US3893849A - Oxidation-resistant ferritic stainless steel - Google Patents

Oxidation-resistant ferritic stainless steel Download PDF

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Publication number
US3893849A
US3893849A US085738A US8573870A US3893849A US 3893849 A US3893849 A US 3893849A US 085738 A US085738 A US 085738A US 8573870 A US8573870 A US 8573870A US 3893849 A US3893849 A US 3893849A
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United States
Prior art keywords
percent
steel
chromium
alloy
max
Prior art date
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Expired - Lifetime
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US085738A
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English (en)
Inventor
Kenneth G Brickner
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United States Steel Corp
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United States Steel Corp
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Filing date
Publication date
Application filed by United States Steel Corp filed Critical United States Steel Corp
Priority to US085738A priority Critical patent/US3893849A/en
Priority to CA124,491,A priority patent/CA951148A/en
Priority to GB4727371A priority patent/GB1373231A/en
Priority to BE774362A priority patent/BE774362A/xx
Priority to IT70499/71A priority patent/IT945777B/it
Priority to NL7114656A priority patent/NL7114656A/xx
Priority to FR7138379A priority patent/FR2110058A5/fr
Priority to DE19712154148 priority patent/DE2154148A1/de
Application granted granted Critical
Publication of US3893849A publication Critical patent/US3893849A/en
Assigned to USX CORPORATION, A CORP. OF DE reassignment USX CORPORATION, A CORP. OF DE MERGER (SEE DOCUMENT FOR DETAILS). Assignors: UNITED STATES STEEL CORPORATION (MERGED INTO)
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081Heat exchange elements made from metals or metal alloys
    • F28F21/082Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
    • F28F21/083Heat exchange elements made from metals or metal alloys from steel or ferrous alloys from stainless steel

Definitions

  • ABSTRACT A ferritic stainless steel having the composition:
  • the steel has good high-temperature oxidation resistance at all temperatures up to about 2,200F and has sufficient ductility to be hot and cold worked into sheet and strip.
  • high aluminum steels have been developed for comparable hightemperature applications. These high aluminum steels (i.e., above 4 percent aluminum) have excellent oxidation resistance up to about 2,200F. These aluminum steels do, however, have two serious disadvantages in that they are very difficult to produce in wrought form, and they exhibit relatively high and erratic oxidation rates between about l,0OO and l,400F. These high aluminum steels, therefore, cannot be used in applications where service temperatures will be in the l,lOl,400F range or where cyclic temperatures through this range may be encountered.
  • a new chromium-aluminum alloy which is not only oxidation-resistant at all temperatures up to about 2,200F but which possesses a high degree of ductility without complex deoxidation or degassing.
  • the ductility of this inventive alloy is sufficient to permit cold rolling of the alloy to sheet and strip products in accordance with conventional cold rolling practices.
  • this inventive steel utilizes lesser amounts of alloy additives, notably chromium, and is therefore more economical than the comparable prior art alloy discussed above.
  • Another object of this invention is to provide a new chromium-aluminum steel alloy having good oxidation resistance at all temperatures up to about 2,200F, and further having sufficient ductility when produced by conventional steelmaking practices to be cold rolled into sheet and strip products.
  • a further object of this invention is to provide a new, high-temperature oxidation-resistant, chromiumaluminum stainless steel alloy which utilizes less chromium and is therefore more economical than similar prior art alloys.
  • the prior art chromium-aluminum high-temperature steel alloy contains 7.0 to 8.0 percent chromium and 6.5 to 8.0 percent aluminum. The balance thereof is of course iron with incidental impurities. Because of the high alloy content, this steel cannot be cold rolled without excessive edge cracking when produced in accordance with conventional steelmaking practices. In order to have any useful degree of ductility, this alloy must have exceptional low oxygen and gas contents, i.e., such low gas levels as can only be achieved by vacuum melting practices or by specialized chemical degassing procedures.
  • the alloy of this invention is a similar chromium-aluminum steel alloy, but further having exceptional ductility even when produced in accordance with conventional steelmaking practices.
  • the crux of this invention resides in my discovery that slight reductions in the alloy content to levels below certain critical limits will yield such a ductile alloy without any marked sacrifice in the desired high-temperature oxidation resistance.
  • the essential critical feature of this inventive alloy is the restriction of chromium contents to not more than 6.25 percent, and the restriction of aluminum contents to not more than 7.0 percent.
  • the composition limits of this alloy are as follows:
  • the alloy of this invention is further limited to the relationship in which the percent chromium plus two times the percent molybedenum is at least equal to the integer 5. In the absence of molybdenum, therefore, the inventive alloy must contain from 5 to 6.25 percent chromium. With given additions of molybdenum up to 2 percent, however, chromium reductions equal to twice the molybdenum content can be tolerated, down to a minimum of about 2.75 percent chromium.
  • the more basic embodiment contains only chromium and aluminum without molybdenum, as has been the prior art practice. Unlike the prior art practice, however, this embodiment of the invention contains not more than a critical 6.25 percent chromium, for a chromium content of from 5.0 to 6.25 percent.
  • the aluminum content of this alloy must be restricted to the range 5.0 to 7.0 percent. As has been noted, this contrasts with prior art limits of 7.0 to 8.0 percent chromium and 6.5 to 8.0 percent aluminum. 1n limiting the alloy additives to such lower levels, I have found that there is not a marked sacrifice in the alloys high-temperature oxidation resistance. Because of these possible lower alloy additions while maintaining useful high-temperature oxidation resistance, the economic advantages of this invention become readily apparent.
  • ductility Another advantage more significant than economy is that of ductility. That is to say, I have discovered that if the chromium, aluminum and normal residual elements are all maintained below given critical maximum limits, the alloy will have a rather high degree of ductility. In fact, the alloy will possess sufficient ductility to be readily cold rolled into sheet and strip products using conventional commercial equipment and procedures. Of most significance is the fact that this ductility is achieved without any highly special processing to degas or purify the alloy.
  • the chromium content in the alloy must not exceed a critical 6.25 percent, the aluminum content must not exceed a critical 7.0 percent and the residual elements must be limited as follows: carbon, 0.03 percent maximum; manganese, 0.5 percent maximum; silicon 0.10 percent maximum; phosphorus, 0.025 percent maximum; and sulfur, 0.025 percent maximum.
  • at least 5.0 percent chromium and 5.0 percent aluminum must be provided.
  • molybdenum may be present in amounts not exceeding 2 percent.
  • composition limits will provide an alloy having good high-temperature oxidation resistance and exceptional ductility as stated, there are certain more preferred embodiments of this inventive alloy which will provide even better properties for specific given applications.
  • Another embodiment of this invention is an alloy substantially as described above, but further containing molybdenum in amounts not exceeding about 2 percent, and preferably about 1 percent molybdenum.
  • molybdenum is in the alloy in quantities exceeding about 2 percent, even with substantially reduced chromium contents, an alloy is produced that is difficult to hot work and that has a marked tendency towards edge cracking when cold rolled to sheet thicknesses.
  • molybdenum contents in excess of about 2 percent should be avoided, and molybdenum contents of about 1 percent or less are preferred.
  • the alloy of this invention is limited to compositions within the above discussed ranges wherein the percent chromium plus two times the percent molybdenum is at least equal to the integer 5.
  • a molybdenum-free alloy having 6.25 percent chromium is comparable, for the objectives of this invention, to an alloy having 4.25 percent chromium and 1 percent molybdenum, or to an alloy having 5.25 percent chromium and 0.5 percent molybdenum and so on. It is not essential, however, that the chromium content be reduced proportionally, or at all, when molybdenum is used.
  • Steel 1 was a conventional AISI Type 430 stainless steel
  • Steel 2 was a conventional AISl Type 446 stainless steel
  • Steel 3 was a high-temperature aluminum steel as known in the prior art
  • Steels and 11 were chromium-aluminum steels having compositions in accordance with prior art teaching. but not specially degassed.
  • Steels 4 through 9 and 12 were steels having compositions in accordance with this invention, except that Steels 6 and 9 had molybdenum contents in excess of that taught and Steel 4 contained insufficient chromium without molybdenum.
  • Steels 5, 7, 8 and 12 had compositions completely within the scope of this invention.
  • Steel 2 the Type 446 steel, had a small weight loss at 1,500F but, as expected, the weight loss increased substantially at 2,000 and 2,200F.
  • Steel 1 was not tested at 2,000 and 2.200F because the sample would have been completely oxidized at these temperatures.
  • Steel 3 the 6 percent aluminum steel, exhibited relatively high and erratic weight losses at 1,200F and substantially lower weight losses between l,500 and 2,200F.
  • the addition of 1 percent molybdenum to such a steel as Steel 3, i.e., Steel 5 resulted in a substantial reduction in weight loss at 1,200F.
  • Table II further shows that the addition of 1 percent molybdenum to a 6 percent chromium-6percent aluminum alloy (Steel 8) had no appreciable detrimental or beneficial effect on oxidation resistance. however, 3 percent molybdenum in such a steel (Steel 9) resulted in a relatively high weight loss at 1,800F. In addition, Steel 9, as well as Steel 6, was difficult to hot work, and cold rolled sheets thereof had marked tendencies toward edge cracking.
  • a ferritic stainless steel consisting essentially of carbon 0.03% max. manganese 0.50% max. silicon 0.10% max. phosphorus 0.025% max. sulfur 0.025% max. chromium 2.75 to 5.0% aluminum 5.0 to 7.0% molybdenum about 1% iron balance plus incidental impurities.
  • the percent chromium plus two times the percent molybdenum is at least equal to the integer 5, said steel characterized by high-temperature oxidation resistance at all temperatures up to about 2,200F, and sufficient ductility to be hot and cold worked into sheet and strip products.
  • A1 should be 6.55

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)
US085738A 1970-10-30 1970-10-30 Oxidation-resistant ferritic stainless steel Expired - Lifetime US3893849A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US085738A US3893849A (en) 1970-10-30 1970-10-30 Oxidation-resistant ferritic stainless steel
CA124,491,A CA951148A (en) 1970-10-30 1971-10-05 Oxidation-resistant steel
GB4727371A GB1373231A (en) 1970-10-30 1971-10-11 Oxidation-resistant steel
BE774362A BE774362A (fr) 1970-10-30 1971-10-22 Acier inoxydable
IT70499/71A IT945777B (it) 1970-10-30 1971-10-25 Acciaio inossidabile ferrittico
NL7114656A NL7114656A (de) 1970-10-30 1971-10-25
FR7138379A FR2110058A5 (de) 1970-10-30 1971-10-26
DE19712154148 DE2154148A1 (de) 1970-10-30 1971-10-29 Ferritischer, nichtrostender Stahl

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US085738A US3893849A (en) 1970-10-30 1970-10-30 Oxidation-resistant ferritic stainless steel

Publications (1)

Publication Number Publication Date
US3893849A true US3893849A (en) 1975-07-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
US085738A Expired - Lifetime US3893849A (en) 1970-10-30 1970-10-30 Oxidation-resistant ferritic stainless steel

Country Status (8)

Country Link
US (1) US3893849A (de)
BE (1) BE774362A (de)
CA (1) CA951148A (de)
DE (1) DE2154148A1 (de)
FR (1) FR2110058A5 (de)
GB (1) GB1373231A (de)
IT (1) IT945777B (de)
NL (1) NL7114656A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4141724A (en) * 1978-06-21 1979-02-27 United States Steel Corporation Low-cost, high temperature oxidation-resistant steel
US4316743A (en) * 1973-10-29 1982-02-23 Tokyo Shibaura Electric Co., Ltd. High damping Fe-Cr-Al alloy
US5720920A (en) * 1993-07-06 1998-02-24 Nippon Steel Corporation Steel having excellent corrosion resistance and steel having excellent corrosion resistance and workability
US6524405B1 (en) * 2000-02-11 2003-02-25 Hui Lin Iron base high temperature alloy
WO2013178629A1 (de) * 2012-05-29 2013-12-05 Thyssenkrupp Steel Europe Ag Warmfester fe-al-cr-stahl

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL180683C (nl) * 1975-12-12 1987-04-01 Estel Hoogovens Bv Werkwijze voor het bereiden van een ijzerlegering met goede bestendigheid tegen in het bijzonder zeewatercorrosie, en een verdamperinstallatie geheel of ten dele vervaardigd uit deze ijzerlegering.
DE19820806B4 (de) * 1998-05-09 2004-03-04 Max-Planck-Institut Für Eisenforschung GmbH Verwendungen eines Leichtbaustahls

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1920934A (en) * 1928-07-10 1933-08-01 Chas W Guttzeit Corrosion resisting steel
US2232705A (en) * 1938-01-21 1941-02-25 Eastman Kodak Co Process and apparatus for making lower aliphatic acid anhydrides
US2387980A (en) * 1945-02-17 1945-10-30 Hugh S Cooper Electrical resistance alloys
US3068094A (en) * 1959-01-27 1962-12-11 Ford Motor Co Alloy of iron, aluminum, and chromium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1920934A (en) * 1928-07-10 1933-08-01 Chas W Guttzeit Corrosion resisting steel
US2232705A (en) * 1938-01-21 1941-02-25 Eastman Kodak Co Process and apparatus for making lower aliphatic acid anhydrides
US2387980A (en) * 1945-02-17 1945-10-30 Hugh S Cooper Electrical resistance alloys
US3068094A (en) * 1959-01-27 1962-12-11 Ford Motor Co Alloy of iron, aluminum, and chromium

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4316743A (en) * 1973-10-29 1982-02-23 Tokyo Shibaura Electric Co., Ltd. High damping Fe-Cr-Al alloy
US4141724A (en) * 1978-06-21 1979-02-27 United States Steel Corporation Low-cost, high temperature oxidation-resistant steel
US5720920A (en) * 1993-07-06 1998-02-24 Nippon Steel Corporation Steel having excellent corrosion resistance and steel having excellent corrosion resistance and workability
US6524405B1 (en) * 2000-02-11 2003-02-25 Hui Lin Iron base high temperature alloy
US20030070732A1 (en) * 2000-02-11 2003-04-17 Hui Lin Iron base high temperature alloy
US6841011B2 (en) 2000-02-11 2005-01-11 Hui Lin Iron base high temperature alloy and method of making
WO2013178629A1 (de) * 2012-05-29 2013-12-05 Thyssenkrupp Steel Europe Ag Warmfester fe-al-cr-stahl

Also Published As

Publication number Publication date
CA951148A (en) 1974-07-16
IT945777B (it) 1973-05-10
NL7114656A (de) 1972-05-03
GB1373231A (en) 1974-11-06
BE774362A (fr) 1972-04-24
FR2110058A5 (de) 1972-05-26
DE2154148A1 (de) 1972-05-04

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AS Assignment

Owner name: USX CORPORATION, A CORP. OF DE, STATELESS

Free format text: MERGER;ASSIGNOR:UNITED STATES STEEL CORPORATION (MERGED INTO);REEL/FRAME:005060/0960

Effective date: 19880112