US3443934A - Steel alloys resistant to sulfuric acid and containing small quantity of alloying elements of copper,chromium,and tin or antimony - Google Patents

Steel alloys resistant to sulfuric acid and containing small quantity of alloying elements of copper,chromium,and tin or antimony Download PDF

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Publication number
US3443934A
US3443934A US540343A US3443934DA US3443934A US 3443934 A US3443934 A US 3443934A US 540343 A US540343 A US 540343A US 3443934D A US3443934D A US 3443934DA US 3443934 A US3443934 A US 3443934A
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Prior art keywords
sulfuric acid
steel
antimony
tin
copper
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Expired - Lifetime
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US540343A
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English (en)
Inventor
Hirovuki Kubota
Tohru Mimino
Yuh Fukuda
Yoshio Ishizu
Toshio Nago
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JFE Engineering Corp
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Nippon Kokan Ltd
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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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • B23K35/3053—Fe as the principal constituent
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • a steel resistant to sulfuric acid consists essentially of carbon less than about .15 silicon less than about .40%, manganese in an amount less than about .50% phosphorus in an amount less than .03, sulfur in an amount less than about .03, copper in an amount of about .2.6%, chromium in amount 0.30.9% at least one substance selected from the group consisting of antimony and tin in an amount of about .050.5% and the balance iron.
  • This invention relates to steel alloys containing a relatively small quantity of alloying elements and more particularly to steel alloys containing a small quantity of carbon, copper and chromium, wherein antimony or tin or both of them is incorporated in the steel alloys for the purpose of greatly improving the corrosion resistance of the alloys against sulfuric acid.
  • Another object of this invention is to provide an improved welding material which can produce welded articles having high resistance to sulfuric acid.
  • the novel steel alloy consists of less than 0.15 of carbon, less than 0.40% of silicon, less than 0.50% of manganese, less than 0.03% of phosphorus, less than 0.03% of sulfur from 0.2 to 0.6% of copper, from 0.3 to 0 .9% of chromium, from 0.05 to 0.5% of antimony or tin or both, and the balance of iron and impurities.
  • the novel alloy further contains from 0.30 to 0.80% of nickel in addition to various ingredients mentioned above.
  • this last mentioned steel alloy which contains nickel is utilized as welding electrodes or welding wires.
  • FIG. 1 shows the manner of dissolving of ordinary steel in hot sulfuric acid
  • FIG. 2 is a chart that shows the result of corrosion test in hot sulfuric acid made on the novel steel alloys containing lesser quantities of alloying elements and on control samples;
  • FIG. 3 shows the relation between piercing temperature and limiting reduction percentage
  • FIG. 4 shows the test results of corrosion by hot sulfuric acid made on the novel steel alloy and on contrast material
  • FIG. 5 are photographs showing macro-structure of the contrast material caused by piercing test
  • FIG. 6 are photographs showing macro-structures of the steel alloy according to this invention caused by piercing test and FIG. 7 are photographs which show the results of comparison tests utilizing hot sulfuric acid made on welds prepared by the novel welding rod and conventional welding rod.
  • a basic steel alloy consisting of less than 0.15% of carbon, less than 0.40% of silicon, less than 0.50% of manganese, less than 0.03% of phosphorus, less than 0.03% of sulfur, from 0.2 to 0.6% of copper, from 0.3 to 0.9% of chromium, from 0.05 to 0.5% of antimony and the balance of iron and impurities, said basic steel alloy being characterized by its low contents of alloying 3 4 elements and high resistance against the corrosive effect corrosion resistance property of the steel alloy in the of sulfuric acid.
  • tin may be substituted for anregion IV shown in FIG. 1,
  • the cumulative effect timony in the above mentioned composition, in which caused by the coexistence of tin and antimony is more case the steel alloy consists of less than 0.40% of silicon, effective than the incorporation of either tin or antimony.
  • Ranges of silicon and manganese of less than 0.4% and of les h 050%, TABLE 1.EFFECTIVE ADDITIVE ELEMENTS IN VARIOUS respectively, are the ranges of deoxrdizlng agents re- REGIONS quired to be used in the process of steel manufacturing. 1 n In W Upper limits of 0.03% for prosphorus and 0.03% for sulfur represent the limits below which it is difficult to Efiecfiveaddime918mm,, SB reduce the quantity of these elements in steel manufac- Sb Sn +Sn) turing art.
  • phosphorus has a tendency of promoting corrosion, it is essential to limit its upper range to the prescribed value.
  • copper is an element effective to impart a corrosion resistant property, incorporation thereof of less than 0.2% is not effective and Table 2 below Shows ypi l Chemical compositions of copper in excess of 0.6% results in difiiculties in the steel samples of steel alloys of this invention and those of conmanufacturing process.
  • Chromium in the range of from trol samples and Table 3 shows the results of immersion 0.3 to 0.9% exhibits a corrosion resistant property when tests in hot sulfuric acid.
  • FIG. 2 shows the test result shown in Table pointed out before, this invention is characterized by in- 3.
  • Co-existence of tin and antimony in the steel alloy satisfying these requirements consists of less range of from 0.05 to 0.5% is intended for improving the than 0.15% of carbon, less than 0.40% of silicon, less than 0.50% of manganese, less than 0.3% of phosphorus, less than 0.03% of sulfur, from 0.20 to 0.60% of copper, from 0.30 to 0.90% of chromium, from 0.30 to 0.80% of nickel, from 0.05 to 0.50% of the sum of antimony and tin, and the balance of iron and impurities.
  • the modified embodiment is characterized by containing from 0.30 to 0.80% of nickel in addition to the various elements employed in the first embodiment. Incorporation of nickel in the range specified hereinabove 6 interfaces, thus forming cracks there and causing poor hot workability. However, incorporation of Ni has an efiect of preventing easy oxidation of iron. Further, Cu, Sb and Sn which are precipitated and accumulated at the interfaces of grains will be mixed with nickel and form compounds of high melting points which contributes to preserving good hot workability.
  • Nickel also prevents accumulation of additive elements effective to impart the desired corrosion resistant property at interfaces between crystalline particles which is caused by the selective oxidation of the iron component at the time of hot working. In order to impart satisfactory hot workability under severe operating conditions it is necessary to select the lower limit of 0.30%, whereas when the upper limit of 0.80% is exceeded the corrosion resistant property of the steel alloys decreases gradually. This range of nickel is also suitable Each of these samples were immersed for 5 hours in sulfuric acids of diiferent concentrations and maintained at different temperatures to test its corrosion, and the results are tabulated in the following Table 5. As can be noted from this table samples of this invention, namely samples, B, C, E and F each containing nickel showed lesser corrosion than control samples. In Table 5, percentages show the concentration of sulfuric acid, C. indicates the temperature of sulfuric acid and other numerical data represent corrosion expressed in term of mg./cm. /5 hrs.
  • FIGS. 5 and 6 Macro-structures of test pieces which have undergone the above test are shown by photographs in FIGS. 5 and 6 which clearly show excellent internal characteristics of the steel alloys embodying this invention.
  • the internal flexibility of each of the test pieces shown in FIGS. 5 and 6 becomes lost as the temperature of the test piece is decreased, thus obscuring the interfaces between grains. This condition is more prominent in the control sample shown in FIG. 5, especially so in 18-8 stainless steel (FIG. 5B).
  • the sample shown in FIG. 5, which contains antimony, shows fairly good internal characteristics at a temperature of 1250 C., which is the appropriate temperature for piercing, but its limiting reduction percentage was 50%.
  • FIG. 6 shows the internal characteristic of samples C and F which are incorporated with nickel in accordance with this invention. As can be noted from this figure internal characteristics as well as the limiting reduction percentage have been greatly improved. (The limiting percentages being 90 and 63%, respectively for samples C and F.)
  • steel alloys according to the first embodiment of this invention are suitable for use as steel tubes or steel plates at low temperature portions of boilers burning heavy oil wherein a circumstance in which corrosion by sulfuric acid prevails.
  • a relatively low amount of nickel is added to the composition of the first embodiment whereby hot workability and processability of steel alloys are greatly improved, thus making it possible to prepare at lower cost such steel products as special steel plates, structural steel members, steel tubes and the like which are vigorously required to have precise dimensions.
  • These products find their use in steam power plants, petroleum refining plants, city gas refining plants, synthetic chemical industry, and various chemical plants for manufacturing ethylene, olefines and derivatives thereof.
  • steel alloys containing nickel and prepared according to the second embodiment of this invention also suitable for use as welding rod or wire for oxygen or acetylene gas welding.
  • Such welding rod or wire can also be used in consumptive or non-consumptive welding, such as TIG (tungsten inert gas) Welding.
  • TIG tungsten inert gas
  • Welding rods or Wires of this invention are especially suitable for welding together mother metals having high resistance to corrosion caused by sulfuric acid, such as those having compositions according to the above described first and second embodiments, whereby the Welded article will have homogeneous metallurgical structure.
  • welded products as steel plates, structural steels, steel tubes and the like. These products can be welded and treated in the same manner as the case wherein ordinary welding rods available on the market are utilized.
  • elements such as Cu, Sb, Sn, et cetera are incorporated in steel alloys, these elements will form solid solutions in ferrite.
  • Table 7.Chemical composition of the welding rod In order to investigate the ability and characteristics of the novel welding rod, two types of welding rods were prepared, i.e. one being a gas welding rod GA 43) having a tensile strength of more than 44 kg./mm. and an elongation of more than 20%) for mild steels prepared in accordance with Japanese Industrial Standards (JIS) Z 3201 and the other being the novel welding rod, each having a diameter of 3.2 mm. Two sheets of 5 x 100 x 200 mm.
  • JIS Japanese Industrial Standards
  • steel plates having high resistance against sulfuric acid were prepared each consisting of 0.08% of carbon, 0.19% of silicon, 0.47% of manganese, 0.012% of phosphorus, 0.013% of sulfur, 0.42% of copper, 0.50% of chromium, 0.35% of nickel and 0.11% of antimony. These plates were then butt welded with 60 V shaped groove provided at their center by means of one pass manual welding procedure utilizing oxygen and acetylene gas test pieces of the dimensions of 3 x 20 x 40 mm. thus obtained was finished by machining, and tested their corrosion by immersing them for 5 hours in sulfuric acids of various concentrations and maintained at different temperatures. The result of the test is shown in Table 8 below and attached photographs denoted by FIG. 7. The table and photographs show that welds obtained by using the novel welding rod have sufiicient corrosion resistance.
  • steel alloys of the type used herein exhibit a high value of corrosion at test conditions of about 40%, 50 C. and 50%, 60 C., so that corrosions under these conditions are most important.
  • Conventional mild steel generally shows values of corrosion of approximately from 100 to 400 mg./cm. /5 hrs. under these test conditions, so that numerical data shown in the above Table 8 prove that the novel welding electrode has made a great advance in the Welding art.
  • Sulfuric acid-resistant steel alloy consisting essentially of carbon in an amount less than about 0.15%, silicon in an amount less than about 0.40%, manganese in an amount less than about 0.50%, phosphorus in an amount less than about 0.03%, sulfur in an amount less than about 0.03%, copper in an amount of about 0.2- 06%, chromium in an amount of about 03-09%, at least one substance selected from the group consisting of antimony and tin in an amount of about 0.05-0.5%, and the balance iron.
  • Sulfuric acid-resistant steel alloy consisting essentially of carbon in an amount less than about 0.15%, silicon in an amount less than about 0.40%, manganese in an amount less than about 0.50%, phosphorus in an amount less than about 0.03%, sulfur in an amount less than about 0.03%, copper in an amount of about 0.2- 06%, chromium in an amount of about 03-09%, at least one substance selected from the group consisting of antimony and tin in an amount of about 0.050.5%, nickel in an amount of about 0.3-0.80%, and the balance iron.
  • Elongated welding material formed of an alloy consisting essentially of carbon in an amount less than about 0.15%, silicon in an amount less than about 0.40%, manganese in an amount less than about 0.50%, phosphorus in an amount less than about 0.03%, sulfur in an amount less than about 0.03%, copper in an amount of about 02-06%, chromium in an amount of about 03-09%, at least one substance selected from the group consisting of antimony and tin in an amount of about 0.050.5%, nickel in an amount of about 0.3-0.80%, and the balance iron.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Arc Welding In General (AREA)
  • Heat Treatment Of Steel (AREA)
  • Nonmetallic Welding Materials (AREA)
US540343A 1965-04-12 1966-04-05 Steel alloys resistant to sulfuric acid and containing small quantity of alloying elements of copper,chromium,and tin or antimony Expired - Lifetime US3443934A (en)

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JP2117365 1965-04-12
JP5224565 1965-08-27
JP6067565 1965-10-04

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853544A (en) * 1970-01-14 1974-12-10 Nippon Steel Corp Corrosion resistant steels having improved weldability
US3909251A (en) * 1974-12-05 1975-09-30 Us Interior Prevention of surface cracking due to formation of copper alloys of tin and antimony during reheating of steel
EP0393522A1 (en) * 1989-04-13 1990-10-24 Kawasaki Steel Corporation Steel pipe and a method for welding thereof and pipeline resistant to carbon dioxide corrosion
EP0394943A2 (en) 1989-04-25 1990-10-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0772087A1 (en) 1995-10-31 1997-05-07 Fuji Photo Film Co., Ltd. Pyrazolylazophenol dye
WO2003044236A1 (fr) * 2001-11-19 2003-05-30 Nippon Steel Corporation Acier faiblement allie tres resistant a la corrosion engendree par l'acide chlorique et l'acide sulfurique et joint soude renfermant celui-ci
US20080166256A1 (en) * 2005-02-28 2008-07-10 Shunji Sakamoto Steel Excellent in Resistance to Sulfuric Acid Dew Point Corrosion
CN105239007A (zh) * 2015-11-25 2016-01-13 莱芜钢铁集团有限公司 一种无镍高韧性耐候钢板及其制造方法
US20180148811A1 (en) * 2015-05-28 2018-05-31 Posco Hot-rolled steel sheet having excellent composite corrosion resistance to sulfuric acid and hydrochloric acid and manufacturing method therefor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111066680B (zh) * 2019-12-20 2021-11-19 柳州钢铁股份有限公司 一种畜牧业用耐候耐酸盘条

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2013600A (en) * 1929-05-11 1935-09-03 Vereinigte Stahlwerke Ag Articles which must have a reduced tendency to rust
US2150342A (en) * 1938-05-05 1939-03-14 Byramji D Saklatwalla Alloy steel and structural member
US2867531A (en) * 1957-01-31 1959-01-06 Gen Motors Corp Corrosion-resistant low alloy steel
US3177070A (en) * 1961-04-25 1965-04-06 Metallurg D Esperance Longdoz Steel for drawing, and method of manufacturing this steel

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT112813B (de) * 1922-08-26 1929-04-10 Byramji Dorabji Saklatwalla Chrom und Kupfer enthaltende Eisenlegierungen.
DE142900C (de) * 1931-09-09 1903-08-22 Katharina Geishecker Gewirktes unterbeinkleid u dgl mit eingesetztem, geschlitzten gesässtell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2013600A (en) * 1929-05-11 1935-09-03 Vereinigte Stahlwerke Ag Articles which must have a reduced tendency to rust
US2150342A (en) * 1938-05-05 1939-03-14 Byramji D Saklatwalla Alloy steel and structural member
US2867531A (en) * 1957-01-31 1959-01-06 Gen Motors Corp Corrosion-resistant low alloy steel
US3177070A (en) * 1961-04-25 1965-04-06 Metallurg D Esperance Longdoz Steel for drawing, and method of manufacturing this steel

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853544A (en) * 1970-01-14 1974-12-10 Nippon Steel Corp Corrosion resistant steels having improved weldability
US3909251A (en) * 1974-12-05 1975-09-30 Us Interior Prevention of surface cracking due to formation of copper alloys of tin and antimony during reheating of steel
EP0393522A1 (en) * 1989-04-13 1990-10-24 Kawasaki Steel Corporation Steel pipe and a method for welding thereof and pipeline resistant to carbon dioxide corrosion
EP0394943A2 (en) 1989-04-25 1990-10-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0772087A1 (en) 1995-10-31 1997-05-07 Fuji Photo Film Co., Ltd. Pyrazolylazophenol dye
US20050013722A1 (en) * 2001-11-19 2005-01-20 Akira Usami Low alloy steel excellent in resistance to corrosion by hydrochloric acid and corrosion by sulfuric acid and weld joint comprising the same
WO2003044236A1 (fr) * 2001-11-19 2003-05-30 Nippon Steel Corporation Acier faiblement allie tres resistant a la corrosion engendree par l'acide chlorique et l'acide sulfurique et joint soude renfermant celui-ci
US20070269335A1 (en) * 2001-11-19 2007-11-22 Nippon Steel Corporation Low alloy steel and weld joint thereof excellent in corrosion resistance to hydrochloric acid and sulfuric acid
US7718014B2 (en) 2001-11-19 2010-05-18 Nippon Steel Corporation Low alloy steel and weld joint thereof excellent in corrosion resistance to hydrochloric acid and sulfuric acid
US7731896B2 (en) 2001-11-19 2010-06-08 Nippon Steel Corporation Low alloy steel and weld joint thereof excellent in corrosion resistance to hydrochloric acid and sulfuric acid
US20080166256A1 (en) * 2005-02-28 2008-07-10 Shunji Sakamoto Steel Excellent in Resistance to Sulfuric Acid Dew Point Corrosion
US8361245B2 (en) 2005-02-28 2013-01-29 Nippon Steel Corporation Steel excellent in resistance to sulfuric acid dew point corrosion
US20180148811A1 (en) * 2015-05-28 2018-05-31 Posco Hot-rolled steel sheet having excellent composite corrosion resistance to sulfuric acid and hydrochloric acid and manufacturing method therefor
CN105239007A (zh) * 2015-11-25 2016-01-13 莱芜钢铁集团有限公司 一种无镍高韧性耐候钢板及其制造方法
CN105239007B (zh) * 2015-11-25 2018-03-23 山东钢铁股份有限公司 一种无镍高韧性耐候钢板及其制造方法

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Publication number Publication date
DE1783151A1 (de) 1973-04-19
DE1783151B2 (de) 1973-11-29
DE1783151C3 (pt) 1974-06-27
GB1101728A (en) 1968-01-31
DE1533332B1 (de) 1972-08-17

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