EP2808411B1 - Korrosionsbeständiger stahl zum halten eines kohlegefäss oder eines kohle/erz-gefässes - Google Patents

Korrosionsbeständiger stahl zum halten eines kohlegefäss oder eines kohle/erz-gefässes Download PDF

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EP2808411B1
EP2808411B1 EP12866465.3A EP12866465A EP2808411B1 EP 2808411 B1 EP2808411 B1 EP 2808411B1 EP 12866465 A EP12866465 A EP 12866465A EP 2808411 B1 EP2808411 B1 EP 2808411B1
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mass
percent
steel
corrosion
coal
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French (fr)
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EP2808411A4 (de
EP2808411A1 (de
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Masataka OMODA
Shiro Tsuri
Tsutomu Komori
Toshiyuki Hoshino
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JFE Steel Corp
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JFE Steel Corp
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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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations

Definitions

  • the present invention relates to a steel with excellent corrosion resistance used for a coal carrier or ore/coal carrier hold (may be referred to as belly of a ship).
  • Non Patent Literature 1 stipulates that renewal of a hold side shell steel is required in the case of 70% or less of the as-built thickness and renewal of a hold side frame steel is required in the case of 75% or less of the as-built thickness (where a value larger than the as-built thickness - corrosion allowance - voluntary thickness addition is not required).
  • the side shell of a bulk carrier in which the above-described pitting corrosion occurs is a single-hull, and a cargo and the seawater is separated by only a plate of steel. Then, the temperature in the hold increases on the basis of self-heating inherent in the coal. Consequently, dew condensation water is generated easily on the hold side shell because of a temperature difference between the seawater and the inside of the hold.
  • the inside of the hold is in a low pH environment in which sulfuric acid corrosion occurs easily because SO 4 2- in the coal is eluted into the above-described place where dew condensation water has been generated on the hold side shell and reacts with the dew condensation water to generate sulfuric acid.
  • Modified epoxy resin coating having a coating thickness of about 150 to 200 ⁇ m is applied to the inside of the hold as the above-described corrosion control method in the hold.
  • the coatings are peeled because of mechanical damages by coals and iron ores and flaws abrasions due to heavy machinery in cargo carrying out, so that a sufficient effect of corrosion protection is not obtained.
  • Patent Literature 1 proposes a corrosion-resistant steel by utilizing corrosion protection mechanisms for "improvement in corrosion resistance on the basis of inhibition of pH reduction” and "improvement in local corrosion resistance on the basis of sulfide fine dispersion".
  • ballast tank when no cargo is loaded, the ballast tank is poured with the seawater to perform a function of allowing a ship to achieve stable navigation and, therefore, is placed in a very severe corrosive environment.
  • the upper deck of ballast tank side is not immersed into the seawater, nor is in the state of being sprayed with the seawater. Consequently, cathodic protection does not function and, in addition, this area comes into a severe corrosive environment because the temperature of the steel increases by sunshine, and undergoes severe corrosion. Meanwhile, the side shell surface and the bottom of the ballast tank are portions immersed in the seawater completely and are in a corrosive environment, although a cathodic protection action functions.
  • Patent Literature 2 proposes that Cl - permeation is inhibited by densification of rust and Patent Literature 3 proposes a corrosion-resistant steel by utilizing a corrosion protection mechanism in which Cl - permeation is electrochemically inhibited by WO 4 2- .
  • Patent Literatures 1, 4, and 5 are mentioned as the related art referring to the coal carrier or ore/coal carrier hold use.
  • Patent Literature 1 discloses a steel containing Cu and Mg as indispensable chemical compositions
  • Patent Literature 4 discloses a steel containing Cu, Ni, and Sn as indispensable chemical compositions
  • Patent Literature 5 discloses a steel containing Cu and Sn as indispensable chemical compositions for the purpose of further improving the cost.
  • Patent Literature 6 (PTL 6) relates to a corrosion-resistant steel material for ship and vessel containing, in mass percent, C of 0.03 to 0.25%, Si of 0.05 to 0.50%, Mn of 0.1 to 2.0%, P of 0.025% or less, S of 0.01% or less, Al of 0.005 to 0.10%, W of 0.01 to 1.0%, Cr of 0.01% or more and less than 0.20%, and furthermore containing as needed one or two selected from Sb of 0.001 to 0.3% and Sn of 0.001 to 0.3% and/or one or at least two selected from Ni of 0.005 to 0.25%, Mo of 0.01 to 0.5% and Co of 0.01 to 1.0%, and containing the remainder including Fe and inevitable impurities.
  • Patent Literature 7 discloses a low alloy steel and weld joint thereof containing, in mass, C of 0.001 to 0.2%, Si of 0.01 to 2.5%, Mn of 0.1 to 2%, Cu of 0.1 to 1%, Mo of 0.001 to 1%, Sb of 0.01 to 0.2%, P of 0.05% or less and S of 0.05% or less with the balance consisting of Fe and unavoidable impurities.
  • Patent Literature 1 the subject of the steel shown in Patent Literature 1 is a steel excellent in the use environment common to ship shells, ballast tanks, cargo oil tanks, ore carrier cargo holds, and the like. Therefore, good results in the corrosion test of the cargo oil tank and the ballast tank are mentioned as the method for evaluating the corrosion resistance of the steel, although test results in consideration of the use environments of the coal carrier and ore/coal carrier holds are not shown.
  • Patent Literatures 4 and 5 the corrosion resistance under coating film is evaluated, where an environment of the coal carrier or ore/coal carrier hold is simulated.
  • an evaluation test simulating the case where peeling occurs easily because of mechanical damages by coals and iron ores, which can be said to be unavoidable in the use environment of the hold, and an evaluation of maximum pitting corrosion depth serving as a renewal guideline of the steel plate are not performed.
  • a ship is built by welding steels, e.g., steel plates, steel sheets, shaped steels, and steel bars, and corrosion protection coating films are applied to the surfaces of the steels to be used.
  • steels e.g., steel plates, steel sheets, shaped steels, and steel bars
  • corrosion protection coating films are applied to the surfaces of the steels to be used.
  • the coating is in the circumstances of being peeled easily because of mechanical damages by coals and ores, and the steel is exposed to a cyclic wet and dry environment and a low pH environment.
  • a steel capable of exerting the corrosion resistance even after peeling of a surface corrosion protection coating film of the steel has been developed.
  • the present inventors developed a testing method simulating an environment in a coal carrier or ore/coal carrier hold, and studied influences of the individual alloy elements by using the resulting testing method. As a result, it was found that the corrosion resistance of the steel after peeling of a coating film of the coal carrier or ore/coal carrier hold was improved by adding Sb or further adding Cu and Ni and, thereby, the present invention has been completed. Meanwhile, the testing method simulating an environment in the coal carrier or ore/coal carrier hold will be described later in the example.
  • a corrosion-resistant steel for a coal carrier or ore/coal carrier hold can be obtained, wherein corrosion after peeling of a coating film can be inhibited under a cyclic wet and dry environment and a low pH environment in the coal carrier or ore/coal carrier hold.
  • Carbon is an element effective in enhancing the strength of the steel.
  • the content be 0.010 percent by mass or more to ensure the strength.
  • the content is more than 0.200 percent by mass, the weldability and the toughness of a heat-affected zone are degraded. Therefore, C is specified to be within the range of 0.010 to 0.200 percent by mass, and preferably within the range of 0.050 to 0.150 percent by mass.
  • Si 0.05 to 0.50 percent by mass
  • Silicon is added as a deoxidizing agent and is an element to enhance the strength of the steel.
  • the content is specified to be 0.05 percent by mass or more. However, if the content is more than 0.50 percent by mass, the toughness of the steel is degraded. Therefore, the upper limit of Si is specified to be 0.50 percent by mass.
  • Si forms a corrosion protection film in an acidic environment to improve corrosion resistance. In order to obtain this effect, Si is preferably within the range of 0.20 to 0.40 percent by mass.
  • Manganese is an element capable of enhancing the strength of the steel at a low cost and, furthermore, capable of preventing hot brittleness. Therefore, the content is specified to be 0.10 percent by mass or more. However, if the content is more than 2.0 percent by mass, the toughness and the weldability of the steel are degraded. Therefore, Mn is specified to be within the range of 2.0 percent by mass or less, and preferably within the range of 0.80 to 1.4 percent by mass from the viewpoint of ensuring of the strength and reduction of inclusions.
  • Phosphorus is a harmful element which degrades not only the base material toughness of the steel but also the weldability and the welded portion toughness and, therefore, is desirably minimized.
  • P content is more than 0.0250 percent by mass, degradation in the base material toughness and the welded portion toughness become significant. Therefore, P is specified to be 0.0250 percent by mass or less, and preferably 0.0150 percent by mass or less.
  • Sulfur forms MnS serving as a start point of local corrosion and degrades the local corrosion resistance.
  • sulfur is a harmful element which degrades the toughness and the weldability of the steel and, therefore, is desirably minimized.
  • S is limited to 0.010 percent by mass or less, preferably 0.007 percent by mass or less, and further preferably 0.005 percent by mass or less.
  • Aluminum is added as a deoxidizing agent.
  • the content be 0.0050 percent by mass or more. If the content is more than 0.10 percent by mass, when welding is performed, the toughness of a welded metal portion is degraded. Therefore, Al is limited to within the range of 0.0050 to 0.10 percent by mass, and preferably 0.010 to 0.050 percent by mass.
  • Sb When 0.010 percent by mass or more of Sb is contained as an alloy element in the steel, Sb is concentrated in the vicinity of the steel in a low pH environment. Antimony has a large hydrogen overvoltage, so that a hydrogen generation reaction is inhibited in a portion where Sb has been precipitated and the corrosion resistance is improved. Furthermore, Sb densifies corrosion products and inhibits diffusion of H 2 O, O 2 , SO 4 2- , and Cl - into the steel.
  • Sb is limited to within the range of 0.010 to 0.50 percent by mass, preferably within the range of 0.010 to 0.30 percent by mass, and further preferably within the range of 0.010 to 0.20 percent by mass.
  • N is an element to degrade the toughness and is desirably minimized. However, it is difficult to decrease to less than 0.0010 percent by mass industrially. On the other hand, if the content is more than 0.0080 percent by mass, significant reduction in the toughness is caused. Therefore, in the present invention, N is limited to within the range of 0.0010 to 0.0080 percent by mass, and preferably 0.0010 to 0.0050 percent by mass.
  • the steel according to the present invention contains at least one selected from Cu and Ni within the following range in addition to the above-described indispensable components.
  • Cu densifies corrosion products and inhibits diffusion of H 2 O, O 2 , SO 4 2- , and Cl - into the steel. Consequently, the corrosion resistance of the steel is improved. This effect is exerted when the content is 0.010 percent by mass or more. However, as the amount of addition increases, the weldability and the toughness of the base material are degraded. Therefore, in the case where Cu is contained, Cu is preferably within the range of 0.010 to 1.0 percent by mass, further preferably within the range of 0.010 to 0.50 percent by mass, and still more preferably within the range of 0.010 to 0.35 percent by mass. Also, Cu forms Cu 2 Sb, which is an intermetallic compound, under coexistence with Sb and, therefore, has an effect in improving the corrosion resistance.
  • Ni 0.010 to 1.0 percent by mass
  • Nickel densifies corrosion products and inhibits diffusion of H 2 O, O 2 , SO 4 2- , and Cl - into the steel as with Cu. Consequently, the corrosion resistance of the steel is improved.
  • This effect is exerted when the content is 0.010 percent by mass or more. However, if the content is more than 1.0 percent by mass, the effect is saturated and, in addition, the cost increases. Therefore, in the case where Ni is contained, Ni is preferably within the range of 0.010 to 1.0 percent by mass, and further preferably within the range of 0.010 to 0.50 percent by mass.
  • the steel according to the present invention can contain Cr within the following range in addition to the above-described components.
  • Chromium is an element to cause hydrolysis in a low pH environment and, thereby, degrade the corrosion resistance. Therefore, Cr is not necessarily added. Chromium can be added to adjust the strength. However, in particular, if the content is more than 0.050 percent by mass, the corrosion resistance is degraded significantly. Therefore, in the case where Cr is contained, the content is preferably 0.050 percent by mass or less, and further preferably 0.030 percent by mass or less.
  • Tungsten and molybdenum form oxoacids when being eluted from the base material, the oxoacids electrically repel anions and prevent anions from entering up to the steel surface, so that the corrosion resistance is improved.
  • Mo and W improve the corrosion resistance by forming sparingly soluble corrosive materials, e.g., FeMoO 4 and FeWO 4 .
  • the content of each of them is preferably 0.005 percent by mass or more. However, even when addition is more than 0.5 percent by mass, not only the effect is saturated but also the cost increases. Therefore, in the case where W and Mo are contained, the content is preferably 0.5 percent by mass or less, and further preferably 0.010 to 0.3 percent by mass.
  • the steel according to the present invention can further contain at least one selected from Ti, Nb, Zr, and V within the following range in addition to the above-described components for the purpose of enhancing the strength.
  • Each of Ti, Nb, Zr, and V is an element to enhance the strength of the steel and can be selected and contained in accordance with the required strength.
  • the contents of Ti, Nb, and Zr are preferably 0.0010 percent by mass or more and the content of V is preferably 0.0020 percent by mass or more.
  • the toughness is degraded.
  • the content of each of them is preferably within the above-described range, and Ti: 0.0050 to 0.020 percent by mass, Nb: 0.0050 to 0.020 percent by mass, Zr: 0.0050 to 0.020 percent by mass, and V: 0.0050 to 0.10 percent by mass are further preferable.
  • the steel according to the present invention can contain Ca within the following range in addition to the above-described components.
  • the content is preferably at least 0.0005 percent by mass. However, if the content is too large, coarse inclusions are formed and the toughness of the base material is degraded. Therefore, in the case where Ca is contained, the upper limit is specified to be preferably 0.0040 percent by mass, and 0.0010 to 0.0030 percent by mass is further preferable.
  • the steel according to the present invention can further contain at least one selected from REM and Y within the following range in addition to the above-described components for the purpose of improving the toughness.
  • Each of REM (rare earth metal) and Y is an element to enhance the toughness of a heat-affected zone and can be contained as necessary. This effect is obtained when the content of each of REM and Y is 0.0001 percent by mass or more. However, if the content of REM is more than 0.0150 percent by mass or the content of Y is more than 0.10 percent by mass, degradation in the toughness is caused. Therefore, in the case where REM and Y are contained, the content of each of them is preferably within the above-described range.
  • the steel according to the present invention can further contain at least one selected from Se, Te, and Co within the following range in addition to the above-described components for the purpose of enhancing the strength.
  • Se and Te are elements to enhance the strength of the steel and can be contained as necessary.
  • the contents of Se and Te are preferably 0.0005 percent by mass or more and the content of Co is preferably 0.010 percent by mass or more.
  • the contents of Se, Te, and Co are preferably specified to be within the above-described range.
  • the components other than those described above are Fe and inevitable impurities.
  • components other than those described above may be contained within the bounds of not impairing the effects of the present invention.
  • Mg: 0.0001 to 0.010 percent by mass can be contained for the purpose of improving the toughness.
  • a steel produced by continuous casting or the like is hot-rolled on an "as is" basis or while reheat is performed after cooling.
  • the heat treatment condition to exhibit the corrosion resistance is not specifically limited, but it is preferable that an appropriate reduction ratio be ensured from the viewpoint of the mechanical property. If the finishing temperature of hot rolling is lower than 750°C, deformation resistance increases and a defective shape is caused. Therefore, the finishing temperature is specified to be preferably 750°C or higher.
  • a steel having a tensile strength of 490 MPa-grade or more can be produced by specifying the finishing temperature to be 750°C or higher and, thereafter, controlling the cooling rate in such a way that cooling to 600°C or lower is performed at a cooling rate of 150°C/min or more.
  • a steel to contain components shown in Table 1 was smelted with a vacuum melting furnace or smelted with a converter and, thereafter, a slab was produced by continuous casting. Subsequently, the slab was put into a furnace and was heated to 1,200°C. A steel plate having a thickness of 25 mm was produced by hot rolling at a finishing temperature of 800°C.
  • the present inventors examined the mechanism of an occurrence of pitting corrosion which has a largest influence on breakage of ship among corrosion in a coal carrier or ore/coal carrier hold. The results were as described below.
  • the side shell of a bulk carrier is a single-hull, and a cargo and the seawater is separated by only a plate of steel. Consequently, dew condensation water is generated on the hold side shell because of a temperature difference between the seawater and the inside of the hold, so that the surfaces of the steel and the coal are wetted and H 2 SO 4 -derived substances adsorbed to the coal surface are leached into a water film.
  • Pitting corrosion proceeds under the coal forming a meniscus, and H + is consumed in corrosion of the steel, so that the H + concentration is reduced in the meniscus portion.
  • the coal surface is rich in H + , and a difference in the H + concentration occurs between the coal surface and the meniscus portion. It is considered that the difference in the chemical potential serves as a driving force and H + is fed from the coal surface to the meniscus portion. Then, in a drying step, unreacted H + adheres to the coal surface again and is used for a corrosion reaction in the next dew condensation step. This steps occur over a long-term cycle, corrosion is facilitated in the meniscus portion, and pitting corrosion proceeds. In order to perform laboratory simulation of pitting corrosion in a coal carrier or ore/coal carrier hold, the following condition was employed on the basis of the present mechanism.
  • Corrosion test a A test piece of 5 mm t ⁇ 50 mm W ⁇ 75 mm L was taken from the steel plate containing components shown in Table 1. The surface of the test piece was subjected to shot blasting to remove scales and oil contents on the surface. The resulting surface was specified to be a test surface and the corrosion resistance of the steel after peeling of a coating film was evaluated. The back and the end surface were coated with silicon base adhesive tape, the test piece was fit into an acrylic cell, and 5 g of coal was laid thereon.
  • Atmosphere A temperature 60°C, humidity 95%, and 20 hours
  • Atmosphere B temperature 30°C, humidity 95%, and 3 hours
  • transition time transition time of 0.5 hours, as shown in Fig. 1
  • the symbol " ⁇ " is used in the sense of repetition (the same goes hereafter).
  • the coal employed was specified in such a way that when 5 g of coal was weighed and immersed in 100 ml of distilled water at ambient temperature for 2 hours and, thereafter, filtration was performed, the pH of a liquid leached from the coal and diluted to 200 ml became 3.0.
  • the present example was allowed to simulate the temperature-humidity environment and the dew condensation situation having a large influence on corrosion in a coal carrier or ore/coal carrier hold by performing an examination under such conditions. After the test, rust of each test piece was peeled by using a rust peeling liquid, and the amount of weight decrease of the steel was measured and taken as the amount of corrosion. Also, the resulting maximum pitting corrosion depth was measured with a depth meter. The results thereof are shown in Table 2.
  • Example 2 a test piece of 5 mm t ⁇ 50 mm W ⁇ 75 mm L was taken from the steel plate shown in Table 1. The surface of the test piece was subjected to shot blasting to remove scales and oil contents on the surface. The resulting surface was specified to be a test surface and the corrosion resistance of the steel after peeling of a coating film was evaluated. The back and the end surface were coated with silicon base adhesive tape, the test piece was fit into an acrylic cell, and 5 g of coal was laid thereon.
  • Atmosphere A temperature 60°C, humidity 95%, and 20 hours
  • Atmosphere B temperature 30°C, humidity 95%, and 3 hours
  • transition time transition time of 0.5 hours, as shown in Fig. 1
  • Corrosion test b the present testing method is referred to as Corrosion test b.
  • the coal employed was specified in such a way that when 5 g of coal was weighed and immersed in 100 ml of distilled water at ambient temperature for 2 hours and, thereafter, filtration was performed, the pH of a liquid leached from the coal and diluted to 200 ml became 3.0.
  • the present example was allowed to simulate the temperature-humidity environment and the dew condensation situation having a large influence on corrosion in a coal carrier or ore/coal carrier hold by performing an examination under such conditions. After the test, rust of each test piece was peeled by using a rust peeling liquid, and the maximum pitting corrosion depth in each time period was measured. However, the value of maximum pitting corrosion depth increased as a subject area increased.
  • the maximum pitting corrosion depth in an area equivalent to the actual ship hold area was calculated from the measurement value in the present test piece area by using extreme value statistics.
  • the hold side frame portion which is an application area of the present development steel, is corroded from both surfaces. Therefore, the maximum pitting corrosion depth in each time period was doubled, and the maximum thickness decrease 25 years later, which was a life time of ship, was estimated by extrapolation of those values. The results thereof are shown in Table 3.
  • the criteria of the maximum thickness decrease 25 years later were specified to be 4.0 mm on the basis of the steel plate renewal guideline of RULES FOR THE SURVEY AND CONSTRUCTION OF STEEL SHIPS PART CSR-B (IACS common structure rule for bulk carrier) on the precondition that the plate thickness of the application area was 15 to 20 mm, the corrosion allowance was 3.5 to 4.0 mm, and the voluntary thickness addition was 0.5 mm.
  • S mapping of rust cross-sections of Invention example No. 37-b and Comparative example No. 44-b after the test for 84 days were performed on the basis of the electron probe micro-analysis.
  • EPMA1600 produced by SHIMADZU CORPORATION was used, and a region of 100 x 100 ⁇ m was measured at acceleration voltage: 20 kV, beam diameter: 1 ⁇ m, and 0.4 ⁇ m pitch in the X and Y directions.
  • Fig. 2 shows a graph to estimate a maximum thickness decrease 25 years later.
  • the maximum thickness decrease refers to the thickness of steel plate in the portion which has been lost by local corrosion and at which the thickness decrease from the as-built thickness of a ship is maximum.
  • Invention example No. 37-b and Comparative example No. 44-b are described.
  • the maximum thickness decrease in each time period used for forming Fig. 2 was as described below in Invention example No. 37-b. 28 days: 0.85 mm, 56 days: 1.11 mm, 84 days: 1.28 mm, 168 days: 1.36 mm, and 336 days: 1.47 mm.
  • those in Comparative example No. 44-b were as described below.
  • FIG. 3 shows the results of S mapping of rust portion cross-sections after 84 days in Corrosion test b on the basis of the electron probe micro-analysis.
  • Comparative example No. 44-b an interface layer rich in S is present between a rust layer and a steel, whereas in Invention example No. 37-b, an interface layer rich in S is hardly observed. Consequently, it is estimated that in Invention example, SO 4 2- permeation to rust/steel interface is inhibited by densification of rust due to Sb and electrical repulsion of SO 4 2- due to an oxoacid of W. Accordingly, it is clear that the present invention is a steel which forms a rust layer to inhibit SO 4 2- permeation in a coal carrier or ore/coal carrier hold environment.
  • the effects of the present invention were ascertained.
  • the method shown in Fig. 1 was employed as the testing method simulating the coal carrier or ore/coal carrier hold environment, and results very consistent with those in the case where evaluation was performed on the basis of placement in an actual coal carrier or ore/coal carrier hold were obtained.
  • the conditions of Atmospheres A and B, the transition times, the cycle, the method for adjusting the coal, and the conditions, e.g., the value of pH of the liquid leached from the coal are not limited to the above-described examples and can be changed appropriately in accordance with the use environment of the steel in the hold.
  • the steel according to the present invention can be used as a constituent member of a coal carrier or ore/coal carrier hold, where the coating film is peeled easily because of mechanical damages by coals and ores, and the steel is exposed to a cyclic wet and dry environment and a low pH environment.
  • Table 1-1 (mass%) Steel plate No.

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Claims (7)

  1. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme, wobei
    die chemische Zusammensetzung des Stahls aus C: 0,010 bis 0,200 Massenprozent, Si: 0,05 bis 0,50 Massenprozent, Mn: 0,10 bis 2,0 Massenprozent, P: 0,0250 Massenprozent oder weniger, S: 0,010 Massenprozent oder weniger, Al: 0,0050 bis 0,10 Massenprozent, Sb: 0,010 bis 0,50 Massenprozent, N: 0,0010 bis 0,0080 Massenprozent besteht und ferner zumindest eines ausgewählt aus Cu: 0,010 bis 1,0 Massenprozent und Ni: 0,010 bis 1,0 Massenprozent aufweist und ferner optional zumindest eines ausgewählt aus Cr: 0,050 Massenprozent oder weniger, W: 0,005 bis 0,5 Massenprozent, Mo: 0,005 bis 0,5 Massenprozent, Ti: 0,0010 bis 0,030 Massenprozent, Nb: 0,0010 bis 0,030 Massenprozent, Zr: 0,0010 bis 0,030 Massenprozent, V: 0,0020 bis 0,20 Massenprozent, Ca: 0,0005 bis 0,0040 Massenprozent, REM: 0,0001 bis 0,0150 Massenprozent, Y: 0,0001 bis 0,10 Massenprozent, Se: 0,0005 bis 0,50 Massenprozent, Te: 0,0005 bis 0,50 Massenprozent und Co: 0,010 bis 0,50 Massenprozent aufweist und zusätzlich der Rest Eisen und unvermeidbare Verunreinigen ist.
  2. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme nach Anspruch 1, wobei
    in dem Stahl Cr etwa 0,050 Massenprozent oder weniger beträgt.
  3. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme nach Anspruch 1 oder Anspruch 2, der
    mindestens eines ausgewählt aus W: 0,005 bis 0,5 Massenprozent und Mo: 0,005 bis 0,5 Massenprozent zusätzlich zu dem Stahl aufweist.
  4. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme nach einem der Ansprüche 1 bis 3, der
    zumindest eines ausgewählt aus Ti: 0,0010 bis 0,030 Massenprozent, Nb: 0,0010 bis 0,030 Massenprozent, Zr: 0,0010 bis 0,030 Massenprozent und V: 0,0020 bis 0,20 Massenprozent zusätzlich zu dem Stahl aufweist.
  5. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme nach einem der Ansprüche 1 bis 4, der
    zusätzlich zu dem Stahl Ca: 0,0005 bis 0,0040 Massenprozent aufweist.
  6. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme nach einem der Ansprüche 1 bis 5, der
    zumindestens einen ausgewählt aus REM: 0,0001 bis 0,0150 Massenprozent und Y: 0,0001 bis 0,10 Massenprozent zusätzlich zu dem Stahl aufweist.
  7. Korrosionsbeständiger Stahl für einen Kohletransporter oder Erz-/Kohle-Transporteraufnahme nach einem der Ansprüche 1 bis 6, der
    zumindestens eines ausgewählt aus Se: 0,0005 bis 0,50 Massenprozent, Te: 0,0005 bis 0,50 Massenprozent und Co: 0,010 bis 0,50 Massenprozent zusätzlich zu dem Stahl aufweist.
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WO2013111355A1 (ja) 2013-08-01
CN104105806A (zh) 2014-10-15
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