US20150132177A1 - Stainless clad steel with excellent corrosion resistance - Google Patents

Stainless clad steel with excellent corrosion resistance Download PDF

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US20150132177A1
US20150132177A1 US14/383,825 US201314383825A US2015132177A1 US 20150132177 A1 US20150132177 A1 US 20150132177A1 US 201314383825 A US201314383825 A US 201314383825A US 2015132177 A1 US2015132177 A1 US 2015132177A1
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steel
concentration
stainless
cladding material
glossiness
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Yoshihiro Yazawa
Shunichi Tachibana
Keiichiro Kishi
Yota Kuronuma
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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
    • 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
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • 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
    • C22C38/18—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
    • 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
    • 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
    • C21D2251/00—Treating composite or clad material
    • C21D2251/02—Clad material

Definitions

  • This disclosure relates to a stainless clad steel with excellent corrosion resistance, used for various application purposes typified by offshore structures, heat exchangers, chemical tankers, chemical plants, and pressure vessels.
  • Stainless clad steel refers to a steel product in which two types of metals having different properties are bonded together, where a cladding material is a stainless steel and a base material is a carbon steel.
  • the clad steel is produced by metallurgically bonding different types of metals so that, in contrast to coating, there is no fear of peeling and new characteristics, which are not exhibited by a single metal or an alloy, can be provided.
  • the type of stainless steel serving as a cladding material is selected on a use environment basis and, thereby, the corrosion resistance equivalent to that in the case where the stainless steel is employed throughout the thickness (hereafter may be referred to as “solid material”).
  • stainless clad steel has advantages that compatibility between economy and functionality can be ensured because a usage of the stainless steel is reduced and the rusting resistance equivalent to that of a solid material can be ensured. Consequently, it is believed that stainless clad steel is a very useful functional steel product, and needs for the stainless clad steel have increased in various industrial fields.
  • stainless clad steel is used for application purposes requiring corrosion resistance. Therefore, enhancement in functionality of the surface is an important technical issue.
  • a technique in which the corrosion resistance conforming to the requirement is ensured by selecting a stainless steel used as a cladding material is employed in general to ensure the corrosion resistance of the stainless clad steel sheet required on an application purpose (for example, offshore structures, heat exchangers, chemical plants, chemical tankers, and pressure vessels, etc.) basis.
  • an application purpose for example, offshore structures, heat exchangers, chemical plants, chemical tankers, and pressure vessels, etc.
  • Examples of technologies to improve the corrosion resistance of the stainless clad steel include Japanese Patent No. 4179133, Japanese Patent No. 3409660, Japanese Patent No. 3514889 and Japanese Patent No. 3401538.
  • Japanese Patent No. 4179133 discloses a method in which, in a method of manufacturing a stainless clad steel pipe by employing a stainless steel with excellent corrosion resistance in sea water as a cladding material and carbon steel as a base material, the solid solution heat treatment condition is specified and the components of the base material carbon steel are specified to be within appropriate component ranges to recover degradation in the corrosion resistance of a seam weld zone.
  • that method prevents precipitation of a second phase that degrades the corrosion resistance, and study on the surface quality of the stainless steel is not performed. That is, the surface quality, e.g., a Cr concentration ratio in a passivation film and the glossiness of the surface, has not been studied. Therefore, a dramatic improvement in the corrosion resistance is not expected.
  • Japanese Patent No. 3409660 discloses a thin stainless clad steel sheet by employing an austenite stainless steel as a cladding material and a low-carbon steel as a base material among thin stainless clad steel sheets suitable for raw materials to be subjected to working, e.g., deep drawing, punch stretching, and bending.
  • Japanese Patent No. 3409660 does not disclose improvement of corrosion resistance, although a technology to reduce uneven shapes of the steel sheet surface in working is disclosed.
  • Japanese Patent No. 3514889 discloses an austenite stainless clad steel sheet used in fields, e.g., line pipes used in a sour gas environment, tanks in chemical tankers, and absorption containers for flue gas desulfurization apparatuses, in which high corrosion resistance is required and a manufacturing method, e.g., a heat treatment condition, thereof.
  • Japanese Patent No. 3514889 only discloses ensuring the steel sheet corrosion resistance basically by specifying the types of alloy components and adjusting the content, and a relationship with the technology related to the surface quality has not been studied.
  • Japanese Patent No. 3401538 discloses a super stainless/stainless clad steel sheet formed from a composite metal sheet with excellent corrosion resistance and formability.
  • a super stainless steel containing Ni, Cr, Mo, and N and having a composition satisfying the condition of (Cr+2 ⁇ Mo+9 ⁇ N) ⁇ 27% (percent by weight), 16% ⁇ Ni ⁇ 30%, 18% ⁇ Cr ⁇ 30%, 7% ⁇ Mo ⁇ 8%, and 0.10% ⁇ N is employed as a cladding material on both surfaces or one surface of the stainless steel and the interface between the super stainless steel and the stainless steel is metallurgically bonded.
  • corrosion resistance is enhanced by alloy elements and, therefore, it is difficult to improve the characteristics without increasing the amount of addition of the alloy elements.
  • Stainless steel is a generic name for the steel product which is a Fe—Cr or Fe—Cr—Ni alloy steel having the corrosion resistance in such a way as to become applicable to uses in need of corrosion resistance in sea water and which is characterized by containing Cr at a high content (for example, 20% or more) and Mo (for example, 2% or more), wherein a ⁇ phase (intermetallic compound) is precipitated in a manufacturing process.
  • a high content for example, 20% or more
  • Mo for example, 2% or more
  • Gs(60) (Gs(60) L +2 ⁇ Gs(60) D +Gs(60) C )/4 Formula (2).
  • a stainless clad steel with improved corrosion resistance, in particular, rusting resistance can be provided, wherein an appearance is improved because of prevention of discoloration of the surface and outflow rust can be improved.
  • a stainless clad steel with excellent appearance due to corrosion resistance, especially prevention of outflow rust is favorably used for various application purposes typified by offshore structures, heat exchangers, chemical tankers, chemical plants, and pressure vessels.
  • FIG. 1 is a diagram showing measurement examples of the Cr concentrations (atomic percent) and the Fe concentrations (atomic percent) of a passivation film and a stainless steel parent phase portion.
  • FIG. 2 is a diagram showing the measurement condition of the surface glossiness.
  • the stainless clad steel is a stainless clad steel by using a stainless steel having Pitting Index represented by Formula (1) of 35 or more as a cladding material.
  • Pitting Index (Cr+3.3Mo+16N) . . .
  • Cr, Mo, and N indicate the contents (percent by mass) of their respective elements, and the case of no inclusion is specified to be 0.
  • Pitting Index (Cr+3.3Mo+16N) ⁇ 35 is selected because when uses in need of the corrosion resistance (in particular, crevice corrosion resistance) are considered among various application purposes typified by offshore structures, heat exchangers, chemical tankers, chemical plants, and pressure vessels, it is believed to be necessary to contain much Cr and Mo effective in preventing occurrence and growth of pitting and have Pitting Index serving as an indicator of pitting resistance of 35 or more.
  • the relationship between Pitting Index and CPT Critical Pitting Temperature (ASTM G48-03 Method E)
  • CCT Critical Crevice Temperature
  • the amount of precipitation of a ⁇ (sigma) phase of the surface of the cladding material is 2.0% or less on an area ratio basis.
  • a high-alloy stainless clad steel which can improve an appearance because of the corrosion resistance, in particular, rusting resistance, and prevention of discoloration of the surface and which can improve outflow rust is obtained by controlling the surface quality and, in addition, specifying precipitation of the ⁇ phase in the steel to be 2.0% or less.
  • a ⁇ phase precipitated in the steel containing Mo was an intermetallic compound containing FeCrMo by identifying a residue extracted by a Speed method in a 10% acetylacetone-1% tetramethylammonium mixed electrolytic solution (commonly called AA solution) on the basis of X-ray diffraction.
  • AA solution 10% acetylacetone-1% tetramethylammonium mixed electrolytic solution
  • ⁇ phase is precipitated, Cr and Mo in the steel are reduced. It is preferable that the amount of precipitation of ⁇ phase be minimized because Cr and Mo in the steel are alloy elements effective in improving the corrosion resistance.
  • a heat treatment (Q-T treatment) is performed in consideration of a production process of a clad steel and strength-toughness of a base material.
  • Q-T treatment a heat treatment
  • precipitation of a ⁇ phase in the heat treatment and a cooling process thereof is not avoided depending on the heat treatment and cooling conditions.
  • precipitation of a ⁇ phase may occur to cause significant degradation in corrosion resistance.
  • the relationship between the amount of precipitation of the ⁇ phase and the corrosion resistance of the stainless steel (cladding material) surface was examined. As a result, we found that when the amount of precipitation of the ⁇ phase was more than 2.0%, the corrosion resistance was degraded significantly and an occurrence of rusting of the surface was conspicuous. The reason for this is believed to be that if the amount of precipitation of the ⁇ phase is more than 2.0%, ⁇ phases precipitated at grain boundaries are joined and cover the grain boundaries and, thereby, corrosion is conspicuous.
  • the ratio of Cr concentration (atomic percent)/Fe concentration (atomic percent) in a passivation film portion of the cladding material to Cr concentration (atomic percent)/Fe concentration (atomic percent) of a parent phase portion of the above-described cladding material is 1.20 or more.
  • the Cr concentration (atomic percent)/Fe concentration (atomic percent) in the passivation film portion of the cladding material is very important factor in an improvement of pitting resistance.
  • the ratio (I 1 /I 2 hereafter abbreviated as Cr/Fe concentration ratio) of Cr concentration (atomic percent)/Fe concentration (atomic percent); I 1 in the passivation film portion of the stainless steel serving as the cladding material to Cr concentration (atomic percent)/Fe concentration (atomic percent); I 2 in a parent phase portion becomes high, a stable passivation film with excellent pitting resistance is disposed as the surface layer. Therefore, a higher Cr/Fe concentration ratio is better from the viewpoint of the corrosion resistance.
  • the Cr/Fe concentration ratio of 1.20 or more was necessary to exert a corrosion resistance (pitting resistance) improving effect clearly on the basis of an atmospheric corrosion test or an accelerated corrosion test as compared with an abrasive.
  • the Cr/Fe concentration ratio is specified to be 1.20 or more on the basis of this finding.
  • the Cr/Fe concentration ratio is 1.50 or more.
  • the stainless clad steel sheet is a clad steel sheet of a carbon steel and a stainless steel. Therefore, in a dipping treatment in a predetermined solution, it is necessary to make considerations in such a way that the common steel is not dissolved, and an application of a load is necessary to improve the degree of concentration of Cr in the surface layer to higher than or equal to that of a solid material (stainless steel). As described above, an equipment load is required for an excessive improvement in the Cr/Fe concentration ratio. Therefore, preferable upper limit is 5.0 or less.
  • the surface-controlling technique can be a combination of various known surface-polishing techniques, e.g., common belt polishing, grinder polishing, abrasive wheel polishing, electrolytic polishing, and a pickling treatment.
  • the surface roughness and the anisotropy thereof are controlled at low levels by combining the above-described techniques and, in addition, the passivation film is strengthened, so that desired characteristics are obtained.
  • methods of strengthening the passivation film of the surface include a technique by using a pickling treatment with nitric acid or fluoro-nitric acid or electrolytic polishing. It is also possible to combine these methods with an electrolytic neutral pickling treatment in a neutral salt solution (for example, Ruther process: 20% sodium sulfate solution and sodium nitrate).
  • the Cr/Fe concentration ratio can be determined by, for example, measuring the concentration profile (atomic percent) of an element while the steel surface is sputtered in the depth direction and determining an atomic ratio of Cr to Fe from the individual element (Fe, Cr, and the like) concentration profiles.
  • a region in which the values (atomic percent) of Cr and Fe are almost constant values is assumed to be a parent phase portion, and a region with a sputtering time shorter than that is defined as a passivation film portion.
  • the passivation film portion the value at the site exhibiting a highest Cr/Fe value is defined as the Cr concentration (atomic percent)/Fe concentration (atomic percent) in the passivation film portion.
  • the average glossiness indicator Gs(60) calculated by Formula (2) be 60 or more, where the specular glossiness at a measurement angle of 60° defined in JIS Z 8741 (1997) (Specular glossiness-methods of measurement) is measured in a rolling direction (Gs(60) L ), in a direction perpendicular to the rolling direction (Gs(60) C ), and in a direction at an angle of 45 degrees with respect to the rolling direction (Gs(60) D ).
  • Gs(60) (Gs(60) L +2 ⁇ Gs(60) D +Gs(60) C )/4 (2)
  • the average glossiness indicators Gs(60) L , Gs(60) C , Gs(60) D and Gs(60) are 60 or more, where the specular glossiness at a measurement angle of 60° defined in JIS Z 8741.
  • the surface glossiness is an indicator showing fine unevenness of the surface and is an evaluation indicator of the surface quality. Fine surface roughness evaluated by the surface glossiness influences not only the indicator of appearance of the stainless clad steel, but also degradation in pitting resistance and the form of outflow rust to a great extent.
  • the glossiness (Gs(60)) is higher.
  • polishing of the stainless steel to increase the glossiness requires a significant load. Consequently, in consideration of the production load, the upper value of Gs(60) measured in the individual directions of the rolling direction (L), the perpendicular direction (C), and the direction at an angle of 45 degrees with respect to the rolling direction (D) is 300, and preferably 150 or less.
  • the surface glossiness can be measured on the basis of JIS Z 8741 “Specular glossiness-methods of measurement” by using a multi-angle gloss meter under the condition shown in FIG. 2 .
  • Gs(60) can be derived by an average of five points.
  • any of a hot-rolled steel sheet and a steel sheet subjected to an annealing heat treatment after a hot-rolling treatment is included, and the same effect is obtained.
  • surface-controlling technique can be a combination of various known surface-polishing techniques, e.g., common belt polishing, grinder polishing, abrasive wheel polishing, electrolytic polishing, and a pickling treatment.
  • the surface roughness and the anisotropy thereof are controlled at low levels by combining the above-described techniques and, in addition, the passivation film is strengthened so that desired characteristics are obtained.
  • methods of strengthening the passivation film of the surface include a technique by using a pickling treatment with nitric acid or fluoro-nitric acid or electrolytic polishing. It is also possible to combine these methods with an electrolytic neutral pickling treatment in a neutral salt solution (for example, Ruther process: 20% sodium sulfate solution and sodium nitrate).
  • a carbon steel and a low-alloy steel can be used as the base material of the stainless clad steel.
  • one surface or both surfaces of this base material is clad with stainless steel serving as a cladding material, and the method of cladding the base material with the cladding material is not specifically limited.
  • a hot-rolling method, an explosive rolling method, a diffusion bonding method, a cast-in insert method, and the like can be used.
  • an annealing treatment to hold at a temperature of 700° C. to 1,000° C. for 1 minute to 2 hours can also be performed.
  • Cr and Mo contents contained in stainless steel used as a cladding material of a stainless clad steel are large, for example, in the case of high-alloy steel having a Cr content of 20% or more and containing 2% or more of Mo, a ⁇ (sigma) phase, a ⁇ (chi) phase, and furthermore, M 23 C 6 , M 6 C (primary components of M are Fe, Cr), and the like are generated, so that effective Cr may be reduced and considerable degradation in corrosion resistance may be caused by sensitization.
  • the stainless clad steel with a controlled surface is effective and can contribute to removal of a Cr-removing layer and putting of a sensitized portion into a sound basis.
  • cold rolling and finish annealing for example, continuous annealing
  • a cold-rolled annealed sheet was used as a cladding material (austenite stainless steel) and a base material of a clad and a stainless clad steel was produced under the production conditions shown in Table 2.
  • the cladding material (austenite stainless steel, sheet thickness 20 mm) and the base material (common structural steel: steel equivalent to EH36) shown in Table 1 were made into an assembled slab dimension 1,890 mm wide by 2,060 mm long, and a stainless clad steel (cladding material: sheet thickness 4.0 mm, base material: sheet thickness 14.0 mm, width 2,500 mm, length 8,000 mm) was produced under the condition of slab heating temperature (° C.): 1,150° C.
  • the stainless clad steel obtained as described above was subjected to a combination of various known surface polishing techniques, e.g., common belt polishing, grinder polishing, abrasive wheel polishing, electrolytic polishing, and a pickling treatment so that the surface roughness and the anisotropy thereof were controlled at low levels. Furthermore, in addition to them, a pickling treatment with nitric acid, fluoro-nitric acid, or sulfuric acid or electrolytic polishing was performed for the purpose of strengthening the passivation film of the surface, so that desired characteristics were obtained.
  • various known surface polishing techniques e.g., common belt polishing, grinder polishing, abrasive wheel polishing, electrolytic polishing, and a pickling treatment so that the surface roughness and the anisotropy thereof were controlled at low levels. Furthermore, in addition to them, a pickling treatment with nitric acid, fluoro-nitric acid, or sulfuric acid or electrolytic polishing was performed for the purpose of strengthening the passivation film of
  • the atomic ratio (atomic percent) of each element was determined from each element profile measured by using AES (Auger Electron Spectroscopy) (name of apparatus: PHI MODEL 660 produced by PHISICAL ELECTONICS accelerating voltage: 5 kV amount of current of sample: 0.2 ⁇ A measurement region: 5 ⁇ m ⁇ 5 ⁇ m) while sputtering was performed in the depth direction.
  • AES Alger Electron Spectroscopy
  • Table 6 shows an example of Cr/Fe distribution in the depth direction.
  • Cr/Fe ratio in a passivation file varies by a circumstance and a corrosion resistance is improved by a concentration of Cr in the passivation film.
  • A is defined Cr/Fe ratio in a parent stainless steel and B is defined Cr/Fe ratio in a passivation file.
  • Values of B/A are listed in a column of Ratio of Cr/Fe relative to parent phase. The higher B/A, the more excellent corrosion resistance can be obtained for increased Cr concentration.
  • FIG. 1 shows the relationship between the measurement time and the values of Cr and Fe.
  • “Ratio of Cr/Fe relative to parent phase” refers to a ratio of Cr/Fe measured with respect to time of sputtering from the surface layer to the Cr/Fe atomic ratio (here 0.33) in the parent phase.
  • a region in which the values of Cr and Fe were almost constant values was specified to be a parent phase portion, and a region with a sputtering time shorter than that was defined as a passivation film portion.
  • the passivation film portion the value at the site exhibiting a highest Cr/Fe value was defined as the Cr/Fe concentration and was compared with the Cr/Fe concentration in the parent phase portion.
  • the surface glossiness was measured in conformity with JIS Z 8741 (1997) “Specular glossiness-methods of measurement” by using a multi-angle gloss meter GS series GS-1K produced by Suga Test Instruments Co., Ltd., at an angle of 60 degrees. Measurements were performed in three directions of the rolling direction (L), the perpendicular direction (C), and the direction at an angle of 45 degrees with respect to the rolling direction (D), the average glossiness indicator was determined on the basis of Formula (2) described below, and the resulting average glossiness indicator was specified to be the anisotropy of the surface glossiness.
  • average Gs(60) represents average glossiness indicator
  • Gs(60) L represents glossiness in the rolling direction (L)
  • Gs(60) C represents glossiness in the perpendicular direction (C)
  • Gs(60) D represents glossiness in the direction at an angle of 45 degrees with respect to the rolling direction (D).
  • the indicator of the corrosion resistance in a salt damage environment As for the indicator of the corrosion resistance in a salt damage environment, a pitting potential measurement was performed, where the measurement temperature was specified to be 70° C. and other measurement conditions were in conformity with JIS G 0577. The potential when the current density reached 100 ⁇ A/cm 2 was specified to be the pitting potential and was expressed in V′c100 (mV vs. SCE). The case where this pitting potential was 300 mV or more, the corrosion resistance was evaluated as good.
  • CPT refers to a critical pitting corrosion occurrence temperature and the threshold value of evaluation was specified to be 40° C.
  • a symbol ‘ ⁇ ’ indicates CPT of 40° C. or higher (acceptable) and a symbol ‘X’ indicates CPT of lower than 40° C. (unacceptable).
  • the pitting potential is low or at least one of CPT evaluation is inferior.

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US20150292069A1 (en) * 2012-12-05 2015-10-15 Jfe Steel Corporation Stainless steel-clad steel plate having exceptional corrosion resistance to seawater
CN105839003A (zh) * 2016-05-31 2016-08-10 江阴兴澄特种钢铁有限公司 一种正火态交货的180～200mm厚EH36钢板及其制备方法
US20180243809A1 (en) * 2015-03-12 2018-08-30 Jfe Steel Corporation Electric resistance welded stainless clad steel pipe and method of manufacturing the same
US10765898B2 (en) 2016-07-07 2020-09-08 Bull Moose Tube Company Steel coated metal structures and methods of fabricating the same

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CN107385353B (zh) * 2017-06-19 2019-06-25 江阴兴澄特种钢铁有限公司 一种海洋平台用250mm 特厚EH36钢板及其制备方法

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KR20140129139A (ko) 2014-11-06
WO2013132838A1 (ja) 2013-09-12
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