US3811873A - High strength cost steel for use at cryogenic temperatures - Google Patents

High strength cost steel for use at cryogenic temperatures Download PDF

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Publication number
US3811873A
US3811873A US00222021A US22202172A US3811873A US 3811873 A US3811873 A US 3811873A US 00222021 A US00222021 A US 00222021A US 22202172 A US22202172 A US 22202172A US 3811873 A US3811873 A US 3811873A
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United States
Prior art keywords
percent
nickel
steel
toughness
manganese
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Expired - Lifetime
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US00222021A
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English (en)
Inventor
Barbadillo J De
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Huntington Alloys Corp
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International Nickel Co Inc
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Publication date
Priority to BE794796D priority Critical patent/BE794796A/fr
Application filed by International Nickel Co Inc filed Critical International Nickel Co Inc
Priority to US00222021A priority patent/US3811873A/en
Priority to CA160,251A priority patent/CA976390A/en
Priority to GB208473A priority patent/GB1413877A/en
Priority to AT76373*#A priority patent/AT329101B/de
Priority to IT47959/73A priority patent/IT977137B/it
Priority to ES411095A priority patent/ES411095A1/es
Priority to FR7303269A priority patent/FR2170039B1/fr
Priority to NL7301281A priority patent/NL7301281A/xx
Priority to AU51613/73A priority patent/AU464046B2/en
Priority to DE2304553A priority patent/DE2304553A1/de
Priority to JP1280573A priority patent/JPS5543069B2/ja
Application granted granted Critical
Publication of US3811873A publication Critical patent/US3811873A/en
Anticipated expiration legal-status Critical
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    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel

Definitions

  • cryogenic properties may be brought together in one steel provided the steel contains correlated amounts of nickel, manganese, molybdenum, carbon, calcium, etc.,"as will be described more fully herein.
  • lt is an object of this invention to provide a steel having a yield strength above about 85 ksi and an ultimate tensile strength above about 100 ksi together with Charpy V-notch toughness values of about 25, advantageously at least 30 ft.-lbs., or more in the longitudinal direction and about 20, preferably at least 25 ft.-lbs., or higher in the transverse direction at temperatures as low as -320F.
  • manganese and nickel being correlated so as to represent a point within the area ACDEA of the accompanying drawing, from 0.01 to 0.5 percent molybdenum, the molybdenum and nickel being interrelated as set forth hereinafter, calcium in a small. but effective amount to enhance toughness and up to about 0.1 percent, from about 0.05 to 0.14 percent carbon, up to about 0.5 percent silicon, up to about 0.1 percent columbium, the balance being essentially iron, the steel upon tempering, say at about l,ll0 to 1,200F., having a duplex microstructure comprised of a martensitic matrix containing dispersed austenite.
  • Nickel is essential in accordance herewith for strength and toughness since it acts as a stabilizer for the precipitated austenite dispersion. Amounts above 7.5 percent are unnecessary and a nickel range of 5.5
  • the percentages of nickel and manganese should be correlated to represent a point in the area ACDEA of the accompanying drawing and advantageously within the area BCDEB.
  • the effect of manganese on the toughness properties, both longitudinal and transverse, is related to the nickel content.
  • a manganese range of 1.75 to 2.5 percent together with 5.5 percent or 5.75 to 6.5 percent nickel affords good results.
  • the austenite dispersion is believed to be associated with or directly responsible for the outstanding cryogenie toughness in these nickel steels.
  • Manganese however, even at the low concentrations in these steels, to wit, 0.4-2.8 percent, has been found to be beneficial mostly, if not completely, in respect of longitudinal toughness. Actually, it is deemed detrimental to transverse toughness, particularly in amounts of about 1 per cent and higher, because it produces or contributes to a stringer-like inclusion morphology, the stringers seemingly being mostly sulfides.
  • Transverse toughness can, as is well known, be brought to a level comparable I to that in the longitudinal direction by employing more than the normal amount of cross rolling. This is expensive and thus unattractive (though full cross rolling is not excluded from the invention). Alternatively, high purity-materials devoid of sulfur and other contaminants can be used as well as processing techniques designed to prevent or minimize the same. This too', also involves high cost and is thus not the most acceptable panacea.
  • the present invention is directed to a steel'containing (by weight) from about 5 percent of stringers or stringer-like to globular form.
  • Calcium is particularly beneficial in this regard in amounts up to about 0.1 percent and in so doing contributes to bringing about'an improvement in transverse properties.
  • a retained, calcium percentage of about 0.0l5, to 0.025 percent is quite beneficial, although a range of 0.005 percent or 0.01 to 0.05 percent is satisfactory.
  • Other additives, such as magnesium, barium, strontium, zirconium and rare earths (particularly cerium), may also be employed in similar amounts.
  • the subject steel can contain even up to as high as 0.04 percent sulfur although lower levels, up to 0.015 or 0.02 percent, are preferred for weldability.
  • Molybdenum is uscd for toughness and solid solution strengthening. Additions of only 0.1 percent markedly enhance impact properties, both longitudinal and transverse, and increase strength. But it should be correlated to the nickel content, such that at percent nickel it is at least 0.12 percent, at 5.5 percent nickel it is at least 0.08 percent, at 6 percent nickel it is at least 0.05 percent and at 7 percent nickel it is at least 0.01 percent. Above 7 percent nickel, molybdenum might be omitted but it is to be expected that properties would be lowered. (Interpolation can be used for intermediate percentages). Over the range of 5.5 to 6.5 per- I cent nickel a molybdenum level of 0.08 to 0.15 percent is highly satisfactory.
  • Carbon has an important effect on toughness. Contrary to the general rule in these types of steels that toughness increases as carbon decreases, it was found thatover the range of 0.05 to 0.13 percent or 0.14 percent there is a maximum level of toughness at approximately about 0.08 percent, i.e., about 0.07 to 0.09 percent. Toughness decreases gradually as the carbon content increases much above 0.08 percent but decreases rather sharply as it is lowered from 0.08 percent. To achieve the desired toughnessthe carbon should be maintained advantageously above 0.05 percent, e.g., 0.06 percent or more, with the 0.08 percent level being most preferred. Although up to 0.2 percent might be tolerated, an upper limit of about 0.14 percent is beneficial since higher levels also contribute to welding problems. I
  • the steels can be produced in accordance with conventional procedures as those skilled in the art will appreciate. Both the melting steps and the casting and hot rolling steps may be carried out following conventional practices.
  • the steel should be deoxidized with a material such as aluminum, e.g., up to 0.15 percent aluminum, according to fine grain practice.' No unusual processing restrictions are required.
  • heat treatment it is preferred that the steels be austenitized forl hour at about 1,500F., water quenched, and thereafter tempered for about 2 hours at about l,1251,l50F. followed by a water quench.
  • the austenitizing temperature can be from l,425 to 1,600F. and the tempering temperature can be from l,100 to 1,200F. Air cooling can be used.
  • N'l' dou- .ble normalize and temper
  • the important consideration is tempering such that a two phase structure is achieved, to wit, a tempered martensitic matrix with a relatively f ne and uniform dispersion of austenite, the austenite content being at least 3 percent, preferably at least 5 percent and most beneficially at least 10 percent by volume.
  • the amount of austenite need not exceed 25 percent or 30 percent.
  • a number of steels were air-induction melted and cast into ingots. High purity raw materials were used. Electrolytic nickel and iron were used together with ferromanganese, ferrosilicon, etc. Deliberate additions of ferrophosphorus and ferrosulfide were made to simulate the purity in commercial 9 percent nickel steel. The charge was initially deoxidized with carbon and silicon-manganese. Final deoxidation was with aluminum. Calcium (calcium-silicon master alloy) was plunged into the melt after aluminum deoxidation. All the steels were unidirectionally rolled to inch plate at 1,900F. The steels were then given a uniform austenitizing treatment consisting of heating for one hour at 1,500F., water quenching, tempering for 2 hours at 1,135F. and again water quenching.
  • the steels were of the following nominal composition (weight percent 0.10 Mo, 0.25 Si, 0.12 C, 0.008 P, 0.015 S, 0.06 Al, 0.05 Cb and 0.015 Ca, the nickel and manganese contents being given in Table I together with tensile properties, including ir'npact toughness, and the percentage of austenite.
  • Table l reflects the desirability and advantage in correlating the nickel and manganese contents.
  • the manganese content should be maintained at the upper part of its range to achieve the desired transverse toughness (Alloys 3 or 4).
  • Alloy l is at best a marginal steel and falls within the area ABEA of the drawing. in contrast, the more advantageous steels (Nos. 2-l 2) fall within the area defined by BCDEB. It might be added that at the higher nickel contents, toughness is not nearly as sensitive to changes in the manganese content, this being due to.
  • the nickel and manganese together with other austenite formers should be balanced against the ferrite formers. This can be accomplished by procedures well known to those skilled in the art (e.g., Schaefflers diagram or modified versions thereof) so as to provide for a microstructure containing preferably at least 5 percent by volume of austenite.
  • Carbon as mentioned above and as can be seen from Table ll, has the unexpected effect of producing a maximum toughness, both longitudinal and transverse, as the level is increased-up to about 0.08 percent.
  • the toughness decreases relatively rapidly at levels outside the range of about 0.07 to about 0.12 percent, particularly at the lower carbon levels.
  • the alloys of Table ll, apart from carbon, have the nominal composition (weight percent) of 6.1% Ni, 2.2% Mn, 0.1% Mo, 0.25% Si,'0.0l2% P,.0.0l6% S, 0.07% Cb and 0.015% Ca. it perhaps should be mentioned that, all other factors remaining the same, the impact strength of steels 13-1 6 would'be expected to be higher if the steels were cent nickel steel. Welding tests have shown that the weld metal and heat-affected zone have adequate toughness at 320F.
  • the present invention contemplates articles, including structural elements, made from the nickel steels described herein, andsubjected in use to load at temperatures as low as 320F.
  • Illustrative examples of such articles include tanks, containers, reservoirs, vessels,'heat exchangers, and the like for producing, processing, storing and/or distributing liquified gas, and associated equipment such as valves, pumps, piping, tubes, conduits, structural shapes for reinforcing or restraining vessels, etc.
  • the invention is particularly applicable for vessels containing such liquified gases as hydrocarbon gases, including natural gases, methane, propane, bu-
  • the use of the expression balance or balance essentially in referring tothe iron content of the subject steel does not exclude the presence of other elements, such as those commonly present as incidental constituents, e.g., deoxidizing and cleansing elements, and impurities ordinarily associated therewith in small amounts which do not adversely affect the basic characteristic of the steel.
  • Silicon in amounts up to about 0.5 percent, e.g.,.up to 0.3 percent, can be present.
  • Table Ill shows the marked increase in transverse verse directions, respectively, down to temperatures of toughness caused by the addition of calcium or cerium. 5 5' about 320F., and good weldability, said steel consist- The steels, in addition to calcium or cerium, nominally contained 6.1% Ni, 2.1% Mn, 0.09% M0, 0.2% Si, 0.13% C, 0.06% Cb, 0.006% P and 0.013% S.
  • alloys of the invention are weldable usingsuch wires as the standard commercial wire used'for 9 perto represent a point withinthe area ACDEA of the accompanying drawing, at least 0.05 to 0.15 percent moat least percent and up to about 25 percent by volume.
  • An alloy steel in accordance with claim 1 containing from5.5 to 6.5 percent nickel from 1.75 to 2.5 percent manganese, from 0.05 to 0.12 percent molybdenum, about 0.01 to 0.05 percent calcium, at least 0.06

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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 Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
US00222021A 1972-01-31 1972-01-31 High strength cost steel for use at cryogenic temperatures Expired - Lifetime US3811873A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
BE794796D BE794796A (fr) 1972-01-31 Aciers a grande resistance
US00222021A US3811873A (en) 1972-01-31 1972-01-31 High strength cost steel for use at cryogenic temperatures
CA160,251A CA976390A (en) 1972-01-31 1972-12-29 High strength low cost steel for use at cryogenic temperatures
GB208473A GB1413877A (en) 1972-01-31 1973-01-15 High strength steels
AT76373*#A AT329101B (de) 1972-01-31 1973-01-29 Hochfester stahl
ES411095A ES411095A1 (es) 1972-01-31 1973-01-30 Un procedimiento para producir un acero adecuado para uso abajas temperaturas.
IT47959/73A IT977137B (it) 1972-01-31 1973-01-30 Acciaio legato ed oggetti ottenuti da esso
FR7303269A FR2170039B1 (fr) 1972-01-31 1973-01-30
NL7301281A NL7301281A (fr) 1972-01-31 1973-01-30
AU51613/73A AU464046B2 (en) 1972-01-31 1973-01-31 Nickel-molybdenum-steels having toughness and strength at low temperatures
DE2304553A DE2304553A1 (de) 1972-01-31 1973-01-31 Stahllegierung
JP1280573A JPS5543069B2 (fr) 1972-01-31 1973-01-31

Applications Claiming Priority (1)

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US00222021A US3811873A (en) 1972-01-31 1972-01-31 High strength cost steel for use at cryogenic temperatures

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US3811873A true US3811873A (en) 1974-05-21

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US00222021A Expired - Lifetime US3811873A (en) 1972-01-31 1972-01-31 High strength cost steel for use at cryogenic temperatures

Country Status (12)

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US (1) US3811873A (fr)
JP (1) JPS5543069B2 (fr)
AT (1) AT329101B (fr)
AU (1) AU464046B2 (fr)
BE (1) BE794796A (fr)
CA (1) CA976390A (fr)
DE (1) DE2304553A1 (fr)
ES (1) ES411095A1 (fr)
FR (1) FR2170039B1 (fr)
GB (1) GB1413877A (fr)
IT (1) IT977137B (fr)
NL (1) NL7301281A (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960612A (en) * 1973-08-15 1976-06-01 Nippon Steel Corporation Method for producing a low temperature high strength tough steel
US4098622A (en) * 1976-05-14 1978-07-04 International Harvester Company Earth-working implement
US4137104A (en) * 1976-02-23 1979-01-30 Sumitomo Metal Industries, Ltd. As-rolled steel plate having improved low temperature toughness and production thereof
US4292492A (en) * 1976-05-11 1981-09-29 Mannesmann Ag Seam welding of pipes
US4605449A (en) * 1981-05-19 1986-08-12 Arbed S.A. Process for producing a rolled steel product having high weldability, a high yield strength and a good notch impact toughness at very low temperatures

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0053507A1 (fr) * 1980-12-02 1982-06-09 British Steel Corporation Procédé de fabrication de ronds et barres en acier contenant du nickel
KR101271974B1 (ko) * 2010-11-19 2013-06-07 주식회사 포스코 극저온 인성이 우수한 고강도 강재 및 그 제조방법

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960612A (en) * 1973-08-15 1976-06-01 Nippon Steel Corporation Method for producing a low temperature high strength tough steel
US4137104A (en) * 1976-02-23 1979-01-30 Sumitomo Metal Industries, Ltd. As-rolled steel plate having improved low temperature toughness and production thereof
US4292492A (en) * 1976-05-11 1981-09-29 Mannesmann Ag Seam welding of pipes
US4098622A (en) * 1976-05-14 1978-07-04 International Harvester Company Earth-working implement
US4605449A (en) * 1981-05-19 1986-08-12 Arbed S.A. Process for producing a rolled steel product having high weldability, a high yield strength and a good notch impact toughness at very low temperatures

Also Published As

Publication number Publication date
AT329101B (de) 1976-04-26
FR2170039A1 (fr) 1973-09-14
AU464046B2 (en) 1975-08-14
CA976390A (en) 1975-10-21
JPS4888013A (fr) 1973-11-19
GB1413877A (en) 1975-11-12
DE2304553A1 (de) 1973-08-30
ES411095A1 (es) 1976-01-01
JPS5543069B2 (fr) 1980-11-04
IT977137B (it) 1974-09-10
FR2170039B1 (fr) 1977-02-04
ATA76373A (de) 1975-07-15
NL7301281A (fr) 1973-08-02
AU5161373A (en) 1974-08-01
BE794796A (fr) 1973-07-31

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