WO2020111889A1 - Tôle d'acier présentant une résistance à la corrosion dans des environnements de condensation d'acide sulfurique et d'acide sulfurique/acide chlorhydrique et son procédé de fabrication - Google Patents

Tôle d'acier présentant une résistance à la corrosion dans des environnements de condensation d'acide sulfurique et d'acide sulfurique/acide chlorhydrique et son procédé de fabrication Download PDF

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WO2020111889A1
WO2020111889A1 PCT/KR2019/016780 KR2019016780W WO2020111889A1 WO 2020111889 A1 WO2020111889 A1 WO 2020111889A1 KR 2019016780 W KR2019016780 W KR 2019016780W WO 2020111889 A1 WO2020111889 A1 WO 2020111889A1
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steel sheet
corrosion
sulfuric acid
equation
weight
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English (en)
Korean (ko)
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이병호
조민호
홍영광
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주식회사 포스코
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Priority to CN201980079339.6A priority Critical patent/CN113166890A/zh
Priority to JP2021531275A priority patent/JP7333399B2/ja
Publication of WO2020111889A1 publication Critical patent/WO2020111889A1/fr

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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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • 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
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • the present invention relates to a steel sheet having corrosion resistance in a sulfuric acid and sulfuric acid/hydrochloric acid complex condensation environment and a method for manufacturing the same. More specifically, the present invention relates to a steel sheet having a corrosion resistance to a phenomenon in which steel sheets are corroded by condensate generated when the exhaust gas temperature decreases, such as SO x , Cl, etc., present in the exhaust gas after burning fossil fuels and a method of manufacturing the same.
  • Fossil fuels contain various impurities such as S and Cl. There is always a problem of deterioration due to corrosion in piping and equipment, which is a passage through which combustion gas flows using fossil fuels. In particular, this corrosion phenomenon is called condensation corrosion, and typical uses are thermal power plant exhaust gas piping, environmental facilities, and automobile exhaust systems. As the type of condensation corrosion, SO x is formed as the S contained in the flue gas is burned.
  • sulfuric acid condensation in which SO 3 meets moisture in the flue gas to form sulfuric acid, and various chlorine contained in the flue gas or industrial water
  • hydrochloric acid condensation in which hydrochloric acid is produced through the reaction
  • sulfuric acid/hydrochloric acid complex condensation that occurs when the sulfuric acid and hydrochloric acid are mixed together.
  • the starting temperature of the acid condensation is related to the content of SO x and Cl in the flue gas and the water vapor content.
  • the present invention is to provide a steel sheet having corrosion resistance in a sulfuric acid and sulfuric acid/hydrochloric acid complex condensation environment and a method for manufacturing the same. More specifically, an object of the present invention is to provide a steel sheet having a corrosion resistance to a phenomenon in which steel sheets are corroded by condensate generated when the exhaust gas temperature decreases when SO x , Cl, etc., present in the exhaust gas after burning fossil fuel, and a method for manufacturing the same.
  • Corrosion-resistant steel sheet by weight, carbon (C): 0.15% or less (excluding 0%), copper (Cu): 0.05 to 0.5%, nickel (Ni): 0.02 to 0.3 % And antimony (Sb): 0.05 to 0.45%, tin (Sn): 0.05 to 0.45%, tungsten (W): 0.05 to 0.2%, molybdenum (Mo): 0.2 to 1.45% And contains the remaining iron (Fe) and unavoidable impurities, and satisfies Expression 1 below.
  • [Cu], [Sb], [Sn], [W], and [Mo], respectively, refers to the content of Cu, Sb, Sn, W, and Mo (% by weight) in the steel sheet .
  • the steel sheet can satisfy Expression 2 below.
  • [Cu] and [Ni] mean the content of Cu and Ni in a steel sheet (% by weight), respectively.
  • the steel sheet can satisfy the following equation (3).
  • the sulfuric acid immersion corrosion reduction ratio is a value obtained by measuring the weight loss per unit time and per unit surface area after immersing the steel sheet in a 50% by weight sulfuric acid solution at 70° C. for 6 hours. Is a value obtained by measuring the weight loss per unit time and per unit surface area after dipping at 80° C. for 6 hours in a solution of 16.9 vol% sulfuric acid solution and 0.35 vol% hydrochloric acid solution.
  • the sulfuric acid immersion thickening layer and the complex immersion thickening layer include one or more elements of Cu, Sb, Sn, W, and Mo, and the sum of Cu, Sb, Sn, W, and Mo may be 3.5% by weight or more.
  • the sulfuric acid immersion concentrated layer may include at least one of Cu: 7.05 to 23.06% and Sb: 4.3 to 15.58%, W: 0.15 to 0.3%, Sn: 3.5 to 18% and Mo: 0.6 to 2.1%
  • the composite immersion thickening layer may include Cu: 3.5 to 24.58% and Sb: 3.5 to 17.5%, W: 0.1 to 0.45%, Sn: 1.5 to 22%, and Mo: 0.4 to 2.1%.
  • the steel sheet can satisfy the following equation (4).
  • In (n is 1 or 2) means a corrosion resistance index, it is represented by the following equation (5).
  • [Cu], [Sb], [Sn], [W], and [Mo] mean the maximum content (% by weight) of Cu, Sb, Sn, W, and Mo in the thickening layer. .
  • I1 means the corrosion resistance index of the concentrated layer of sulfuric acid immersion
  • I2 means the corrosion index of the complex immersion thickening layer
  • the sum of the thicknesses of the formed thickening layers may satisfy Expression 6 below.
  • the steel sheet may have an average length of cracks occurring at corner portions of the steel sheet of 10 mm or less.
  • the method of manufacturing a corrosion-resistant steel sheet according to an embodiment of the present invention by weight, carbon (C): 0.15% or less (excluding 0%), copper (Cu): 0.05 to 0.5%, nickel (Ni ): 0.02 to 0.3% and antimony (Sb): 0.05 to 0.45%, tin (Sn): 0.05 to 0.45%, tungsten (W): 0.05 to 0.2%, molybdenum (Mo): 0.2 to 1.45%
  • C carbon
  • Cu copper
  • Ni nickel
  • Sb antimony
  • tin (Sn) 0.05 to 0.45%
  • tungsten (W) 0.05 to 0.2%
  • Mo molybdenum
  • Equation 1 [Cu], [Sb], [Sn], [W], and [Mo] mean the content (% by weight) of Cu, Sb, Sn, W, and Mo in the slab, respectively. .
  • the slab is manganese (Mn): 0.5 to 1.5%, aluminum (Al): 0.05% or less (excluding 0%) and chromium (Cr): 8% or less (excluding 0%) or more. It can contain.
  • the finish rolling temperature may be 750 °C or more.
  • Winding the hot rolled steel sheet may be made at 550 to 750 °C.
  • the cold rolled steel sheet may have a thickness of 3 mm or less.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention can be effectively used as a raw material for piping through which flue gas passes after combustion of fossil fuels, hot rolled products for fossil fuel combustion facilities, and cold rolled products.
  • Example 1 is a table showing the element concentration of the surface portion of a steel sheet according to an embodiment of the present invention, (a) is a surface observation after immersion at 70° C. for 6 hours in a 50% by weight sulfuric acid environment of Example 1, (b) ) Is a surface observation after immersion for 24 hours in an environment of 16.9 vol% sulfuric acid and 0.35 vol% hydrochloric acid of Inventive Example 1.
  • FIG. 2 is a photograph showing the degree of crack generation in a hot-rolled edge portion during hot rolling of a steel sheet according to an embodiment of the present invention.
  • (a) is a photograph of the steel sheet of Comparative Example 5 in (a).
  • first, second, and third are used to describe various parts, components, regions, layers, and/or sections, but are not limited thereto. These terms are only used to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first portion, component, region, layer or section described below may be referred to as a second portion, component, region, layer or section without departing from the scope of the present invention.
  • the term "combination of these" included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the elements described in the expression of the marki form, the components It means to include one or more selected from the group consisting of.
  • a part when it is said that a part is “on” or “on” another part, it may be directly on or on another part, or another part may be involved therebetween. In contrast, if one part is referred to as being “just above” another part, no other part is interposed therebetween.
  • % means weight%, and 1 ppm is 0.0001% by weight.
  • the meaning of further including an additional element means that the remaining amount of iron (Fe) is replaced by an additional amount of the additional element.
  • the present inventors during research to solve the above-mentioned problems of the prior art, when a typical low carbon steel sheet is subjected to a sulfuric acid or sulfuric acid/hydrochloric acid complex corrosion environment, corrosion generated according to the type and content of elements contained in the steel and the complex relationship It was confirmed that the product inhibits additional corrosion. At this time, if two or more special elements such as Cu, Sb, Sn, W, Mo, etc. are added to the steel, corrosion resistance in a high concentration of sulfuric acid and a complex of sulfuric acid/hydrochloric acid condensation environment can be improved at the same time. It has been concluded that the corrosion resistance of equipment in the environment can be significantly increased.
  • Fe in steel is generally dissolved as Fe ions, and after being dissociated in an aqueous solution, the steel surface meets and dissolves in SO 4 2 , Cl - etc.
  • the steel plate is corroded by the reaction, resulting in thickness and weight loss.
  • metals which are noble metals than Fe, such as Cu, Sb, Sn, W, and Mo, are used, stable corrosion products can be formed even in an acid aqueous solution on the surface of the steel sheet after immersion corrosion, thereby inhibiting the generation of additional corrosion.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention in weight%, carbon (C): 0.15% or less (excluding 0%), copper (Cu): 0.05 to 0.5%, nickel (Ni): 0.02 to 0.3% and antimony (Sb): 0.05 to 0.45%, tin (Sn): 0.05 to 0.45%, tungsten (W): 0.05 to 0.2%, molybdenum (Mo): 0.2 to 1.45%, at least one of It contains, and contains the remaining iron (Fe) and inevitable impurities, and satisfies the following equation (1).
  • [Cu], [Sb], [Sn], [W], and [Mo], respectively, refers to the content of Cu, Sb, Sn, W, and Mo (% by weight) in the steel sheet .
  • the steel sheet can satisfy Expression 2.
  • [Cu] and [Ni] mean the content of Cu and Ni in a steel sheet (% by weight), respectively.
  • the steel sheet may be a low carbon steel sheet.
  • the carbon content of the low carbon steel sheet may be 0.15% or less.
  • the content of carbon in the steel is too large, there is a possibility that a phase containing carbides such as pearlite and bainite that cause local corrosion in the steel may be formed and deteriorate corrosion resistance. More specifically, it may be 0.10% or less.
  • Mn helps to improve the strength and hardenability of steel by solid solution strengthening, and may be included in order to exhibit this effect in the present invention. However, if too much is added, segregation such as central segregation or micro segregation becomes severe, which may adversely affect product quality. More specifically, it may be 0.5 to 1.0%.
  • Cu is a representative element that, when corroded in an acid immersed environment, thickens between the steel surface and corrosion products to prevent further corrosion. In order to show the effect, it is preferable to add 0.05% or more, but if added too much, there is a possibility of causing cracks during manufacturing due to the low melting point of Cu. More specifically, it may be 0.10 to 0.35%.
  • nickel can be added while being limited to the following formula (2).
  • [Cu] and [Ni] mean the content of Cu and Ni in a steel sheet (% by weight), respectively.
  • the reason that can be limited to the above range is to limit the phenomenon that liquid Cu penetrates into the grain boundary due to the low melting point of Cu and causes cracking when added to the steel with only Cu without Ni by raising the melting point due to the addition of Ni. It is for.
  • the content of Ni When the content of Ni is too small, it does not sufficiently serve to increase the melting point of the Cu. On the contrary, when the content of Ni is too large, surface defects due to Ni may occur. More specifically, it may be 0.05 to 0.2%.
  • Sb is added to form a stable thickening layer on the surface, such as Cu. If the content of Sb is too small, a sufficient thickening layer cannot be formed, and if too large, the surface crack may be caused. More specifically, it may be 0.05 to 0.2%.
  • Cr requires a large amount in a normal stainless steel, but is oxidized to Cr 2+ in a film when immersed in a strong acid environment, so that there is a problem that corrosion resistance decreases. More specifically, it may contain 5% by weight or less. More specifically, it may contain 1% by weight or less.
  • one or more corrosion-resistant elements that help corrosion resistance properties other than the above elements may be added. That is, tin (Sn): 0.05 to 0.45%, tungsten (W): 0.05 to 0.2%, molybdenum (Mo): may include one or more of 0.2 to 1.5%.
  • Tin (Sn) 0.05 to 0.45% by weight
  • Sn is an element that forms a thickening layer such as Cu and Sb between the steel surface and the corrosion product after corrosion. In addition, it is further formed on the pole surface of the corrosion product and serves to suppress further corrosion. However, if too much Sn is added, it can cause slab cracking during manufacturing and edge cracking during hot rolling. More specifically, it may be 0.10 to 0.45%.
  • W is characterized by thickening at a very small concentration between the steel surface and the corrosion product upon corrosion. It is also an element that greatly improves the density of the formed amorphous layer and corrosion products. If the content of W is too small, it may not play a sufficient role. On the contrary, when the content of W is too large, the formation of WC by W may cause defects. More specifically, it may be 0.07 to 0.15%.
  • Mo is a representative element that enhances the hardenability of steel. In addition, it concentrates on the pole surfaces of steel and corrosion products to stabilize the layer of corrosion products. When the content of Mo is too large, the strength may be increased due to the formation of a hard phase, and cracking may occur during manufacturing. More specifically, it may be 0.3 to 1.40%.
  • the present invention includes Fe and unavoidable impurities. Unavoidable impurities are widely known in the art, so a detailed description is omitted. In one embodiment of the present invention, addition of effective ingredients other than the above ingredients is not excluded.
  • [Cu], [Sb], [Sn], [W], and [Mo], respectively, refers to the content of Cu, Sb, Sn, W, and Mo (% by weight) in the steel sheet .
  • Such control can promote thickening of the surface corrosion product and improve the density of the corrosion product produced.
  • Corrosion-resistant steel sheet according to an embodiment of the present invention is very excellent corrosion resistance by the above-described alloy components. Specifically, Equation 3 below may be satisfied.
  • the sulfuric acid immersion corrosion reduction ratio is a value obtained by measuring the weight loss per unit time and per unit surface area after immersing the steel sheet in a 50% by weight sulfuric acid solution at 70° C. for 6 hours. Is a value obtained by measuring the weight loss per unit time and per unit surface area after dipping at 80° C. for 6 hours in a solution of 16.9 vol% sulfuric acid solution and 0.35 vol% hydrochloric acid solution.
  • Corrosion-resistant steel sheet according to an embodiment of the present invention, sulfuric acid or sulfuric acid and hydrochloric acid are mixed in a complex state to produce a suitable thickening layer, excellent corrosion resistance properties.
  • a concentrated sulfuric acid immersion layer is formed from the surface of the steel sheet to the inside direction, and the steel sheet is 16.9 vol% sulfuric acid.
  • a complex immersion thickening layer may be formed from the surface of the steel sheet to the inner direction.
  • the sulfuric acid immersion thickening layer and the complex immersion thickening layer include one or more elements of Cu, Sb, Sn, W, and Mo, and the sum of Cu, Sb, Sn, W, and Mo may be 3.5% by weight or more.
  • the total amount of Cu, Sb, Sn, W and Mo forming the thickening layer is 3.5% by weight or more, so that it is distinguished from the base material of the steel sheet rather than the thickening layer.
  • the sulfuric acid immersion thickening layer may include at least one of Cu: 7.05 to 23.06% and Sb: 4.3 to 15.58%, W: 0.15 to 0.3%, Sn: 3.5 to 18% and Mo: 0.6 to 2.1%. More specifically, Mo may be 0.6 to 2.0%.
  • the composite immersion thickening layer may include Cu: 3.5 to 24.58% and Sb: 3.5 to 17.5%, W: 0.1 to 0.45%, Sn: 1.5 to 22%, and Mo: 0.4 to 2.1%. More specifically, W may be 0.15 to 0.34%, Sn may be 15 to 17.5%, and Mo may be 0.65 to 2.0%.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention may satisfy Expression 4 below.
  • In (n is 1 or 2) means a corrosion resistance index, it is represented by the following equation (5).
  • [Cu], [Sb], [Sn], [W], and [Mo] mean the maximum content (% by weight) of Cu, Sb, Sn, W, and Mo in the thickening layer. .
  • I1 means the corrosion resistance index of the concentrated layer of sulfuric acid immersion
  • I2 means the corrosion index of the complex immersion thickening layer
  • the sum of the thickness of the formed thickening layer may satisfy the following equation (6).
  • the thickening layer may include one or more of the elements described above.
  • it may vary depending on the immersion environment, it may have a thickness of 70 to 500 nm or less between the corrosion product and the raw steel.
  • the corrosion-resistant steel sheet according to an embodiment of the present invention may have an average length of cracks occurring at corner portions of the steel sheet of 10 mm or less.
  • Method of manufacturing a corrosion-resistant steel sheet according to an embodiment of the present invention by weight%, carbon (C): 0.15% or less (excluding 0%), copper (Cu): 0.05 to 0.5%, nickel (Ni): 0.02 To 0.3% and antimony (Sb): 0.05 to 0.45%, tin (Sn): 0.05 to 0.45%, tungsten (W): 0.05 to 0.2%, molybdenum (Mo): 0.2 to 1.45% And, including the remaining iron (Fe) and inevitable impurities, preparing a slab satisfying the following formula (1); Heating the slab; Hot rolling a slab to produce a hot rolled steel sheet; And winding the hot rolled steel sheet.
  • Equation 1 [Cu], [Sb], [Sn], [W], and [Mo] mean the contents (% by weight) of Cu, Sb, Sn, W, and Mo in the slab, respectively.
  • the slab is manganese (Mn): 0.5 to 1.5%, aluminum (Al): 0.05% or less (excluding 0%) and chromium (Cr): 8% or less (excluding 0%) or more. It can contain.
  • a slab satisfying the above-described composition is prepared.
  • the reason for limiting the addition ratio of each composition in the slab is the same as the reason for limiting the composition of the steel sheet described above, and thus repeated description is omitted. Since the composition of the slab is not substantially changed in the manufacturing process of hot rolling, hot rolled sheet annealing, cold rolling, final annealing, which will be described later, the composition of the slab and the composition of the non-oriented electrical steel sheet are substantially the same.
  • hot rolled slabs are hot rolled to produce hot rolled steel sheets.
  • the finish rolling temperature of the hot rolling may be 750°C or higher.
  • Winding the hot rolled steel sheet may be made at 550 to 750 °C.
  • the hot rolled sheet is pickled and cold rolled to a predetermined plate thickness to produce a cold rolled steel sheet. It may be applied differently depending on the thickness of the hot rolled steel sheet, but a reduction rate of 70 to 95% may be applied, and the cold rolled steel sheet may have a thickness of 3 mmt or less.
  • an immersion test was performed by the method described in ASTM G31.
  • the immersion test was carried out by preparing a 50% by weight aqueous sulfuric acid solution and immersing it at 70°C for 6 hours.After immersion, the weight loss was measured per unit time and per unit surface area by measuring the weight loss after washing through the surface cleaning method of the test piece of ASTM G1. Was measured.
  • a 16.9 vol% sulfuric acid and 0.35 vol% hydrochloric acid mixed aqueous solution was prepared to simulate the complex condensation of sulfuric acid/hydrochloric acid encountered at low temperature condensation at a Korean thermal power plant, and the corrosion reduction ratio was measured after immersion for 6 hours. Experiments were also performed. The results are shown in Table 2 below. The unit is mg/cm 2 /hr. to be.
  • the sulfuric acid/hydrochloric acid complex immersion test was performed by immersing the test piece in a mixed aqueous solution of 16.9 vol% sulfuric acid and 0.35 vol% hydrochloric acid and measuring the content of the component elements from the steel surface after 24 hours, and the thickness from the interface where Fe and oxide are formed. Through the thickness of the thickening layer was measured.
  • the corrosion resistance index In (n is 1 or 2) is defined as follows.
  • [Cu], [Sb], [Sn], [W], and [Mo] mean the maximum content (% by weight) of Cu, Sb, Sn, W, and Mo in the thickening layer. .
  • Equation 4 the value that satisfies the corrosion resistance of sulfuric acid and sulfuric acid/hydrochloric acid at the same time is expressed by Equation 4 below.
  • I1 means the corrosion resistance index of the concentrated layer of sulfuric acid immersion
  • I2 means the corrosion index of the complex immersion thickening layer
  • the thickness of the formed thickening layer was more than a certain value, which was related to corrosion resistance. This can be expressed by the following equation (6).
  • the length of each crack in the edge portion is considered to be the shape of the wave, and the average position of the positions of all the floors and the valleys is taken as reference (refer to the dotted line in FIG. 2(a)). ), and measure the length from the standard to the end position of the crack. It can also be calculated as follows. First, the area of the steel sheet is measured. Calculate the edge position when the steel plate is the same length and the same area and the edge is flat without crack. The position is taken as a reference, and the length from the reference to the crack end position is measured.
  • the average length of cracks in the edge portion was measured by measuring the lengths of the three longest cracks and dividing them by the number of cracks. As a result of the measurement, it was judged that the crack length was formed by 10 mm or more at the average edge when it was made of the components of Comparative Examples 5, 7, and 10, which could be a problem when using the product later. Therefore, after the hot rolling, the crack length at the average edge was limited to an average of 10 mm or less.
  • the reason for the above feature is that when the steel sheet is subjected to a sulfuric acid or sulfuric acid/hydrochloric acid complex corrosion environment, an amorphous thickening layer that inhibits the continuous reaction of Fe and acid is formed to prevent further corrosion. This is because the thickness of the thickened layer where the thickening of the thickened layer occurs repeatedly, and the thickening/corrosion of the thickened layer is related to the steel component.
  • the researcher has found that the components and thickness of these thickening layers are closely related to the corrosion resistance of sulfuric acid or sulfuric acid/hydrochloric acid based on a large amount of experimental results, and components such as Cu, Sb, and Mo are basically compacting the thickening layer. It was confirmed that Sn and W additionally play the same role, and have a large effect on the content.

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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

La présente invention concerne une tôle d'acier présentant une résistance à la corrosion dans des environnements d'acide sulfurique et d'acide sulfurique/acide chlorhydrique et un procédé pour la fabriquer. Une tôle d'acier résistant à la corrosion selon un mode de réalisation de la présente invention comprend, en % en poids, 0,15 % de carbone (C) ou moins (en excluant 0 %), 0,05 à 0,5 % de cuivre (Cu), 0,02 à 0,3 % de nickel (Ni) et 0,05 à 0,45 % d'antimoine (Sb) et au moins un élément parmi 0,05 à 0,45 % d'étain (Sn), 0,05 à 0,2 % de tungstène (W) et 0,2 à 1,45 % de molybdène (Mo), le reste étant du fer (Fe) et des impuretés inévitables, et satisfait la relation 1 suivante. [Relation 1] [Cu] + 3×[Sb] + 5×[Sn] + 5×[W] + [Mo] > 1 (% en poids) (dans la relation 1, [Cu], [Sb], [Sn], [W] et [Mo] représentent respectivement les quantités (% en poids)) de Cu, Sb, Sn, W et Mo dans la tôle d'acier.)
PCT/KR2019/016780 2018-11-30 2019-11-29 Tôle d'acier présentant une résistance à la corrosion dans des environnements de condensation d'acide sulfurique et d'acide sulfurique/acide chlorhydrique et son procédé de fabrication WO2020111889A1 (fr)

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CN201980079339.6A CN113166890A (zh) 2018-11-30 2019-11-29 硫酸和硫酸/盐酸复合冷凝环境下具有耐腐蚀性的钢板及其制造方法
JP2021531275A JP7333399B2 (ja) 2018-11-30 2019-11-29 硫酸および硫酸／塩酸の複合凝縮環境で耐食性を有する鋼板およびその製造方法

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KR10-2018-0152976 2018-11-30

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