EP0155011B2 - Hochfeste Legierung für Behälter für industrielle Anwendung - Google Patents

Hochfeste Legierung für Behälter für industrielle Anwendung Download PDF

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Publication number
EP0155011B2
EP0155011B2 EP85103129A EP85103129A EP0155011B2 EP 0155011 B2 EP0155011 B2 EP 0155011B2 EP 85103129 A EP85103129 A EP 85103129A EP 85103129 A EP85103129 A EP 85103129A EP 0155011 B2 EP0155011 B2 EP 0155011B2
Authority
EP
European Patent Office
Prior art keywords
content
alloy according
alloy
copper
nickel
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.)
Expired - Lifetime
Application number
EP85103129A
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English (en)
French (fr)
Other versions
EP0155011A2 (de
EP0155011A3 (en
EP0155011B1 (de
Inventor
Thomas Harvey Bassford
James Roy Crum
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.)
Huntington Alloys Corp
Original Assignee
Inco Alloys International Inc
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Publication date
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Application filed by Inco Alloys International Inc filed Critical Inco Alloys International Inc
Publication of EP0155011A2 publication Critical patent/EP0155011A2/de
Publication of EP0155011A3 publication Critical patent/EP0155011A3/en
Application granted granted Critical
Publication of EP0155011B1 publication Critical patent/EP0155011B1/de
Publication of EP0155011B2 publication Critical patent/EP0155011B2/de
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Classifications

    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/087—Heat exchange elements made from metals or metal alloys from nickel or nickel alloys
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0059—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for petrochemical plants

Definitions

  • the instant invention relates to nickel-iron-chromium alloys in general and more particularly to a high strength, corrosion resistant alloy having a low work hardenability rate with variable age hardenable characteristics. Tne alloy reduces copper pick-up in fluid streams.
  • the present invention provides an austenitic alloy having a low work hardening rate especially suitable for, but not limited to, industrial vessels and particularly for heat exchanger tubing for high temperature, high pressure appiications.
  • the instant alloy combines improved corrosion resistance and the requisite high strength in a system that is of lower cost than the more expensive higher alloys.
  • the alloy displays good stress corrosion cracking resistance and good high temperature corrosion resistance.
  • an austenitic, age-hardenable nickel-iron-chromium alloy having a combination of high strength, low work-hardening rate, resistance to stress-corrosion cracking and resistance to corrosion by high-temperature deaerated water and by hydrochloric, sulphuric, phosphoric and polythionic acids consists, by weight, of from 24 to 32% nickel, from 15 to 18% chromium, from 1 to 3.5% molybdenum, from 2 to 5.5% copper, from 0.8 to 2.5% titanium, from 0 to 1.5% manganese, from 0 to 1.5% silicon, e.g.
  • silicon from 0 to 1% niobium plus tantalum, from 0 to 2% aluminum, from 0 to 0.1% cerium, from 0 to 0.01% boron and from 0 to 0.2% nitrogen, the balance, apart from impurities, being iron.
  • impurities used herein includes residual amounts of calcium added as a processing aid.
  • the molybdenum content is advantageously from 1 to 3%, and the copper content from 2 to 5%.
  • the nickel content is from 26 to 29%, the chromium content from 15 to 18%, the molybdenum content not more than 3%, the copper content not more than 5% and the content of niobium plus tantalum not more than 0.4%.
  • the nickel is about 28%, the chromium about 16%, the molybdenum about 2% and the copper about 4%.
  • the incorporation of a measured quantity of titanium can impart an age hardening response of at least 60 ksi (413 MPa) yield strength and 120 ksi (825 MPa) tensile strength in the cold worked and annealed conditions.
  • the titanium raises the work hardening rate of the alloy. Copper, chromium and molybdenum improve the corrosion resistance of the alloy. Aluminum, cerium, boron and calcium assist in the deoxidation of the alloy.
  • Nitrogen serves to boost the ability of the alloy to withstand corrosive attack. The nitrogen raises the strength and increases the work hardening rate of the alloy in the annealed condition.
  • Table I below sets forth the compositions of a number of heats (Nos. 1-3 and 7-9) of alloys according to the invention within the above composition ranges and also, for purposes of comparison, one alloy (No 4) that is substantially free from copper and molybdenum, one alloy (No. 5) that is substantially free from copper, one alloy (No. 6) that is substantially free from molybdenum and titanium three alloys (Nos. 10-12) having lower titanium contents, and three alloys (Nos. 13-15) having lower nickel contents.
  • Heats 1-3 and 12 were vacuum melted and cast to 4 inch (10 cm) diameter ingots. Forged 9/16 inch (1.43 cm) squares plus forged 3/4 x 2 x 12 inch (1.91 x 5.08 x 20.5 cm) flats were made with frequent reheats at 2150°F (1177°C). After overhauling the flats to a uniform thickness, they were hot rolled to 1/4 inch (0.64 cm) at 2150°F. The hot rolled 1/4 inch strip was annealed at 1950°F (1066°C)/one hour water quench and pickled prior to cold rolling. Hardness and tensile tests were taken at various levels of cold work to establish a work hardening response. A low work hardening rate is very desirable in the manufacture of relatively small diameter thin-walled tubing.
  • the instant invention was developed with the attributes of good workability characteristics and ease of processing in mind.
  • Table 5 shows the strength and ductility characteristics in the annealed and aged conditions.
  • Corrosion tests were conducted on heats 4-12. Corrosion test environments relevant to feedwater heater service and other possible applications were examined.
  • Table 6 depicts the SCC test results in sodium chloride and sodium hydroxide solutions.
  • test data also indicates very good resistance of the alloys to polythionic acid cracking. This is a common cause of failure of stainless steels and high nickel alloys in petrochemical service. The influence of high titanium content on carbide precipitation is believed to be responsible for good polythionic acid SCC resistance.
  • Table 7 shows general corrosion test results.
  • Tables 6 and 7 also demonstrate the resistance of the alloy to environments other than that posed by feed- water heaters. Molybdenum addition of 2-3% greatly improves resistance to hydrochloric acid. Copper additions of 4% or more improved sulfuric acid resistance. The combination of copper and molybdenum appears to improve resistance to phosphoric acid. The instant alloy lends itself to chemical and petrochemical applications.
  • the design strength of the alloys destined for tubular applications is usually based on the tensile strength of the alloy comprising the apparatus.- In the cold worked plus stress relieved conditions, the instant alloy system will meet the 824 MPa minimum tensile strength usually specified by design engineers. This value, compares favorably with such alloys as Inconel alloy 625 and Incoloy alloy 801. Table 8 compares minimum tubular wall thicknesses between MONEL alloy 400, 304 stainless and the instant alloy for various temperature and pressure conditions. Table 8 was constructed to compare the mini mum wall thickness between the listed alloys. The next heavier standard well thickness was used to calculate the weight per meter.
  • the object or tube made by methods known to those skilled in the art, may be subjected to a stress relieving heat treatment of about 1100 to 1400°F (593-760°C) for an appropriate period of time.
  • the time period is, of course, a function of the temperature selected and the section size.
  • the non-age hardenable tubes may be drawn to final size, annealed at about 1700-2000°F (767-933°C) for a suitable time, straightened, bent into the appropriate shape (if desired), and stress relieved at about 593-760°C up to about three hours.
  • the age-hardenable tubes may be drawn to final size, annealed at about 767-933°C for a suitable time, straightened, aged for about an hour at 593-760°C, bent into the appropriate shape and stress relieved (which also ages the tube) at about 593-760°C for the appropriate time.
  • the pitting resistance of the alloy is about the same as stainless 304 and is not recommended for service where superior resistance to localized attack is required.
  • the low chromium lowers resistance to intergranular attack and limits use in highly oxidizing environments such as nitric acid.
  • a preferred composition for overall strength, corrosion resistance and economy for feedwater heaters is heat 8 (28 Ni - 16 Cr - 4 Cu - 1.8 Ti - 2 Mo - Bal Fe). This composition appears to have the mechanical and corrosion properties necessary for a high pressure material. It also has excellent general corrosion resistance in hydrochloric, sulfuric and phosphoric acids. The good resistance of this composition to polythionic acid attack also indicates potential petrochemical applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)

Claims (10)

1. Austenitische aushärtbare Nickel-Eisen-Chrom-Legierung mit hoher Festigkeit, geringer Neigung zur Kaltverfestigung, Beständigkeit gegen Spannungsrißkorrosion und entlüftetes Heißwasser, Salz-, Schwefel-, Phosphor- und Polythionsäure aus - in Gewichtsprozent - 24 bis 32% Nickel, 15 bis 18% Chrom, 1 bis 3,5% Molybdän, 2 bis 5,5% Kupfer, 0,8 bis 2,5% Titan, 0 bis 1,5% Mangan, 0 bis 1,5% Silizium, 0 bis 1% Niob und Tantal, 0 bis 0,2% Aluminium, 0 bis 0,1% Cer, 0 bis 0,01% Bor und 0 bis 0,2% Stickstoff, Rest außer Verunreinigungen Eisen.
2. Legierung nach Anspruch 1, deren Kupfergehalt jedoch mindestens 4 % beträgt.
3. Legierung nach Anspruch 1 oder 2, deren Molybdängehalt jedoch 2 bis 3 % beträgt.
4. Legierung nach einem der Ansprüche 1 bis 3, deren Siliziumgehalt jedoch höchstens 0,45 % beträgt.
5. Legierung nach einem der Ansprüche 1 bis 4, die jedoch 26 bis 29 % Nickel, 15 bis 18 % Chrom, höchstens 5 % Kupfer, höchstens 3 % Molybdän und höchstens 0,4 % Niob und Tantal enthält.
6. Legierung nach Anspruch 5, die jedoch etwa 28 % Nickel, etwa 16 % Chrom, etwa 2 % Molybdän, etwa 4 % Kupfer und etwa 1,8 % Titan enthält.
7. Legierung nach einem der Ansprüche 1 bis 6, die jedoch bis 16 Stunden bei 1.100 bis 1.400°F (605 bis 760 ° C) wärmebehandelt worden ist.
8. Rohr aus einer Legierung nach einem der Ansprüche 1 bis 7.
9. Wärmetauscher oder Speisewassererhitzer aus einer Legierung nach einem der Ansprüche 1 bis 7 oder einem Rohr nach Anspruch 8.
10. Verwendung einer Legierung nach den Ansprüchen 1 bis 7 als Werkstoff für Gegenstände, die im Gebrauch Polythionsäure ausgesetzt sind.
EP85103129A 1984-03-16 1985-03-18 Hochfeste Legierung für Behälter für industrielle Anwendung Expired - Lifetime EP0155011B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59039384A 1984-03-16 1984-03-16
US590393 1984-03-16

Publications (4)

Publication Number Publication Date
EP0155011A2 EP0155011A2 (de) 1985-09-18
EP0155011A3 EP0155011A3 (en) 1987-04-08
EP0155011B1 EP0155011B1 (de) 1990-07-18
EP0155011B2 true EP0155011B2 (de) 1994-07-06

Family

ID=24362074

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85103129A Expired - Lifetime EP0155011B2 (de) 1984-03-16 1985-03-18 Hochfeste Legierung für Behälter für industrielle Anwendung

Country Status (9)

Country Link
EP (1) EP0155011B2 (de)
JP (1) JPS60211053A (de)
KR (1) KR900001561B1 (de)
AU (1) AU580758B2 (de)
BR (1) BR8501127A (de)
CA (1) CA1246902A (de)
DE (1) DE3578673D1 (de)
ES (1) ES8608055A1 (de)
FI (1) FI75869C (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3716665A1 (de) * 1987-05-19 1988-12-08 Vdm Nickel Tech Korrosionsbestaendige legierung
JP2002241900A (ja) 1997-08-13 2002-08-28 Sumitomo Metal Ind Ltd 耐硫酸腐食性と加工性に優れたオーステナイト系ステンレス鋼
US5945067A (en) * 1998-10-23 1999-08-31 Inco Alloys International, Inc. High strength corrosion resistant alloy
US7815848B2 (en) 2006-05-08 2010-10-19 Huntington Alloys Corporation Corrosion resistant alloy and components made therefrom
JP5792905B2 (ja) * 2011-09-30 2015-10-14 ユーオーピー エルエルシー 炭化水素流を処理する方法及び装置
KR20150060942A (ko) * 2012-10-30 2015-06-03 가부시키가이샤 고베 세이코쇼 오스테나이트계 스테인리스강
CN109563589B (zh) * 2016-08-03 2020-11-06 新日铁住金株式会社 奥氏体系不锈钢

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU420305B (en) * 1905-09-21 1905-12-19 Oliver Charles Improvements in or relating to electric are lamps
GB708820A (en) * 1951-03-29 1954-05-12 Carpenter Steel Co Improvements in alloys
GB812582A (en) * 1956-07-18 1959-04-29 Universal Cyclops Steel Corp Ferrous base alloys
ZA726262B (en) * 1971-09-20 1973-06-27 Int Nickel Ltd Steels
BE795564A (fr) * 1972-02-16 1973-08-16 Int Nickel Ltd Alliage de nickel-fer resistant a la corrosion
DE2528610A1 (de) * 1974-07-02 1976-01-22 Westinghouse Electric Corp Nickel-chrom-eisen-legierung, deren verwendung und daraus hergestellte gegenstaende
US4040876A (en) * 1974-07-02 1977-08-09 Westinghouse Electric Corporation High temperature alloys and members thereof

Also Published As

Publication number Publication date
FI851036A0 (fi) 1985-03-15
FI851036L (fi) 1985-09-17
EP0155011A2 (de) 1985-09-18
ES8608055A1 (es) 1986-06-01
BR8501127A (pt) 1985-11-05
EP0155011A3 (en) 1987-04-08
AU580758B2 (en) 1989-02-02
AU3969885A (en) 1985-09-19
FI75869C (fi) 1988-08-08
DE3578673D1 (de) 1990-08-23
KR850007098A (ko) 1985-10-30
CA1246902A (en) 1988-12-20
JPS60211053A (ja) 1985-10-23
FI75869B (fi) 1988-04-29
KR900001561B1 (ko) 1990-03-15
JPH0525944B2 (de) 1993-04-14
EP0155011B1 (de) 1990-07-18
ES541303A0 (es) 1986-06-01

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