EP2227572A1 - Alliage austénitique à base de nickel résistant à la chaleur - Google Patents

Alliage austénitique à base de nickel résistant à la chaleur

Info

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
Authority
EP
European Patent Office
Prior art keywords
alloy
max
alloy according
mass
sum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08865541A
Other languages
German (de)
English (en)
Other versions
EP2227572B1 (fr
Inventor
Jutta KLÖWER
Bernd De Boer
Dietmar Schlager
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VDM Metals GmbH
Original Assignee
ThyssenKrupp VDM GmbH
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Publication of EP2227572A1 publication Critical patent/EP2227572A1/fr
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Publication of EP2227572B1 publication Critical patent/EP2227572B1/fr
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Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Lift Valve (AREA)

Abstract

Alliage austénitique à base de nickel résistant à la chaleur avec (en % en masse) : 0,03 à 0,1 % C, 28 à 32 % Cr, 0,01 à ≤ 0,5 % Mn, 0,01 à ≤ 0,3 % Si, 0,01 à ≤ 1,0 % Mo, 2,5 à 3,2 % Ti, 0,01 à ≤ 0,5 % Nb, 0,01 à ≤ 0,5 % Cu, 0,05 à ≤ 2,0 % Fe, 0,7 à 1,0 % Al, 0,001 à ≤ 0,03 % Mg, 0,01 à ≤ 1,0 % Co, 0,01 à 0,10 % Hf, 0,01 à 0,10 % Zr, 0,002 à 0,02 % B, 0,001 à 0,01 % N, au plus 0,01 % S, au plus 0,005 Pb, au plus 0,0005 % Bi, au plus 0,01 % Ag, le reste étant du nickel et des additifs imposés par la fabrication. La somme Ti + Al est comprise entre 3,3 et 4,3 %, la somme C + (10 x B) est comprise entre 0,05 et 0,2 %, la somme Hf + Zr est comprise entre 0,05 et 0,15 %, et le rapport Ti/Al est > 3.
EP08865541.0A 2007-12-20 2008-11-25 Alliage austénitique à base de nickel résistant à la chaleur Active EP2227572B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007062417A DE102007062417B4 (de) 2007-12-20 2007-12-20 Austenitische warmfeste Nickel-Basis-Legierung
PCT/DE2008/001964 WO2009079972A1 (fr) 2007-12-20 2008-11-25 Alliage austénitique à base de nickel résistant à la chaleur

Publications (2)

Publication Number Publication Date
EP2227572A1 true EP2227572A1 (fr) 2010-09-15
EP2227572B1 EP2227572B1 (fr) 2016-01-27

Family

ID=40445808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08865541.0A Active EP2227572B1 (fr) 2007-12-20 2008-11-25 Alliage austénitique à base de nickel résistant à la chaleur

Country Status (7)

Country Link
US (1) US20100310412A1 (fr)
EP (1) EP2227572B1 (fr)
JP (1) JP2011506771A (fr)
KR (1) KR101236222B1 (fr)
CN (1) CN101896630A (fr)
DE (1) DE102007062417B4 (fr)
WO (1) WO2009079972A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9050682B2 (en) 2010-11-16 2015-06-09 Daniel R. Danks Electroslag welding with alternating electrode weld parameters
CN102876953A (zh) * 2012-09-27 2013-01-16 无锡宏昌五金制造有限公司 镍铬高温合金
CN103882263A (zh) * 2012-12-19 2014-06-25 江苏龙鑫特殊钢实业总公司 核电蒸汽发生器抗振条用镍基合金及其应用
CN104451655B (zh) * 2013-09-13 2018-02-16 中国科学院金属研究所 抗高温材料用表面合金涂层复合材料、涂层及其制备方法
DE102014001330B4 (de) 2014-02-04 2016-05-12 VDM Metals GmbH Aushärtende Nickel-Chrom-Kobalt-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
DE102014001329B4 (de) * 2014-02-04 2016-04-28 VDM Metals GmbH Verwendung einer aushärtenden Nickel-Chrom-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
DE102014001328B4 (de) * 2014-02-04 2016-04-21 VDM Metals GmbH Aushärtende Nickel-Chrom-Eisen-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit
CN105838925B (zh) * 2015-01-12 2017-11-28 宝钢特钢有限公司 耐高温氧化镍基合金
CN104862532B (zh) * 2015-04-22 2017-01-11 苏州劲元油压机械有限公司 一种滤油网用镍合金丝及其制造工艺
CN104818430A (zh) * 2015-05-15 2015-08-05 钢铁研究总院 一种节镍耐高温气阀合金
JP6739187B2 (ja) * 2016-02-22 2020-08-12 株式会社神戸製鋼所 溶接用Ｎｉ基合金ソリッドワイヤおよびＮｉ基合金溶接金属の製造方法
CN106498236B (zh) * 2016-10-26 2017-11-10 济宁市北辰金属材料有限公司 一种玻璃纤维生产用合金坩埚及其制备方法
JP6842316B2 (ja) * 2017-02-17 2021-03-17 日本製鋼所Ｍ＆Ｅ株式会社 Ｎｉ基合金、ガスタービン材およびクリープ特性に優れたＮｉ基合金の製造方法
EP3620628A1 (fr) 2018-09-04 2020-03-11 Winterthur Gas & Diesel Ltd. Chambre de précombustion
CN109112363A (zh) * 2018-09-22 2019-01-01 广州宇智科技有限公司 一种溴化锂制冷机用耐腐蚀液态调幅分解型镍合金
CN109022922A (zh) * 2018-09-22 2018-12-18 广州宇智科技有限公司 一种船舶动力系统冷凝器用耐腐蚀液态调幅分解型镍合金

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EP0235075B1 (fr) * 1986-01-20 1992-05-06 Mitsubishi Jukogyo Kabushiki Kaisha Alliage à base de nickel et procédé pour sa fabrication
GB8922161D0 (en) * 1989-10-02 1989-11-15 Inco Alloys Ltd Exhaust valve alloy
EP0521821B1 (fr) * 1991-07-04 1996-07-31 New Sulzer Diesel Ag Soupape d'échappement d'un moteur à combustion interne du type Diesel et son procédé de fabrication
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Also Published As

Publication number Publication date
DE102007062417A1 (de) 2009-06-25
KR20100083847A (ko) 2010-07-22
DE102007062417B4 (de) 2011-07-14
WO2009079972A1 (fr) 2009-07-02
US20100310412A1 (en) 2010-12-09
JP2011506771A (ja) 2011-03-03
CN101896630A (zh) 2010-11-24
EP2227572B1 (fr) 2016-01-27
KR101236222B1 (ko) 2013-02-22

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