieser Legierungen hat also ihre besonderen Vorteile, keine jedoch erfüllt sämtliche Anforderungen an die mechanischen und korrosiven Eigenschaften. Die Abhilfe mit einer zusätzlichen Beschichtung bringt weitere unerwünschte Fertigungs- und Materialkosten mit sich. Unter Kostengesichtspunkten ungünstig ist auch der pulvermetallurgische Fertigungsweg. Derartige Kosten sollen möglichst vermieden werden. Hierauf beziehen sich sowohl die US-A 6,139,660, als auch die US-A 6,039,919, welche eine Legierung folgender Zusammensetzung (in Masse %) für Ein- und Auslassventile von Dieselmotoren beschreiben: ≤ 0,1 % C, ≤ 1 ,0 % Si, ≤ 0,1 % Mn, ≥ 25 - < 32,2 % Cr, ≤ 3 % Ti, > 1 - < 2 % AI, Rest Ni. Aber auch diese Legierung bringt keine ausreichende Heißkorrosionsbeständigkeit mit sich. Hinzu kommt, dass zukünftig leistungsfähigere Motoren, wie Schiffsdieselmotoren, bei Temperaturen bis etwa 850° C betrieben werden, was auch an den Ventilwerkstoff höhere Anforderungen stellt, zumal die Lebensdauer erhalten werden soll und auch keine zusätzlichen Wartungsarbeiten erwünscht sind.At current operating temperatures below 750 ° C, Alloy 80 A has been characterized by a longer life in LCF tests and better abrasion resistance, while Alloy 81 has been tested for its better corrosion resistance under the conditions found in marine diesel engines, for example , Each of these alloys therefore has its own advantages, but none meets all the requirements for mechanical and corrosive properties. The remedy with an additional coating brings with it further undesirable manufacturing and material costs. From a cost point of view unfavorable is also the powder metallurgical manufacturing process. Such costs should be avoided as far as possible. Both US Pat. No. 6,139,660 and US Pat. No. 6,039,919, which describe an alloy of the following composition (in% by mass) for intake and exhaust valves of diesel engines, relate to this: ≦ 0.1% C, ≦ 1.0% Si , ≤ 0.1% Mn, ≥ 25 - <32.2% Cr, ≤ 3% Ti,> 1 - <2% Al, balance Ni. But even this alloy does not provide sufficient hot corrosion resistance. In addition, in the future, more powerful engines, such as marine diesel engines, are operated at temperatures up to about 850 ° C, which also makes higher demands on the valve material, especially since the service life is to be maintained and no additional maintenance is desired.
Durch die DE-C 101 23 566 ist eine austenitische warmfeste Nickel-Basis- Legierung bekannt geworden, die (in Masse %) folgende Zusammensetzung aufweist: 0,03 - 0,1 % C, max. 0,005 % S, max. 0,05 % N, 25 - 35 % Cr, max. 0,2 % Mn, max. 0,1 % Si, max. 0,2 % Mo, 2 - 3 % Ti, 0,02 - 1 ,1 % Nb, max. 0,1 % Cu, max. 1 % Fe, max. 0,08 % P, 0,9 - 1 ,3 % AI, max. 0,01 % Mg, 0,02 - 0,1 % Zr, max. 0,2% Co, wobei die Summe aus Al+Ti+Nb > 3,5 % ist, Rest Ni sowie herstellungsbedingte Bedingungen. Die Legierung ist gekennzeichnet durch Zusätze von (in Masse %) 0,001-0,005 % B, 0,01-0,04 % Hf, sowie 0,01-0,04 % Y.DE-C 101 23 566 discloses an austenitic heat-resistant nickel-based alloy which has the following composition (in% by mass): 0.03-0.1% C, max. 0.005% S, max. 0.05% N, 25-35% Cr, max. 0.2% Mn, max. 0.1% Si, max. 0.2% Mo, 2 - 3% Ti, 0.02 - 1, 1% Nb, max. 0.1% Cu, max. 1% Fe, max. 0.08% P, 0.9-1.3% AI, max. 0.01% Mg, 0.02 - 0.1% Zr, max. 0.2% Co, the sum of Al + Ti + Nb being> 3.5%, the remainder being Ni and production-related conditions. The alloy is characterized by additions of (in% by mass) 0.001-0.005% B, 0.01-0.04% Hf, and 0.01-0.04% Y.
Der Erfindung liegt die Aufgabe zugrunde, einen bis zu Temperaturen von 850° C heißkorrosionsbeständigen Werkstoff mit mechanischen Eigenschaften, welche denen von Alloy 80 A nicht nachstehen, bereitzustellen.The invention has for its object, up to a temperature of 850 ° C hot corrosion resistant material with mechanical properties which are not inferior to those of Alloy 80 A.
Diese Aufgabe wird gelöst durch eine austenitische warmfeste Nickel-Basis- Legierung mit (in Masse %)This object is achieved by an austenitic heat-resistant nickel-based alloy with (in% by mass)
0,03 - 0,1 % C 28 - 32 % Cr 0,01 - < 0,5 % Mn 0,01 - < 0,3 % Si 0,01 - < 1 ,0 % Mo 2,5 - 3,2 % Ti 0,01 - < 0,5 % Nb 0,01 - < 0,5 % Cu 0,05 - < 2,0 % Fe0.03 - 0.1% C 28 - 32% Cr 0.01 - <0.5% Mn 0.01 - <0.3% Si 0.01 - <1.0% Mo 2.5 - 3, 2% Ti 0.01 - <0.5% Nb 0.01 - <0.5% Cu 0.05 - <2.0% Fe
0,7 - 1 ,0 % AI0.7 - 1, 0% AI
0,001 - < 0,03 % Mg0.001 - <0.03% Mg
0,01 - < 1 ,0 % Co0.01 - <1.0% Co
0,01 - 0,10 % Hf0.01 - 0.10% Hf
0,01 - 0,10 % Zr0.01 - 0.10% Zr
0,002 - 0,02 % B0.002-0.02% B
0,001 - 0,01 % N max. 0,01 % S max. 0,005 Pb max. 0,0005 % Bi max. 0,01 % Ag0.001 - 0.01% N max. 0.01% S max. 0.005 Pb max. 0.0005% Bi max. 0.01% Ag
Rest Ni und herstellungsbedingte Beimengungen, wobei die Summe aus Ti + AI zwischen 3,3 und 4,3 % liegt, die Summe aus C + (10 x B) zwischen 0,05 und 0,2 % liegt, die Summe aus Hf + Zr zwischen 0,05 und 0,15 % liegt und das Verhältnis Ti/Al > 3 ist.Remaining Ni and production-related admixtures, where the sum of Ti + Al is between 3.3 and 4.3%, the sum of C + (10 x B) is between 0.05 and 0.2%, the sum of Hf + Zr is between 0.05 and 0.15% and the ratio Ti / Al> 3.
Vorteilhafte Weiterbildungen der erfindungsgemäßen bis zu 850° C heißkorrosionsbeständigen Nickel-Basis-Legierung sind den zugehörigen Unteransprüchen zu entnehmen.Advantageous developments of the inventive up to 850 ° C hot corrosion resistant nickel-based alloy can be found in the associated dependent claims.
Derartige heißkorrosionsbeständige Werkstoffe erreichen mechanische Eigenschaften, welche denen von Alloy 80 A nicht nachstehen. Insofern ist der erfindungsgemäße Werkstoff als Ventilwerkstoff allgemein einsetzbar und im speziellen für zukünftige Generationen von Schiffsdieselmotoren im Temperaturbereich bis maximal 850° C einsetzbar.Such hot corrosion resistant materials achieve mechanical properties that are not inferior to those of Alloy 80 A. In this respect, the material of the invention as a valve material is generally applicable and can be used in particular for future generations of marine diesel engines in the temperature range up to 850 ° C.
Tabelle 1 zeigt beispielhaft die chemische Zusammensetzung zweier erfindungsgemäßer Beispiele E1 und E2. Zum besseren Vergleich sind zwei typische Analysen der handelsüblichen Legierungen Alloy 80 A und Alloy 81 aufgeführt. Die Analysen der Legierungen E1 und E2 gingen aus einer Serie von Laborschmelzen hervor, die in 10 kg schweren Blöcken im Vakuum-Induktionsofen erschmolzen, anschließend warmgewalzt und bei 1180° C für zwei Stunden in Luft mit anschließender Wasserabschreckung lösungsgeglüht wurden. Die Aushärtung der Legierungen erfolgte durch zwei weitere Glühungen:Table 1 shows an example of the chemical composition of two inventive examples E1 and E2. For a better comparison, two typical analyzes of the commercial alloys Alloy 80 A and Alloy 81 are listed. The analyzes of the alloys E1 and E2 were obtained from a series of laboratory melts, which were melted in 10 kg blocks in the vacuum induction furnace, then hot rolled and solution heat treated at 1180 ° C for two hours in air with subsequent water quenching. The hardening of the alloys took place by two further annealing:
6 Stunden bei 850° C mit Luftabkühlung gefolgt von 4 Stunden bei 700° C mit Luftabkühlung6 hours at 850 ° C with air cooling followed by 4 hours at 700 ° C with air cooling
Die Legierungen unterschieden sich im Gehalt der unten diskutierten Elemente, so dass die Auswertung ihrer mechanischen Eigenschaften und ihres Verhaltens im korrosiven Medium zu der erfindungsgemäßen Analyse führte.The alloys differed in the content of the elements discussed below, so that the evaluation of their mechanical properties and their behavior in the corrosive medium led to the analysis according to the invention.
Tabelle 1Table 1
Chemische Zusammensetzung der erfindungsgemäßen Legierungen E1 und E2 imChemical composition of the alloys E1 and E2 according to the invention in
Vergleich zu Alloy 80 A und Alloy 81Compared to Alloy 80 A and Alloy 81
(Masse %) Da ein erfindungsgemäßes Ziel mit Alloy 80 A vergleichbare Warmfestigkeiten bei Einsatztemperatur war, wurden Zugfestigkeit und Streckgrenze bei 600° C und 800° C gemessen. Tabelle 2 zeigt, dass bei 6000C Alloy 80 A vergleichbar und sogar noch fester ist. Bei 800° C sind die Legierungen vergleichbar.(Dimensions %) Since an Alloy 80 A target according to the present invention was comparable in heat resistance at the use temperature, tensile strength and yield strength were measured at 600 ° C and 800 ° C. Table 2 shows that at 600 0 C Alloy 80 A is comparable and even tighter. At 800 ° C, the alloys are comparable.
Tabelle 2Table 2
Zugfestigkeit und Streckgrenze von E1 und E2 im Vergleich mit Alloy 80 A bei 600°Tensile strength and yield strength of E1 and E2 in comparison with Alloy 80 A at 600 °
C und 800° CC and 800 ° C
Für die Untersuchung des Korrosionsverhaltens wurden zunächst Proben im Labor in synthetischer Ölasche folgender Zusammensetzung durchgeführt:For the investigation of the corrosion behavior first samples in the laboratory were carried out in synthetic oil ash of the following composition:
40 % V2O3 + 10 % NaVO3 + 20 % Na2SO4 + 15 % CaSO4 + 15 % NiSO4.40% V 2 O 3 + 10% NaVO 3 + 20% Na 2 SO 4 + 15% CaSO 4 + 15% NiSO 4 .
Die Atmosphäre war Luft mit einem SO2-Gehalt von 0,5 %. Die Proben wurden sowohl bei 750 °C als auch bei 850 °C jeweils für 20 Stunden, 100 Stunden und 400 Stunden ausgelagert. Bei der 400 Stunden Auslagerung wurde die Asche nach 100 Stunden, 200 Stunden und 300 Stunden erneuert, um die Korrosivität aufrecht zu erhalten. Bei den Laborversuchen konnte die Tiefe der inneren Korrosion zuverlässig ausgemessen werden.The atmosphere was air with an SO 2 content of 0.5%. The samples were swapped out at both 750 ° C and 850 ° C for 20 hours, 100 hours and 400 hours, respectively. In the 400 hours aging, the ash was renewed after 100 hours, 200 hours and 300 hours to maintain the corrosiveness. In the laboratory experiments, the depth of the internal corrosion could be reliably measured.
Als zuverlässiger - weil sie zum einen besser auswertbar sind und zum anderen auch erosive Effekte berücksichtigen - sind die Korrosionsuntersuchungen im Schiffsdieselventil selbst einzuschätzen. Es wurden von jeder Laborschmelze und zum Vergleich auch von dem Material Alloy 81 sowie 80 A Proben in einem Schiffsdieselventil eingesetzt. Dieses Schiffsdieselventil lief über 3000 Stunden in der Hauptmaschine eines weltweit fahrenden Hochseeschiffes. Anschließend wurden die Proben dem Ventil entnommen und der Korrosionsangriff metallographisch untersucht. Hier konnten Materialverlust, Schichtdicke und innerer Korrosionsangriff detailliert voneinander unterschieden werden.As a reliable - because they are on the one hand better evaluable and on the other also take into account erosive effects - the corrosion studies in the marine diesel valve itself can be estimated. From each laboratory melt and for comparison also from the material Alloy 81 and 80 A samples were used in a marine diesel valve. This marine diesel valve ran over 3000 hours in the main engine of a high-speed oceangoing ship. Subsequently the samples were taken from the valve and the corrosion attack was examined metallographically. Here, material loss, layer thickness and internal corrosion attack were distinguished in detail from each other.
Aus den Untersuchungen resultierten folgende Abhängigkeiten des Korrosionsverhaltens von dem Gehalt der einzelnen Legierungselemente.The following dependencies of the corrosion behavior on the content of the individual alloying elements resulted from the investigations.
Cr: der Cr-Gehalt muss aus Korrosionssicht so hoch wie möglich sein. Metallurgisch liegt aber bei 32% eine sinnvolle Obergrenze. Das zeigt der deutliche Unterschied zwischen den Legierungsvarianten mit ca. 30% Cr und denen mit 20% Cr. Der Korrosionsangriff bei erstgenannten Legierungen ist im günstigsten Fall nur halb so groß. Die im Ventil getesteten Proben mit einem Cr-Gehalt von 30 % zeigen auf Makroaufnahmen ein pflastersteinartiges Aussehen, das sich in den Schliffbildern als wellige Probenoberfläche widerspiegelt, was als Zeichen für nur mäßigen Korrosionsabtrag ist. Im Gegensatz dazu weisen die Cr ärmeren Proben bereits starke ebenmäßige Abplatzungen auf.Cr: The Cr content must be as high as possible from the corrosion point of view. Metallurgically, however, 32% is a sensible upper limit. This shows the clear difference between the alloy variants with about 30% Cr and those with 20% Cr. The corrosion attack in the first mentioned alloys is at best only half as large. The samples tested in the valve with a Cr content of 30% show a cobblestone-like appearance on macro photographs, which is reflected in the micrographs as a wavy sample surface, which is indicative of only moderate corrosion erosion. In contrast, the poorer samples already show strong even flaking.
Ti, AI: Ein Verhältnis TkAI von > 3 resultiert in einer besseren Korrosionsbeständigkeit als geringere Ti:AI-Verhältnisse. Dies wird auf die Bildung eines Ti-reichen Saums zwischen äußerer Oxidschicht und dem Bereich innerer Sulfidierung bei hohen Ti-Gehalten zurückgeführt. Aluminium und Titan wirken sich durch Bildung von γ'-Phase positiv auf die Warmfestigkeit aus. Die Summe der Elemente AI + Ti sollte vorteilhafterweise zwischen 3,5 und 4,3 % liegen. Ein zu hoher Gesamtgehalt dieser Elemente erschwert die Warmformgebung des Materials.Ti, Al: A TkAI ratio of> 3 results in better corrosion resistance than lower Ti: Al ratios. This is attributed to the formation of a Ti-rich seam between the outer oxide layer and the region of internal sulfidation at high Ti contents. Aluminum and titanium have a positive effect on the heat resistance due to the formation of γ'-phase. The sum of the elements Al + Ti should advantageously be between 3.5 and 4.3%. Too high a total content of these elements makes the thermoforming of the material difficult.
Si: Silizium hat den Untersuchungen zufolge keinen positiven Effekt auf die Korrosionseigenschaften und sollte maximal 0,5 % betragen, besser ist weniger als 0,1%.Si: Silicon has been found to have no positive effect on corrosion properties and should be no more than 0.5%, better less than 0.1%.
Nb: Die Niob-Iegierten Proben haben prinzipiell die dünnste Korrosionsschicht, dies hat jedoch keine Auswirkung auf den Materialverlust selbst. Da eine dicke Korrosionsschicht schützender gegen das Fortschreiten des Korrosionsangriffs wirkt, sollte der Nb- Gehalt auf maximal 0,5% beschränkt werden. Des Weiteren beeinflusst das Nb aufgrund seiner hohen Löslichkeit in der γ'-Phase die Materialfestigkeit. Bei geringeren Nb-Gehalten unter 0,5% müssen der Ti und AI- Gehalt nicht angepasst werden.Nb: The niobium-alloyed samples basically have the thinnest corrosion layer, but this has no effect on the material loss itself Protective corrosion layer acts against the progression of the corrosion attack, the Nb content should be limited to a maximum of 0.5%. Furthermore, the Nb influences the material strength due to its high solubility in the γ'-phase. At lower Nb levels below 0.5%, the Ti and Al content need not be adjusted.
B, C: Die Zugabe von Bor in Gehalten von 0,002 - 0,01 % verbessert die Korrosionsbeständigkeit dahingehend, dass die innere Sulfidierung, die bevorzugt entlang der Korngrenzen verläuft, reduziert und damit der gesamte Korrosionsangriff verringert wird. Kohlenstoff bildet bevorzugt an den Korngrenzen Cr-Carbide. Bor bildet Boride, die zur Stabilisierung der Korngrenzen und damit zur Langzeitfestigkeit beitragen. Insbesondere die sich bildenden Cr-Carbide führen zu einer Cr-Verarmung in der Nähe der Korngrenzen, weshalb bei zu hohem C-Gehalt die Korrosion beschleunigt fortschreitet. Außerdem dürfen Carbide und Boride die Korngrenzen nicht zu stark belegen, da sie dann als harte Ausscheidungen die Duktilität des Materials stark herabsetzen. Als Kompromiss hat sich herausgestellt, dass die Summe von C + (10 x B) 0,1 % nicht überschreiten sollte. Vorteilhafterweise liegt die genannte Summe bei etwa 0,08 %.B, C: The addition of boron at levels of 0.002 - 0.01% improves corrosion resistance by reducing the internal sulfidation, which preferably proceeds along the grain boundaries, and thus reducing overall corrosion attack. Carbon preferably forms Cr carbides at the grain boundaries. Boron forms borides, which contribute to the stabilization of the grain boundaries and thus to long-term stability. In particular, the forming Cr carbides lead to a Cr depletion in the vicinity of the grain boundaries, which is why at a high C content, the corrosion accelerated progresses. In addition, carbides and borides must not overburden the grain boundaries, as they then hard precipitates greatly reduce the ductility of the material. As a compromise, it has been found that the sum of C + (10 x B) should not exceed 0.1%. Advantageously, said sum is about 0.08%.
Hf: Hafnium wird häufig zur Verbesserung der Hochtemperatur- Oxidationsbeständigkeit beigegeben und beeinflusst offensichtlich auch die Beständigkeit der Proben in Vanadiumasche und SO2 - Atmosphäre positiv. Des Weiteren verändert Hf unter Carbid- oder Carbosulfid-Bildung ebenfalls die Korngrenzeneigenschaften. Ein zu hoher Hf-Gehalt ist zu vermeiden, da sonst die Warmformgebung nicht mehr gewährleistet ist. Es ergibt sich daraus ein günstiger Konzentrationsbereich zwischen 0,02 und 0,08%, bevorzugt 0,05%. Die Wirkung des Hf auf die Korngrenzen ist vergleichbar mit der Wirkung des Zr, weshalb sich vorteilhafter Weise die Summenformel Hf + Zr < 0,10 % ergibt.Hf: Hafnium is often added to improve the high temperature oxidation resistance and obviously also influences the durability of the samples in vanadium ash and SO 2 atmosphere positively. Furthermore, Hf also changes the grain boundary properties under carbide or carbosulfide formation. Too high an HF content should be avoided, as otherwise the hot forming is no longer guaranteed. This results in a favorable concentration range between 0.02 and 0.08%, preferably 0.05%. The effect of Hf on the grain boundaries is comparable to the effect of Zr, which is why the empirical formula Hf + Zr <0.10% advantageously results.
Zr: Zirkon bildet Carbosulfide, welche sich positiv auf die Langzeitfestigkeit auswirken und durch die Bindung von Schwefel auch zur Heißkorrosionsbeständigkeit beitragen. Es zeigte sich, dass sich ein Zr-Gehalt zwischen 0,01 und 0,05% positiv auswirkt. Anzustreben ist ein Zr-Gehalt im Bereich von 0,02%.Zr: Zirconium forms carbosulfides, which have a positive effect on the long-term strength and also contribute to the hot corrosion resistance by the binding of sulfur. It turned out that a Zr content between 0.01 and 0.05%. The aim is to have a Zr content in the range of 0.02%.
Co: Co ist ein Element, das prinzipiell die Beständigkeit gegenüber schwefelhaltigen Medien erhöht. Dem gegenüber ist es aber auch sehr teuer, weshalb auf das Zulegieren von Co verzichtet wird. Aufgrund von Beimengungen in den Einsatzstoffen kann der Co-Gehalt jedoch bis zu 2% erreichen, ohne dass erhöhte Kosten entstehen.Co: Co is an element that in principle increases the resistance to sulfur-containing media. On the other hand, it is also very expensive, which is why the co-alloying of Co is dispensed with. Due to admixtures in the feedstocks, however, the Co content can reach up to 2% without incurring increased costs.
Fe: Das Element Eisen tritt u.a. als Begleitelement auf. Eine Reduzierung des Eisengehalts auf deutlich unter 1% erhöht die Kosten, da hochwertigere Einsatzstoffe gewählt werden müssten. Bei einem auf 3% limitierten Fe-Gehalt muss man nicht mit einer deutlichen Verschlechterung der Korrosionsbeständigkeit rechnen und auch nicht mit zu hohen Kosten der Einsatzstoffe. Ein Fe-Gehalt unter 1 % ist jedoch anzustreben.Fe: The element iron occurs i.a. as an accompaniment element. Reducing the iron content to well below 1% increases the costs, since higher-quality starting materials would have to be selected. With a Fe content limited to 3%, you do not have to expect a significant deterioration of the corrosion resistance and not too high costs of the starting materials. However, an Fe content below 1% should be sought.
Mn: Die für Fe erwähnten Bedingungen gelten auch für Mn, wobei sich der Mn- Gehalt ohne großen Aufwand unter 1% reduzieren lässt.Mn: The conditions mentioned for Fe also apply to Mn, whereby the Mn content can be reduced to less than 1% without much effort.
Obwohl der Einfluss der verschiedenen Elemente auf Korrosionsverhalten und Warmfestigkeit häufig gegenläufig ist, konnten mit den Legierungen E1 und E2 Zusammensetzungen gefunden werden, welche die gestellten Anforderungen an das Hochtemperatur-Korrosionsverhalten und die Warmfestigkeit bei Temperaturen im Bereich zwischen 600 0C und 850 °C gleichzeitig erfüllen. Erklärbar ist die gute Korrosionsbeständigkeit durch die Zugabe der reaktiven Elemente, wie Hafnium und Zirkon, ohne dabei das gewählte Optimum (0,05 - 0,10 %) zu überschreiten. Höhere Gehalte verstärken den in das Material hinein gerichteten Korrosionsangriff. Die Limitierungen des Kohlenstoffgehaltes < 0,1 % und die von Mangan < 1 % tragen zusätzlich zur Korrosionsbeständigkeit bei. Für die Warmfestigkeit hat es sich als besonders günstig erwiesen, wenn Aluminium und Titan zugegeben werden, wobei ihr Summengehalt - wie bereits dargelegt - im Bereich zwischen 3,5 und 4,3 % liegen soll. Diese Warmfestigkeiten machen eine Beschichtung der Sitzpartie des Ventils überflüssig, wodurch Fertigungskosten eingespart werden können.Although the influence of various elements on corrosion resistance and heat resistance is often in opposite directions, could with the alloys E1 and E2 compositions are found that the requirements for the high-temperature corrosion behavior detected and the heat resistance at the same time at temperatures ranging between 600 0 C and 850 ° C fulfill. The good corrosion resistance can be explained by the addition of the reactive elements, such as hafnium and zirconium, without exceeding the selected optimum (0.05-0.10%). Higher levels increase the corrosion attack directed into the material. The limitations of the carbon content <0.1% and that of manganese <1% additionally contribute to the corrosion resistance. For the heat resistance, it has proved to be particularly favorable when aluminum and titanium are added, with their Summenge - as already stated - should be in the range between 3.5 and 4.3%. These warmth strengths make one Coating the seat portion of the valve superfluous, thereby manufacturing costs can be saved.
Die Legierung kann mit den üblichen Methoden eines Schmelzbetriebes hergestellt werden, wobei vorteilhafterweise eine Erschmelzung im Vakuum mit einer anschließenden Umschmelzung im Elektroschlackeverfahren sinnvoll ist. Die Umformbarkeit für die Herstellung von Stangen zur Weiterfertigung zu Ventilen, wie beispielsweise Schiffsdieselventilen, ist gegeben.The alloy can be prepared by the usual methods of a melt operation, advantageously a melting in a vacuum with subsequent remelting in the electroslag process is useful. The formability for the production of rods for further processing to valves, such as marine diesel valves, is given.
Die erfindungsgemäße Legierung eignet sich insbesondere auch für die Herstellung von Ventilen für Großdieselmotoren im Allgemeinen, also beispielsweise auch für solche Großdieselmotoren, die in Stationäranlagen zur Stromgewinnung eingesetzt werden. The alloy according to the invention is also particularly suitable for the production of valves for large diesel engines in general, that is, for example, for such large diesel engines that are used in stationary facilities for power generation.

Claims

Patentansprüche claims
1. Austenitische warmfeste Nickel-Basis-Legierung mit (in Masse-%) 0,03-0,1 %C1. Austenitic heat-resistant nickel-based alloy containing (in mass%) 0.03-0.1% C
28 - 32 % Cr28 - 32% Cr
0,01 -<0,5%Mn0.01 - <0.5% Mn
0,01 - < 0,3 % Si0.01 - <0.3% Si
0,01 -≤ 1,0% Mo0.01-≤ 1.0% Mo
2,5 - 3,2 % Ti2.5-3.2% Ti
0,01 -< 0,5% Nb0.01 - <0.5% Nb
0,01 -<0,5% Cu0.01 - <0.5% Cu
0,05 - < 2,0 % Fe0.05 - <2.0% Fe
0,7 -1,0 % AI0.7 -1.0% AI
0,001 -≤ 0,03% Mg0.001-.0.03% Mg
0,01 -≤ 1,0% Co0.01-≤ 1.0% Co
0,01 -0,10% Hf0.01 -0.10% Hf
0,01 -0,10% Zr0.01 -0.10% Zr
0,002 - 0,02 % B0.002-0.02% B
0,001 - 0,01 % N max.0,01 % S max.0,005 Pb max.0,0005 % Bi max.0,01 % Ag0.001 - 0.01% N max.0.01% S max.0.005 Pb max.0.0005% Bi max.0.01% Ag
Rest Ni und herstellungsbedingte Beimengungen, wobei die Summe aus Ti + AI zwischen 3,3 und 4,3 % liegt, die Summe aus C + (10 x B) zwischen 0,05 und 0,2 % liegt, die Summe aus Hf + Zr zwischen 0,05 und 0,15 % liegt und das Verhältnis Ti/Al > 3 ist.Remaining Ni and production-related admixtures, where the sum of Ti + Al is between 3.3 and 4.3%, the sum of C + (10 x B) is between 0.05 and 0.2%, the sum of Hf + Zr is between 0.05 and 0.15% and the ratio Ti / Al> 3.
2. Legierung nach Anspruch 1 , die (in Masse-%) 28 - 31 % Cr enthält.2. An alloy according to claim 1 containing (in mass%) 28-31% Cr.
3. Legierung nach Anspruch 1 oder 2, die (in Masse-%) 29 - 31 % Cr enthält. 3. The alloy of claim 1 or 2, which contains (in mass%) 29 - 31% Cr.
4. Legierung nach einem der Ansprüche 1 bis 3, die (in Masse-%) 2,8 - 3,2 % Ti enthält.4. An alloy according to any one of claims 1 to 3 containing (in mass%) 2.8-3.2% Ti.
5. Legierung nach einem der Ansprüche 1 bis 4, die (in Masse-%) 2,8 - 3,0 % Ti enthält.5. An alloy according to any one of claims 1 to 4 containing (in mass%) 2.8-3.0% Ti.
6. Legierung nach einem der Ansprüche 1 bis 5, die als Zugabe Bor (in Masse-%) 0,002 - 0,01 %, insbesondere 0,002 - 0,005 %, enthält.6. An alloy according to any one of claims 1 to 5, which contains as an addition of boron (in% by mass) 0.002 - 0.01%, in particular 0.002 - 0.005%.
7. Legierung nach einem der Ansprüche 1 bis 6, bei der die Summe aus C + (10 x B) zwischen 0,05 und 0,1 %, insbesondere zwischen 0,05 - 0,08 %, liegt.7. An alloy according to any one of claims 1 to 6, wherein the sum of C + (10 x B) between 0.05 and 0.1%, in particular between 0.05 - 0.08%.
8. Legierung nach einem der Ansprüche 1 bis 7, bei der der Zr-Gehalt zwischen 0,01 und 0,05 % eingestellt ist.8. An alloy according to any one of claims 1 to 7, wherein the Zr content is adjusted between 0.01 and 0.05%.
9. Legierung nach einem der Ansprüche 1 bis 8, bei der der Hf-Gehalt zwischen 0,01 und 0,08 % eingestellt ist.9. An alloy according to any one of claims 1 to 8, wherein the Hf content is set between 0.01 and 0.08%.
10. Legierung nach einem der Ansprüche 1 bis 9, bei der der folgende Verhältnismäßigkeit gegeben ist:10. An alloy according to any one of claims 1 to 9, wherein the following proportionality is given:
Zr / Hf = 0,1 - 0,5 %.Zr / Hf = 0.1-0.5%.
11. Legierung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das Verhältnis Ti / AI zwischen 3,3 und 4,2 beträgt.11. An alloy according to any one of claims 1 to 9, characterized in that the ratio Ti / Al is between 3.3 and 4.2.
12. Verwendung der Legierung gemäß einem der Ansprüche 1 bis 11 , als Ventilwerkstoff, insbesondere für in Dieselmotoren einsetzbare Ventile.12. Use of the alloy according to one of claims 1 to 11, as a valve material, in particular for usable in diesel engines valves.
13. Verwendung der Legierung nach einem der Ansprüche 1 bis 11 , als Ventilwerkstoff für im Temperaturbereich bis 8500C einsetzbare Ventile in Schiffsdieselmotoren. 13. Use of the alloy according to one of claims 1 to 11, as a valve material for usable in the temperature range up to 850 0 C valves in marine diesel engines.
14. Ventil, insbesondere Ventil für einen Großdieselmotor, das zumindest teilweise aus einer Legierung gemäß einem der Ansprüche 1 bis 11 besteht. 14. Valve, in particular valve for a large diesel engine, which consists at least partially of an alloy according to one of claims 1 to 11.
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