WO1998032887A1 - Alliage nickel-chrome-molybdene-silicium austenitique a haute resistance a la corrosion par les chlorures et les gaz chlores a chaud - Google Patents

Alliage nickel-chrome-molybdene-silicium austenitique a haute resistance a la corrosion par les chlorures et les gaz chlores a chaud Download PDF

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Publication number
WO1998032887A1
WO1998032887A1 PCT/EP1997/006592 EP9706592W WO9832887A1 WO 1998032887 A1 WO1998032887 A1 WO 1998032887A1 EP 9706592 W EP9706592 W EP 9706592W WO 9832887 A1 WO9832887 A1 WO 9832887A1
Authority
WO
WIPO (PCT)
Prior art keywords
max
alloy
chloride
molybdenum
chromium
Prior art date
Application number
PCT/EP1997/006592
Other languages
German (de)
English (en)
Inventor
Jutta KLÖWER
Ulrich Heubner
Original Assignee
Krupp Vdm Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Krupp Vdm Gmbh filed Critical Krupp Vdm Gmbh
Priority to EP97951980A priority Critical patent/EP0956371A1/fr
Priority to JP53151598A priority patent/JP2001509210A/ja
Priority to CA002279294A priority patent/CA2279294A1/fr
Publication of WO1998032887A1 publication Critical patent/WO1998032887A1/fr

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
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033—Ni as the principal constituent
    • B23K35/304—Ni as the principal constituent with Cr as the next major constituent
    • 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%
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F7/00—Casings, e.g. crankcases or frames
    • F02F2007/0097—Casings, e.g. crankcases or frames for large diesel engines

Definitions

  • the invention relates to an enitic nickel-chromium-molybdenum alloy with additions of silicon.
  • the alloy with the material number 2.4856 is difficult to process.
  • this alloy suffers a considerable loss of ductility at temperatures above 500 ° C., which can lead to crack formation in components that are pressurized and / or subject to high mechanical stress.
  • the start of excretion of the ductility-reducing excretions can be delayed by lowering the iron content.
  • the new alloy described in this document also has disadvantages.
  • the ductility-increasing measures listed reduce the corrosion resistance against gases containing high chlorine and chloride-containing deposits compared to the alloy with material number 2.4856. Even with this alloy, high corrosion rates occur due to the constantly increasing process and exhaust gas temperatures due to the increase in efficiency. Alloys of the type 2.4856 are also susceptible to hot corrosion due to sulphate-containing deposits, so that there is a considerable need for a different type of alloy with improved resistance to high-temperature corrosion.
  • the invention has for its object to develop an alloy with a significantly improved resistance to chlorine gas corrosion and chloride-containing deposits compared to the prior art with simultaneous increased resistance to sulphate corrosion and with high ductility in the entire temperature range up to 1000 ° C.
  • the task is solved by a silicon-containing nickel-chromium-molybdenum alloy, which (in mass%) consists of the following components:
  • the alloy according to the invention is distinguished by a significantly increased high-temperature corrosion resistance against chlorine-containing gases, chloride-containing ashes, deposits and salt compounds with simultaneous corrosion resistance against sulphate corrosion and wet corrosion as well as high ductility.
  • a preferred alloy is characterized by the following alloy components (in% by mass):
  • the alloy is advantageously suitable, on the one hand, for the production of pipes, in particular composite tubes, sheets, strip material, foils, wires and objects made from these semi-finished products, and on the other hand, corrosion protection applied as cladding or plating.
  • Table 1 shows, by way of example, analyzes of batches from the alloy (AF) according to the invention and the comparison alloys (G, H) lying outside the composition according to the invention. Alloy 2.4856 was used for comparison. All alloy variants were made from cast blocks by hot rolling followed by cold rolling at room temperature. The resistance of the alloy according to the invention to chloride corrosion can be seen from Figures 1 and 2.
  • FIG. 3 shows the metallographically determined corrosion attack of samples which are in a complex medium (chlorine-containing synthetic waste combustion gas (2.5 g / m 3 HC1, 1.3 g / m 3 S0 2 / 9% 0 2 , remainder N 2 ) with simultaneous exposure to boiler ash containing chloride) were stored at 600 ° C for 1000 hours.
  • chlorine-containing synthetic waste combustion gas 2.5 g / m 3 HC1, 1.3 g / m 3 S0 2 / 9% 0 2 , remainder N 2
  • the silicon-containing alloy according to the invention shows a significantly reduced corrosion attack.
  • Figure 4 shows corrosion attack after 1008 hours of cyclical aging of samples which were coated with a coating of Na 2 S0 4 / KCl before being aged at 750 ° C in an atmosphere containing chlorine and sulfur dioxide. This test is used to test the resistance to sulphate corrosion. How as can be seen from the figure, the alloy according to the invention also shows significantly lower corrosion rates than the alloy 2.4856 currently used under such corrosion conditions with this corrosion stress.
  • the excellent properties of the alloy according to the invention can be attributed to the silicon additives and the coordination of the alloy elements molybdenum, chromium and iron.
  • the silicon content of the alloy according to the invention should be between 0.6% and 1.7%, since at lower silicon contents the corrosion-inhibiting effect of the silicon no longer occurs and at higher silicon contents with the appearance of embrittling suicides and significant loss of ductility, particularly in the case of medium-sized ones Temperatures (500-800 ° C), can be expected. With silicon contents between 0.5 and 1.7%, the notched impact strength, measured on ISO V notched impact samples, does not drop below 100 J / cm, even after aging for 100 hours at 600 ° C, as shown in Figure 5.
  • the molybdenum content of the alloy according to the invention is limited to 10%, since, as can be seen from FIG. 4, the susceptibility to sulphate corrosion increases with higher molybdenum contents. A minimum molybdenum content is required to avoid wet corrosion in the event of a drop below the dew point.
  • the chromium content of the alloy according to the invention should be between 18% and 22% in order to ensure adequate corrosion resistance. Higher chromium contents make it difficult to process nickel-chromium-molybdenum alloys.
  • the alloy should also contain hafnium and / or rare earths and / or zirconium and / or yttrium, if an improved adhesion of protective oxide layers is required for specific applications, for example in automotive exhaust systems at high temperatures and / or with rapid temperature changes. However, the sum of these reactive elements should not exceed 0.5%.
  • the iron content of the alloy according to the invention is limited to a maximum of 5%, since at higher iron contents in chloride-containing media there is a risk of the formation of volatile iron chlorides. However, a minimum iron content of 1% is required to ensure the processability of the alloy.
  • the carbon content of the alloy according to the invention is limited to a maximum of 0.05% since there is a risk of intergranular corrosion at higher carbon contents.
  • the titanium and aluminum contents are each reduced to a maximum of 0.5%, the actually undesirable niobium content to a maximum of. 0.5% is limited, since these elements can lead to a loss of ductility due to the formation of intermetallic phases at medium temperatures.
  • the total addition of niobium, aluminum and titanium should not exceed 1%.
  • a minimum content of the oxygen-affine elements aluminum, titanium, magnesium and calcium is required to ensure good oxidation resistance.
  • the manganese content should be at least 0.05%, but not exceed 0.5%, since higher manganese contents have an unfavorable effect on the resistance to oxidation.
  • 0.001-0.01% boron is also added to improve processability.
  • the levels of phosphorus and sulfur should be kept as low as possible since these surface-active elements reduce both the high-temperature corrosion resistance and the ductility of the alloy.
  • the alloy according to the invention can be used for strips, foils, sheets, tubes (seamless or welded), wires, as cladding, as cladding or as a composite tube.
  • the alloy according to the invention can be produced either by block casting or by continuous casting after melting in a vacuum induction furnace or after open melting.
  • the alloy can be remelted, but is not absolutely necessary.
  • the hot shaping is carried out by forging, hot rolling or extrusion, the cold shaping by cold rolling, wire drawing or pilgrims.
  • the production of composite materials, for example plating on carbon steels can be carried out by one of the customary build-up welding processes, by cold or hot rolling of sheets and strips, by explosive plating or by one of the customary processes for producing bimetallic tubes.
  • the alloy is particularly suitable as a strip and sheet, pipe or cladding material for use in hot chlorine-containing gases or in the presence of chloride-containing deposits, such as in plants in the chemical industry, in plants for the thermal treatment of chlorine-containing chemical waste and contaminated soils as well as in automotive exhaust systems (bellows for decoupling the catalytic converter and engine).
  • the excellent resistance of the alloy to complex corrosive salt deposits makes the alloy also suitable for use as a cladding and construction material in plants for thermal waste disposal, in large diesel engines, in plants for energy generation from biomass and in plants of the pulp industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Exhaust Silencers (AREA)

Abstract

L'invention concerne un alliage nickel-chrome-molybdène-silicium austénitique à résistance à la corrosion nettement améliorée vis-à-vis des chlorures et des gaz chlorés à chaud, comme c'est le cas, par exemple, dans des installations de l'industrie chimique, des installations d'incinération d'ordures, des systèmes d'échappement de véhicules et dans des moteurs diesel, renfermant les éléments ci-après: Cr 18-22 %, Mo 6-10 %, Si 0,6-1,7 %, C 0,002-0,05 %, Fe 1-5 %, Mn 0,05-0,5 %, Al 0,1-0,5 %, Ti 0,1-0,5 %, Mg 0,005-0,05 %, Ca 0,001-0,01 %, V max. 0,5 %, P max. 0,02 %, S max. 0,01 %, B 0,001-0,01 %, Cu max. 0,5 %, Co max. 1 %, Hf, Y, Zr et/ou terres rares 0,02-0,5 %, le reste étant constitué par du nickel et des impuretés dues à la fusion.
PCT/EP1997/006592 1997-01-29 1997-11-26 Alliage nickel-chrome-molybdene-silicium austenitique a haute resistance a la corrosion par les chlorures et les gaz chlores a chaud WO1998032887A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97951980A EP0956371A1 (fr) 1997-01-29 1997-11-26 Alliage nickel-chrome-molybdene-silicium austenitique a haute resistance a la corrosion par les chlorures et les gaz chlores a chaud
JP53151598A JP2001509210A (ja) 1997-01-29 1997-11-26 熱い塩素含有ガス及び塩化物に対する高い耐腐食性を有するオーステナイト系ニッケル−クロム−モリブデン−珪素−合金
CA002279294A CA2279294A1 (fr) 1997-01-29 1997-11-26 Alliage nickel-chrome-molybdene-silicium austenitique a haute resistance a la corrosion par les chlorures et les gaz chlores a chaud

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19703035.1 1997-01-29
DE1997103035 DE19703035C2 (de) 1997-01-29 1997-01-29 Verwendung einer austenitischen Nickel-Chrom-Molybdän-Silizium-Legierung mit hoher Korrosionsbeständigkeit gegen heiße chlorhaltige Gase und Chloride

Publications (1)

Publication Number Publication Date
WO1998032887A1 true WO1998032887A1 (fr) 1998-07-30

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/006592 WO1998032887A1 (fr) 1997-01-29 1997-11-26 Alliage nickel-chrome-molybdene-silicium austenitique a haute resistance a la corrosion par les chlorures et les gaz chlores a chaud

Country Status (5)

Country Link
EP (1) EP0956371A1 (fr)
JP (1) JP2001509210A (fr)
CA (1) CA2279294A1 (fr)
DE (1) DE19703035C2 (fr)
WO (1) WO1998032887A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117535559A (zh) * 2024-01-10 2024-02-09 北京北冶功能材料有限公司 一种低密度镍基高温合金箔材及其制备方法与应用

Families Citing this family (6)

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CN101899593B (zh) * 2010-04-06 2012-06-13 江苏立新合金实业总公司 一种镍铬高电阻电热合金
CN102191409B (zh) * 2011-04-22 2012-07-04 江苏新华合金电器有限公司 一种新型高电阻电热合金材料及其制备方法
CN104087768B (zh) * 2014-06-25 2017-02-15 盐城市鑫洋电热材料有限公司 一种改善镍铬铁电热合金性能的方法
CN104087769B (zh) * 2014-06-25 2017-02-15 盐城市鑫洋电热材料有限公司 一种改善镍基电热合金性能的方法
CN109722554B (zh) * 2018-12-22 2020-12-01 北京航空航天大学青岛研究院 一种降低高温合金熔体与氧化物陶瓷坩埚间润湿性的方法
JP7009666B1 (ja) * 2021-07-13 2022-02-15 日本冶金工業株式会社 加工性、耐食性に優れる溶接管用Ｎｉ－Ｃｒ－Ｍｏ系合金

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3785877A (en) * 1972-09-25 1974-01-15 Special Metals Corp Treating nickel base alloys
JPS6199649A (ja) * 1984-10-22 1986-05-17 Kubota Ltd 通電ロ−ル用合金
WO1989001985A1 (fr) * 1987-08-28 1989-03-09 Chas. S. Lewis & Co., Inc. Alliage resistant a la corrosion, coulable, fusible a l'air
WO1995031579A1 (fr) * 1994-05-18 1995-11-23 Sandvik Ab ALLIAGE AUSTENITIQUE A BASE DE Ni PRESENTANT UNE RESISTANCE ELEVEE A LA CORROSION, UNE BONNE APTITUDE AU FAÇONNAGE AINSI QU'UNE BONNE STABILITE DE STRUCTURE

Family Cites Families (3)

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US3272666A (en) * 1963-12-09 1966-09-13 Du Pont Method of heat treating nickel base alloy articles up to 20 mils in thickness
JPS5631345B2 (fr) * 1972-01-27 1981-07-21
EP0092397A1 (fr) * 1982-04-20 1983-10-26 Huntington Alloys, Inc. Alliage nickel-chrome-molybdène

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3785877A (en) * 1972-09-25 1974-01-15 Special Metals Corp Treating nickel base alloys
JPS6199649A (ja) * 1984-10-22 1986-05-17 Kubota Ltd 通電ロ−ル用合金
WO1989001985A1 (fr) * 1987-08-28 1989-03-09 Chas. S. Lewis & Co., Inc. Alliage resistant a la corrosion, coulable, fusible a l'air
WO1995031579A1 (fr) * 1994-05-18 1995-11-23 Sandvik Ab ALLIAGE AUSTENITIQUE A BASE DE Ni PRESENTANT UNE RESISTANCE ELEVEE A LA CORROSION, UNE BONNE APTITUDE AU FAÇONNAGE AINSI QU'UNE BONNE STABILITE DE STRUCTURE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 010, no. 280 (C - 374) 24 September 1986 (1986-09-24) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117535559A (zh) * 2024-01-10 2024-02-09 北京北冶功能材料有限公司 一种低密度镍基高温合金箔材及其制备方法与应用
CN117535559B (zh) * 2024-01-10 2024-05-07 北京北冶功能材料有限公司 一种低密度镍基高温合金箔材及其制备方法与应用

Also Published As

Publication number Publication date
JP2001509210A (ja) 2001-07-10
DE19703035A1 (de) 1998-07-30
EP0956371A1 (fr) 1999-11-17
DE19703035C2 (de) 2000-12-07
CA2279294A1 (fr) 1998-07-30

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