US3778255A - Corrosion resistant low carbon chromium alloy steel - Google Patents

Corrosion resistant low carbon chromium alloy steel Download PDF

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US3778255A
US3778255A US00275072A US3778255DA US3778255A US 3778255 A US3778255 A US 3778255A US 00275072 A US00275072 A US 00275072A US 3778255D A US3778255D A US 3778255DA US 3778255 A US3778255 A US 3778255A
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content
chromium
steel
calcium
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T Ototani
S Shimodaira
Y Kataura
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RES INST METALS OF TOHOKU UNIV
RES INST METALS OF TOHOKU UNIVERSITY JA
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RES INST METALS OF TOHOKU UNIV
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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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten

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  • CORROSION RESISTANT LOW CARBON Inventors: Tohei Ototani, Sendai; Saburo Shimodaira, lzumi; Yasuzi Kataura, Sendai, all of Japan The Research Institute For Iron,
  • ABSTRACT A chromium-containing steel having excellent corrosion resistance whose content of calcium is 0.0005 0.02 weight percent, content of carbon is not more than 0.02 weight percent and content of chromium is 25 38 weight percent.
  • Such a steel can be produced by adding calcium or an alloy thereof to a melt of ferrochromium containing chromiuml within the foregoing range and thereafter carrying out the refining operations of decarbonization, deoxidation and desulfurization.
  • the ferrochromium of the present invention is a chromium-containing ferrite type alloy steel consisting essentially, by weight, of the following constituents:
  • N up to 0.025 percent Cr 25 38 percent, preferably 27 35 percent Mo 0.5 percent Ni. .0 5 percent Cu. .0 3 percent
  • Nonmetallic inclusions up to 0.1 percent Fe remainder.
  • nonmetallic inclusions are those nonmetallic ingredients that become inevitably included in the product as constituents of the slag formed during the refining of the iron chromium alloy. These nonmetallic inclusions are composed on a weight basis of 320% CaO, 5-80% A1 0 5-80% S102 m!
  • the chromium alloy steel of the in v ention can be produced by refining a melt of iron chromium alloy whose content of chromium comes within the range specified herein above, the operation being carried out in either a vacuum furnace or a vacuum degassed apparatus, in vacuo or under an inert atmosphere such as argon, by the addition of decarbonization, deoxidation and desulfurization agents.
  • the austenite stainless steel based on the 18 8 stainless steel has been used chiefly in the past for applications requiring especially great resistance to corrosion as in the chemical industry and for other areas requiring corrosion resistance.
  • the austenite stainless steel are deficient in its resistance to corrosion, especially crystal grain boundary corrosion and stress corrosion cracks.
  • the ferrite type stainless steel is valuable also as an industrial material, and extensive researches have been made with a view to providing a steel which would possess the resistance to corrosion required to overcome the foregoing deficiency. However, none has been found as yet thatis entirely satisfactory.
  • the new stainless steel E-Brite 26-1 (trade name of Airco Company, U.S.A.), which is produced by a method developed by Airco Company, i.e., an arrange ment consisting of combination of the steps of vacuum induction melting, electron beam vacuum skull refining and continuous casting operations, is a chromiumcontaining ferrite stainless steel. Nevertheless, it has a resistance to corrosion that is comparably superior, to that of such austenite type stainless steel containing nickel and chromium, e.g., No. 304 (18 Cr 8 Ni) and No. 316 (18 Cr 10 Ni 3 Mo). It has the drawback that the equipment required in its production process is expensive.
  • a V H In the case of the chromium-containing ferrite type alloy steel of the present invention, there is no need for costly melting equipment, and its production can be carried out readily in either a vacuum furnace or a vacuum degassed apparatus in which the refining operations of decarbonization, deoxidation and desulfuriza tion are carried out by adding either metallic calcium or a calcium alloy.
  • metallic constituents other than calcium in the calcium alloy mentioned can be made of such as Al, Mn, Si, Fe and combinations of these metals.
  • the invention steel is decarbonized and desulfured with calcium and the like under vacuum conditions. Hence, it was found that the carbon content was reduced to below 0.02 percent, e.g., about 0.005 percent, and the content of sulfur was reduced to below 0.025 percent, e.g., about 0.007 percent, with the consequence that the corrosion resistance, workability, resistance to stress corrosion cracks and other properties could be improved.
  • EXPERIMENT 1 Iron chromium alloy containing 30 percent chromium was refined in an alumina crucible, using calcium or a calcium alloy. By way of comparison, the refining operation was also carried out in like manner but using carbon as the reducing agent. The constituents other than Fe of the so obtained products are shown on a weight percentage basis in Table 1.
  • Table 1 Melt No. 1 is the composition of the starting iron chromium alloy, while Melts Nos. 2 5 are the examples where either calcium or the calcium alloy was used as the deoxidant, and Melt No. 7 is the example where carbon used.
  • the composition of Melt No. 8 does not differ greatly from that of Melt No. 7 of Table 1, but the A] content of Melt No. 7 using the alumina crucible is 0.016 percent, a higher value.
  • the A] content of Melt No. 7 using the alumina crucible is 0.016 percent, a higher value.
  • metallic calcium was added in vacuo in each instance. While the oxygen decreased from 0.03 percent to 0.005 0.008 percent, the carbon content decreased to an extremely low value of 0.001 0.002 percent from its original value of 0.005 percent. This phenomenon is believed to be due to an increase in the calcium that participates in the decarbonization reaction as a result of the lesser consumption of calcium by the crucible.
  • Ca 0.0005 0.02 percent The fact that the Ca content that is detected after the vacuum treatment is from 0.0005 to 0.02 percent is very effective in improving the corrosion resistance and other properties of the product. A content of Ca in excess of 0.02 percent impairs the corrosion resistance as well as mechanical workability. On the other hand, when the Ca content is less than 0.0005 percent, this also impairs the properties, of the product, since its decarbonization is not complete. Preferable content of Ca is 0.001 0.005 percent.
  • the previously mentioned E Brite 26-] has been proposed, as having reduced the C content.
  • the content of C is reduced to below 0.02 percent, and preferably to about 0.001 percent thus achieving a great improvement of the corrosion resistance.
  • the invention alloy also possesses good resistance to brine water. 4.
  • Cr 25 38 percent Cr is an indispensable element for enhancing the resistance to corrosion. Hence, it is desirable that the content of Cr is as great as possible. However, when Cr exceeds 38 percent, the hot workability of the product suffers. On the other hand, when the content of Cr falls to below 25 percent, not only is it not possible to achieve an improvement in the corrosion resistance of the product, but also the properties possessed as a ferrite type stainless steel are sacrificed. Preferable content of Cr is 27 35 percent. 5.
  • M0 0.5 5 percent M0 is an element which not only improves the resistance to corrosion but also has the ability of forming ferrite. Hence, the lower limit of Mo has been set at 0.5 percent, so as to enable it to demonstrate these effects.
  • the upper limit of Mo was set at 5 percent, since an amount exceeding this value was not necessary in view of its relationship with the other constituents such as the contents of Cr, C and 0 as well as its high cost. 6.
  • Ni 0 5 percent Ni is added chiefly for improving the impact value at low temperatures. However, since Ni not only is expensive but also is a powerful austenite-forming element, the addition of Ni in excess impairs the properties of the product as a ferrite steel. Hence, the upper limit was set at 5 percent. 7.
  • Nonmetallic inclusions not exceeding 0.1 percent the composition of the inclusions being as follows: CaO 3 20 percent, A1 0 5 percent, and traces of Cr O MnO, FeO and CaS This value has been established on the basis of measurements of the upper and lower limits experimentally of the changes of the composition of the nonmetallic inclusions, i.e., the slag, that varies depending upon the composition of of the metallic Ca or Ca alloy that is added in vacuo or in an atmosphere of argon gas to the chromium-containing molten steel in the vacuum furnace or vacuum degassed apparatus in producing the chromium alloy steel of the present. invention. If slag in i an amount in excess of 0.1 percent remains, the corrosion resistance and mechanical properties of the product are impaired.
  • FIGS. 1 and 2 are graphs showing comparisons of the corrosion resistance of the invention steels with that of the conventional 18-8 austenite type stainless steel.
  • the corrosion resistance was tested by immersing the steel samples in an aqueous sodium chloride solution and measuring the polarization properties.
  • FIG. 1 shows the results obtained when measurements were made under the conditions of 0.1N aqueous solution of NaCl, 25C., absence of oxygen, and rate of potential raise of V/27.5 minute.
  • FIG. 2 the results in the case of FIG. 2 were obtained by measurements made using a 3 percent aqueous solution of NaCl solution at room temperature.
  • the invention steels that were tested were 25Cr-5Ni- 1.5Mo, 28Cr-4Mo, 28Cr-5Ni-l.5Mo, 30Cr-lMo, 35Cr-1Mo and 30Cr-2Mo steels. All of these steels were products that were refined with either calcium or a calcium alloy, as described in the foregoing Experiments 1 and 2, and the compositions in all cases fall within the range as defined by the present invention. On the other hand, the 18-8 austenite type stainless steel used as the comparative sample was a commercially available product.
  • the invention steels demonstrate a better anti-pitting property in all cases than the l8Cr-8Ni austenite type stainless steel.
  • the anti-pitting property of the invention steels becomes better as the pitting potential is raised.
  • the pitting potential becomes higher in the order of l8Cr-8Ni, 25Cr-5Ni-1.5Mo, 28Cr-4Mo and 28Cr-5Ni-l.5Mo.
  • a corrosion-resistant low carbon chromium alloy steel consisting essentially, percent by weight, of 0.0005 0.02 ofCa, up to 0.02 of C, up to 0.015 of 0 up to 0.015 of S, with the limitation that the sum of O and S does not exceed 0.025, up to 0.025 of N 25 38 ofCr,0.55ofMo,0-5ofNi,0-3 ofCu,upto 0.1 of nonmetallic inclusions, and the remainder being Fe; said nonmetallic inclusions being the nonmetallic ingredients that become inevitably included in the product as constituents of the slag that is formed during the refining process and consist, on a weight basis, of 3 20% CaO, 5 A1 0 5 80% SiO and traces of Cr O MnO, FeO and CaS.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
US00275072A 1972-04-05 1972-07-25 Corrosion resistant low carbon chromium alloy steel Expired - Lifetime US3778255A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3937646A (en) * 1973-11-29 1976-02-10 Hooker Chemicals & Plastics Corporation Evaporation apparatus of special material
US3967935A (en) * 1972-09-11 1976-07-06 Deutsche Edelstahlwerke Gesellschaft Mit Beschrankter Haftung Corrosion and wear resistant steel sinter alloy
JPS53118218A (en) * 1977-03-25 1978-10-16 Nippon Steel Corp Stainless steel use in apparatus for purifying automotive exhaust gas
US4139377A (en) * 1976-01-13 1979-02-13 Granges Nyby Ab Ferritic chrome steels of high notched bar impact strength and method of making same
EP0020793A1 (fr) * 1979-06-08 1981-01-07 Henrik Giflo Acier inoxydable, à haute résistance, apte au polissage et résistant aux acides
US4252561A (en) * 1976-09-21 1981-02-24 Showa Denko Kabushiki Kaisha Chromium-alloyed steel which is corrosion resistant to caustic alkaline solution
US4294613A (en) * 1979-07-03 1981-10-13 Henrik Giflo Acid resistant, high-strength steel suitable for polishing
FR2480312A1 (fr) * 1980-04-11 1981-10-16 Sumitomo Metal Ind Acier inoxydable ferritique ayant une bonne resistance a la corrosion
GB2193726A (en) * 1986-07-23 1988-02-17 Jgc Corp Carbon containing compound treating apparatus with resistance to carbon deposition
US20110044838A1 (en) * 2002-09-11 2011-02-24 Jx Nippon Mining & Metals Corporation Iron Silicide Sputtering Target and Method for Production Thereof
US20110139632A1 (en) * 2009-12-10 2011-06-16 Hamilton Sundstrand Corporation Long-term storage of potable water in metallic vessels
CN113215475A (zh) * 2021-03-26 2021-08-06 舞阳钢铁有限责任公司 一种高合金钢控氮、控夹杂的生产方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4854039A (enrdf_load_stackoverflow) * 1971-11-15 1973-07-30
JPS5634626B2 (enrdf_load_stackoverflow) * 1974-05-11 1981-08-11
JPS5333917A (en) * 1976-09-10 1978-03-30 Nisshin Steel Co Ltd High chrome ferritic stainless steel
JPS6063493U (ja) * 1983-10-04 1985-05-04 日立プラント建設株式会社 紫外線水殺菌装置
JPH02166217A (ja) * 1988-12-20 1990-06-26 Metal Res Corp:Kk 低炭素鉄クローム合金の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3231709A (en) * 1963-06-17 1966-01-25 Mckay Co Welding method and electrode
US3235417A (en) * 1965-01-11 1966-02-15 Chrysler Corp High temperature alloys and process of making the same
US3368889A (en) * 1963-11-11 1968-02-13 Baumel Anton Wear- and oxidation-resisting hard alloys
US3561953A (en) * 1968-03-19 1971-02-09 Toyota Motor Co Ltd Austenitic heat-resisting steel containing nickel, chromium and manganese
US3630723A (en) * 1967-09-19 1971-12-28 Daido Steel Co Ltd Free cutting steels

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3231709A (en) * 1963-06-17 1966-01-25 Mckay Co Welding method and electrode
US3368889A (en) * 1963-11-11 1968-02-13 Baumel Anton Wear- and oxidation-resisting hard alloys
US3235417A (en) * 1965-01-11 1966-02-15 Chrysler Corp High temperature alloys and process of making the same
US3630723A (en) * 1967-09-19 1971-12-28 Daido Steel Co Ltd Free cutting steels
US3561953A (en) * 1968-03-19 1971-02-09 Toyota Motor Co Ltd Austenitic heat-resisting steel containing nickel, chromium and manganese

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3967935A (en) * 1972-09-11 1976-07-06 Deutsche Edelstahlwerke Gesellschaft Mit Beschrankter Haftung Corrosion and wear resistant steel sinter alloy
US3937646A (en) * 1973-11-29 1976-02-10 Hooker Chemicals & Plastics Corporation Evaporation apparatus of special material
US4139377A (en) * 1976-01-13 1979-02-13 Granges Nyby Ab Ferritic chrome steels of high notched bar impact strength and method of making same
US4252561A (en) * 1976-09-21 1981-02-24 Showa Denko Kabushiki Kaisha Chromium-alloyed steel which is corrosion resistant to caustic alkaline solution
JPS53118218A (en) * 1977-03-25 1978-10-16 Nippon Steel Corp Stainless steel use in apparatus for purifying automotive exhaust gas
EP0020793A1 (fr) * 1979-06-08 1981-01-07 Henrik Giflo Acier inoxydable, à haute résistance, apte au polissage et résistant aux acides
US4294613A (en) * 1979-07-03 1981-10-13 Henrik Giflo Acid resistant, high-strength steel suitable for polishing
FR2480312A1 (fr) * 1980-04-11 1981-10-16 Sumitomo Metal Ind Acier inoxydable ferritique ayant une bonne resistance a la corrosion
GB2193726A (en) * 1986-07-23 1988-02-17 Jgc Corp Carbon containing compound treating apparatus with resistance to carbon deposition
GB2193726B (en) * 1986-07-23 1991-05-22 Jgc Corp Carbon containing compound treating apparatus with resistance to carbon deposition
US20110044838A1 (en) * 2002-09-11 2011-02-24 Jx Nippon Mining & Metals Corporation Iron Silicide Sputtering Target and Method for Production Thereof
US7972583B2 (en) * 2002-09-11 2011-07-05 Jx Nippon Mining & Metals Corporation Iron silicide sputtering target and method for production thereof
US20110139632A1 (en) * 2009-12-10 2011-06-16 Hamilton Sundstrand Corporation Long-term storage of potable water in metallic vessels
US8685257B2 (en) * 2009-12-10 2014-04-01 Hamilton Sundstrand Space Systems International, Inc. Long-term storage of potable water in metallic vessels
CN113215475A (zh) * 2021-03-26 2021-08-06 舞阳钢铁有限责任公司 一种高合金钢控氮、控夹杂的生产方法

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JPS48101316A (enrdf_load_stackoverflow) 1973-12-20

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