CN114182180A - Steel plate containing Sn and Sb and resisting to corrosion of sulfuric acid and chloride ions and manufacturing method thereof - Google Patents
Steel plate containing Sn and Sb and resisting to corrosion of sulfuric acid and chloride ions and manufacturing method thereof Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 50
- 239000010959 steel Substances 0.000 title claims abstract description 50
- 230000007797 corrosion Effects 0.000 title claims abstract description 46
- 238000005260 corrosion Methods 0.000 title claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 229910052718 tin Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000005096 rolling process Methods 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000010935 stainless steel Substances 0.000 claims description 16
- 238000007670 refining Methods 0.000 claims description 8
- 229910000859 α-Fe Inorganic materials 0.000 claims description 8
- 238000009749 continuous casting Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 4
- 229910001562 pearlite Inorganic materials 0.000 claims description 4
- 238000010079 rubber tapping Methods 0.000 claims description 3
- 238000005452 bending Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 16
- 230000004580 weight loss Effects 0.000 description 11
- 238000005266 casting Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- 229910001563 bainite Inorganic materials 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- 229910000870 Weathering steel Inorganic materials 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Classifications
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B1/24—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process
- B21B1/26—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process by hot-rolling, e.g. Steckel hot mill
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/004—Heating the product
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- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- 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
-
- 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
- C22C38/18—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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
- C22C38/60—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
- C21D2211/005—Ferrite
-
- 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
- C21D2211/009—Pearlite
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- Chemical & Material Sciences (AREA)
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- Mechanical Engineering (AREA)
- 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
The invention provides a steel plate containing Sn and Sb and resisting sulfuric acid and chloride ion corrosion and a manufacturing method thereof, and the steel plate comprises the following components: c: 0.050-0.079%; si: 0.20% -0.45%; mn: 0.60-1.00%; p is less than or equal to 0.025 percent; s is less than or equal to 0.0040 percent; cr: 0.90-1.10%; ni: 0.05 to 0.30 percent; cu: 0.20-0.40%; and Als: 0.025-0.050%; ti: 0.035 to 0.050 percent; sb: 0.08-0.14%; sn: 0.10 to 0.15 percent; n is less than or equal to 0.0040 percent; the balance of Fe and inevitable impurities. And a steel plate containing Sn and Sb and resisting the corrosion of sulfuric acid and chloride ions is formed by matching with key field control processes such as a plate blank heating process and the like; the surface quality and the cold bending performance are good; the yield strength is more than or equal to 345MPa, the tensile strength is more than or equal to 470MPa, and the elongation is more than or equal to 25 percent.
Description
Technical Field
The invention belongs to the field of steel materials and manufacturing thereof, and particularly relates to a steel plate containing Sn and Sb and resisting to corrosion of sulfuric acid and chloride ions and a manufacturing method thereof.
Background
The weathering steel is atmospheric corrosion resistant steel, can greatly reduce the manufacturing cost compared with stainless steel, has good welding performance, and has good atmospheric corrosion resistance compared with common carbon steel.
In the existing corrosion-resistant steel manufacturing technology, publication No. CN 101775544A published on 7/14/2010 discloses sulfuric acid dew point corrosion-resistant steel KNS and a rolling method thereof, and the chemical components of the corrosion-resistant steel KNS are as follows: c is less than or equal to 0.10%, Si: 0.30-0.40%, Mn: 0.70-0.80%, V is less than or equal to 0.010%, Cu: 0.20-0.30%, Cr: 0.60-0.90%, Ti: 0.015% -0.025%, Sb: less than or equal to 0.010 percent, S: less than or equal to 0.020%, P: less than or equal to 0.020%, and the balance of Fe and inevitable impurities. The corrosion resistance of the obtained sulfuric acid dew point corrosion resistant steel is 5.3 times that of the common steel Q195 and 2.89 times that of SPA-H, and the sulfuric acid corrosion resistant steel has better sulfuric acid corrosion resistance than plain carbon steel and weathering resistant steel. But the material can not meet the requirement of corrosion resistance under the coexistence environment of sulfuric acid and chloride ions.
Publication No. CN 103060712A published 24.4.2013 discloses stainless acid-resistant steel for boilers, which is characterized by comprising the following components in percentage by mass: c: 0.06-0.28%, Mn: 1.2-1.4%, Si: 0.2-0.3%, S is less than or equal to 0.020%, P is less than or equal to 0.02%, Cr: 18-20%, Ni: 3.5-4.5%, Mo: 0.8-1.0%, Cu: 0.6-1.2%, Ti: 0.2 to 0.4%, Nb: 0.1-0.2%, Sn: 0.2-0.4%, and the balance of Fe and inevitable impurities, wherein the ratio of Sn, Cu, Ti and Nb is 2:6:2: 1. Soaking in 50% sulfuric acid at 70 deg.C for 48 hr, with corrosion rate less than 1.8 mm/a. The material can not meet the requirement of corrosion resistance in the coexistence environment of sulfuric acid and chloride ions.
Patent No. CN 110157982A published in 2019, 8, 23 and discloses a seawater corrosion resistant steel plate and a production method thereof, and the seawater corrosion resistant steel plate is characterized in that C: 0.08-0.12%, Si: 0.25 to 0.35 percent of Mn, 1.0 to 1.6 percent of Mn, less than or equal to 0.012 percent of P, less than or equal to 0.008 percent of S, less than or equal to 1.2 percent of Cr + Ni + Cu, and the mass ratio of Sn: 0.025-0.050%, Nb + V + Ti is less than or equal to 0.05%, the thickness is 20-50 mm, and the annual corrosion thickness under the seawater full immersion condition is less than or equal to 2 mm. The material steel plate is suitable for the environment of seawater corrosion and is not suitable for the environment of coexistence of sulfuric acid and chloride ions.
Therefore, it is necessary to develop a steel sheet having excellent corrosion resistance against sulfuric acid and chlorine ions.
Disclosure of Invention
The invention provides a steel plate containing Sn and Sb and resisting corrosion of sulfuric acid and chloride ions and a manufacturing method thereof.
The specific technical scheme of the invention is as follows:
the steel plate containing Sn and Sb and resisting to corrosion of sulfuric acid and chloride ions comprises the following components in percentage by mass:
c: 0.050-0.079%; si: 0.20% -0.45%; mn: 0.60-1.00%; p is less than or equal to 0.025 percent; s is less than or equal to 0.0040 percent; cr: 0.90-1.10%; ni: 0.05-0.30%; cu: 0.20-0.40%; and Als: 0.025-0.050%; ti: 0.035 to 0.050 percent; sb: 0.08-0.14%; sn: 0.10 to 0.15 percent; n is less than or equal to 0.0040 percent; the balance of Fe and inevitable impurities.
The steel plate containing Sn and Sb and resisting to the corrosion of sulfuric acid and chloride ions has the components that Ti-3.42N-1.5S is more than 0.015 percent;
the metallographic structure of the steel plate containing Sn and Sb and resisting corrosion of sulfuric acid and chloride ions is ferrite and pearlite; the volume percentage of pearlite structure is 5-15%, the volume percentage of ferrite is 85-95%, and the grain size of ferrite is 10-12 grade.
The invention provides a method for manufacturing a steel plate containing Sn and Sb and resisting sulfuric acid and chloride ion corrosion, which comprises the following process flows of:
molten iron pretreatment → converter smelting → refining → continuous casting → slab heating → hot continuous rolling → laminar cooling → coiling.
The process flow comprises the following steps:
in the molten iron pretreatment process, the target S is less than or equal to 0.0040 percent after molten iron desulfurization, the converter adopts strong bottom blowing, the complementary blowing is forbidden at the end point, and the content of N is controlled;
the refining adopts a clean steel smelting process of LF refining;
in the continuous casting process, the special covering slag is adopted for protection casting in the whole process of molten steel casting, N is controlled to be less than or equal to 0.0040%, and the thickness of a plate blank is 230 mm.
After continuous casting, hot charging rolling is preferentially adopted for the plate blank, and the time interval from the cutting to the furnace entering of the plate blank is less than or equal to 4 hours; the slab which does not meet the hot charging condition needs to be subjected to off-line inspection, and rolling is carried out after the surface of the casting blank is confirmed to have no cracks; if cracks are found, the steel is rolled after being cleaned.
In the slab heating process, the temperature of the slab at the last two sections of inlets of the heating furnace is less than or equal to 1000 ℃, the excess coefficient of the atmosphere air in the furnace is less than 1.0, and the target range is controlled to be 0.90-0.95. The method creates conditions for shortening the slab in-furnace time, controls the slab discharging temperature to 1170-1210 ℃, and controls the slab in-furnace time to be less than 150 min.
And (3) after the slab is discharged from the furnace, descaling by high-pressure water, and then carrying out rough rolling and finish rolling on the slab in a hot continuous rolling unit.
The rough rolling is carried out by adopting 3+3 or 3+5 pass back and forth rolling, the temperature of the plate blank in the last pass of the rough rolling is more than or equal to 1030 ℃, the temperature of the plate blank is lower than 1030 ℃, and after the plate blank enters a finishing mill, the rolling force has overload risk;
and in the finish rolling stage, 7 stands are adopted for continuous rolling, and the finish rolling temperature is 840-890 ℃.
And after finish rolling, front-section concentrated laminar cooling is adopted, the cooling speed is 10-30 ℃/s, then the temperature is controlled at 550-630 ℃ for coiling, the coiling temperature is lower than the bainite transformation temperature of the composition, a large amount of bainite possibly appears in a microstructure, the cold bending forming performance is influenced by overhigh hardness, the coiling temperature is overhigh, the proportion of soft-phase ferrite is overhigh, the grain size is large, the fine-grain strengthening effect is insufficient, and further the strength of the steel plate is insufficient.
The design idea and the effect of the invention are as follows:
sn is added into stainless steel or coated on the surface of a steel plate, and the main purpose is to improve the corrosion resistance of the steel plate. However, since Sn is a low-melting point element, and its melting point is only 232 ℃, Sn-rich brittle phases are easily precipitated along grain boundaries, which adversely affect the high-temperature plasticity of a cast slab, the toughness of a steel sheet, and the surface quality, the technical idea of adding Sn to steel is few at present.
Sn and Sb are formed into a layer of SnO on the surface of a material2、Sb2O5The outer film of (2) hinders the progress of the corrosion of the matrix and simultaneously inhibits the dissolution of the anode, thereby achieving the effect of resisting the corrosion of sulfuric acid and chloride ions. At present, domestic sulfuric acid dew point corrosion resistant steel plateThe invention further improves the sulfuric acid corrosion resistance of the Sb-containing acid-resistant steel by adding Sn into the Sb-containing acid-resistant steel, and can resist the corrosion of chloride ions, so that the steel plate can be used in a high-temperature and severe sulfuric acid and chloride ion coexistence environment.
In the invention, because Sn and Sb both belong to low-melting-point elements and are easy to precipitate along a grain boundary to form a brittle phase, thereby generating adverse effects on the high-temperature plasticity of a casting blank, the toughness and the surface quality of a steel plate, the invention requires that the slab is preferentially hot-charge rolled (the time interval from slab cutting to furnace charging is less than or equal to 4h), the slab which does not meet the hot-charge condition needs to be off-line checked, rolling is carried out after no crack is found on the surface of the casting blank, and rolling is carried out after the crack is found. The target temperature of the plate blank at the last two sections of inlets of the heating furnace is less than or equal to 1000 ℃, the excess coefficient of the air in the furnace atmosphere is less than 1.0, the target range is controlled to be 0.90-0.95, the reducing atmosphere is ensured, and the adverse effect of the oxide layer on the surface of the plate blank on the surface quality of the rolled steel plate is reduced. The tapping temperature of the plate blank is controlled at 1170-1210 ℃, the heating temperature is reduced, the melting speed of the low-melting-point element is reduced, and meanwhile, conditions are created for shortening the in-furnace time of the plate blank. The furnace time of the plate blank is controlled to be less than 150min, the precipitation time of Sn and Sb brittle phases is shortened, and the amount of the brittle precipitated phases is reduced.
In addition, carbon steel with the carbon content of 0.08-0.17% is subjected to peritectic reaction when being cooled to 1495 ℃ from a liquid phase, the linear shrinkage amount is large during the peritectic reaction, air gaps are easily formed between the blank shell and the wall of the crystallizer, the premature formation of the air gaps can cause uneven shrinkage and uneven blank shell thickness, cracks are easily formed at weak positions, and the surface quality defect of the casting blank is easily caused, so the content of C in the chemical components is controlled to be less than 0.080%, and the peritectic reaction is avoided. Simultaneously, 0.030-0.050% of Ti is added, N is controlled to be less than or equal to 0.0040%, S is controlled to be less than or equal to 0.0040%, Ti-3.42N-1.5S is guaranteed to be more than 0.015%, grain growth is inhibited, and grain boundary gaps are reduced, so that the content of Sn and Sb brittle phases separated out along the grain boundaries is reduced, and the surface quality and the toughness of the plate blank and the steel plate are improved.
Compared with the prior art, the method adds proper Sn addition amount into the Sb-containing steel, controls the C, N, S content upper limit, adds Ti and matches with a slab heaterThe key processes such as the process and the like are controlled on site to form the steel plate containing Sn and Sb and resisting the corrosion of sulfuric acid and chloride ions and the manufacturing method thereof, and the steel plate has good surface quality and cold bending performance; the yield strength is more than or equal to 345MPa, the tensile strength is more than or equal to 470MPa, and the elongation is more than or equal to 25 percent; the impact work is more than or equal to 100J (the size of an impact sample is 7.5mm multiplied by 10mm multiplied by 55 mm); according to the test method specified in JB/T7901, the temperature is 70 ℃, and the etching solution is 50% H2SO4+3×104mg/L of Cl-Under the condition, the corrosion weight loss rate is less than 5.50g/m2·h。
Drawings
FIG. 1 is a graph showing that the surface quality of example 1 is good;
FIG. 2 is a graph showing surface cracks in comparative example 3;
FIG. 3 is the microstructure of example 1;
FIG. 4 is a microstructure of comparative example 5;
FIG. 5 shows the corrosion weight loss rate-Sn content variation trend.
Detailed Description
A manufacturing method of a steel plate containing Sn and Sb and resisting corrosion of sulfuric acid and chloride ions comprises the following process flows:
molten iron pretreatment → converter smelting → refining → continuous casting → slab heating → hot continuous rolling → laminar cooling → coiling.
The method comprises the steps of adopting molten iron pretreatment → converter steelmaking → LF external refining → continuous casting process smelting, wherein the target [ S ] after molten iron desulphurization is less than or equal to 0.0040%, adopting strong bottom blowing in a converter, prohibiting after-blowing at the end point, adopting a clean steel smelting process of LF refining, adopting special protective slag for protective casting in the whole process of molten steel casting, controlling the content of N to be less than or equal to 0.0040%, and controlling the thickness of a plate blank to be 230 mm. After LF external refining, the chemical components in the steel meet the following weight percentages (wt%): c: 0.050-0.079%; si: 0.20% -0.45%; mn: 0.60-1.00%; p is less than or equal to 0.025 percent; s is less than or equal to 0.0040 percent; cr: 0.90-1.10%; ni: 0.05 to 0.30 percent; cu: 0.20-0.40%; and Als: 0.025-0.050%; ti: 0.035 to 0.050 percent; sb: 0.08-0.14%; sn: 0.10 to 0.15 percent; n is less than or equal to 0.0040 percent; and satisfies Ti-3.42N-1.5S > 0.015%; the balance of Fe and inevitable impurities.
Of these, 3 furnaces of steel were used as 3 examples (example 1 to example 3) of the present invention, and the components of each example and comparative example are shown in table 1, with the balance not shown in table 1 being Fe and unavoidable structure.
The specific chemical component tests of the examples and comparative examples were carried out in accordance with GB/T4336 atomic emission spectrometry (conventional method) for spark sources of carbon steel and medium and low alloy steel, and the results are shown in Table 1, with the balance, not shown in Table 1, being Fe and unavoidable impurities.
In the production process, hot charging rolling is preferentially adopted for slabs, the time interval from slab cutting to furnace entering is less than or equal to 4 hours, slabs which do not meet the hot charging condition need to be checked off line, rolling is carried out after no crack is confirmed on the surface of a casting blank, and if cracks are found, rolling is carried out after cleaning. The temperature of the plate blank at the last two sections of the inlet of the heating furnace is controlled to be less than or equal to 1000 ℃, the air excess coefficient of the atmosphere in the heating furnace is less than 1.0, the target range is controlled to be 0.90-0.95, the heating temperature is reduced, the melting speed of low-melting-point elements is slowed down, the reducing atmosphere in the heating furnace is ensured, and the adverse effect of an oxide layer on the surface of the plate blank on the surface quality of a rolled steel plate is reduced. The furnace time of the plate blank is controlled to be less than 150min, the precipitation time of Sn and Sb brittle phases is shortened, and the amount of the brittle precipitated phases is reduced.
In order to create conditions for shortening the time of the slab in the furnace, the tapping temperature of the slab is controlled at 1170-1210 ℃. And (3) after the slab is discharged from the furnace, descaling by high-pressure water, and then carrying out rough rolling and finish rolling on the slab in a hot continuous rolling unit. 2, rough rolling by a frame, and finish rolling by a 7-frame; the rough rolling adopts 3+3 or 3+5 pass back and forth rolling, the temperature of the plate blank in the last pass of the rough rolling is more than or equal to 1030 ℃, the temperature of the plate blank is lower than 1030 ℃, the rolling force after the plate blank enters a finishing mill has overload risk, the finishing rolling stage adopts 7 stand continuous rolling, and the finishing temperature of the finishing rolling is 840-890 ℃. And after finish rolling, front-section concentrated laminar cooling is adopted, the cooling speed is 10-30 ℃/s, then the temperature is controlled at 550-630 ℃ for coiling, the coiling temperature is lower than the bainite transformation temperature of the composition, a large amount of bainite possibly appears in a microstructure, the cold bending forming performance is influenced by overhigh hardness, the coiling temperature is overhigh, the proportion of soft-phase ferrite is overhigh, the grain size is large, the fine-grain strengthening effect is insufficient, and further the strength of the steel plate is insufficient.
The main rolling process parameters, properties and surface quality of the examples and comparative examples are shown in table 2. The mechanical property test is carried out according to GB/T228.1-2010 metallic material tensile test part 1: the test method is carried out according to the room temperature test method, the cold bending performance test is carried out according to GB/T232-.
The microstructures of example 1 and comparative example 5 are shown in fig. 3 and fig. 4, the P-microstructure volume ratio of example 1 is about 5.49%, the F-microstructure volume ratio is about 94.51%, and the grain size is grade 10.5, the P-microstructure volume ratio of comparative example 5 is about 3.12%, the F-microstructure volume ratio is about 96.88%, and the grain size is grade 9.5.
TABLE 1 compositions of steel sheets of examples and comparative examples
TABLE 2 Main Process parameters, Properties and surface quality of the Rolling Process in the examples and comparative examples
Comparative examples 1 and 2 are based on example 1, and only the Sn content control requirement in the chemical composition is changed, and the technical requirements of example 1 are all performed. The chemical composition of comparative example 3 does not meet the requirements of the present invention, and the chemical compositions of comparative examples 4 and 5 are the same as example 1, but the process parameters do not meet the requirements of the present invention.
Each of examples 1-3 and comparative examples 1-2 was tested according to the test method specified in JB/T7901 at a temperature of 70 ℃ with a 50% H etching solution2SO4+3×104mg/L of Cl-The test results are shown in Table 3, and the test results show that the corrosion inhibitor has good sulfuric acid and chloride ion corrosion resistance.
The corrosion weight loss ratio (W) was calculated as follows:
in the formula: w-weight loss on corrosion, g/(m)2·h)；G0-sample original weight, g; g1-the post-test weight of the sample, g; a-specimen length, mm; b-sample width, mm; c-specimen thickness, mm; t-test time, h.
TABLE 3 Corrosion test data for each of examples 1-3 and comparative examples 1-2
| Corrosion weight loss ratio, g/m2·h | |
| Example 1 | 5.25 |
| Example 2 | 5.35 |
| Example 3 | 5.22 |
| Comparative example 1 | 13.11 |
| Comparative example 2 | 13.33 |
Under the conditions of the formula system and the production process of the example 1, the corrosion test is carried out only by changing the Sn content to be 0.10 percent and 0.15 percent, and the influence of the Sn content range of 0 to 0.15 percent in the Sb-containing acid-proof steel on the corrosion weight loss rate is shown in Table 4 and figure 5.
TABLE 4 Corrosion weight loss ratio of Sn, Sb containing steels
| Sn(％) | Corrosion weight loss ratio (g/m)2·h) |
| 0 | 13.33 |
| 0.05 | 13.11 |
| 0.10 | 5.39 |
| 0.15 | 5.18 |
Adding 0-0.15% Sn into Sb-containing steel, and testing according to JB/T7901 method at 70 deg.C with 50% H corrosive solution2SO4+3×104mg/L of Cl-Under the condition, the corrosion weight loss rate is shown in figure 5 along with the change of the Sn content, when the addition amount of Sn exceeds 0.05 percent, the corrosion weight loss rate of the steel plate is greatly reduced, and when the addition amount of Sn reaches 0.10 to 0.15 percent, the reduction trend of the corrosion weight loss rate is relatively gentle. Because the excessively high Sn content has adverse effects on the high-temperature plasticity of a casting blank, the toughness and the surface quality of a steel plate, the corrosion resistance is comprehensively considered, and the Sn content is controlled to be 0.10-0.15%.
In summary, the yield strength of the embodiment obtained according to the design range of the chemical components of the steel grade and the control requirement of the rolling process is as follows: 383-413 MPa, tensile strength: 495-527 MPa, A: 27.0-33.0%, and-40 ℃ impact energy is more than or equal to 100J (impact sample size:7.5mm × 10mm × 55 mm); according to the test method specified in JB/T7901, the etching solution is 50% H at a temperature of 70 DEG C2SO4+3×104mg/L of Cl-The corrosion weight loss rate of the embodiment is 5.18-5.35g/m2H. The steel has good sulfuric acid and chloride ion corrosion resistance, can be applied to the manufacturing of structural parts serving under the high-temperature and severe sulfuric acid and chloride ion coexistence environment, and can be further expanded and applied to other fields with sulfuric acid and chloride ion corrosion resistance requirements.
Claims (10)
1. The steel plate containing Sn and Sb and resisting to the corrosion of sulfuric acid and chloride ions is characterized by comprising the following components in percentage by mass:
c: 0.050-0.079%; si: 0.20% -0.45%; mn: 0.60-1.00%; p is less than or equal to 0.025 percent; s is less than or equal to 0.0040 percent; cr: 0.90-1.10%; ni: 0.05-0.30%; cu: 0.20-0.40%; and Als: 0.025-0.050%; ti: 0.035 to 0.050 percent; sb: 0.08-0.14%; sn: 0.10 to 0.15 percent; n is less than or equal to 0.0040 percent; the balance of Fe and inevitable impurities.
2. The Sn-and Sb sulfuric acid and chloride ion corrosion resistant steel sheet according to claim 1, wherein the Sn-and Sb sulfuric acid and chloride ion corrosion resistant steel sheet satisfies Ti-3.42N-1.5S > 0.015%.
3. The Sn-and Sb sulfuric acid and chloride ion corrosion resistant steel sheet according to claim 1 or 2, wherein the metallographic structure of the Sn-and Sb sulfuric acid and chloride ion corrosion resistant steel sheet is ferrite + pearlite; the volume percentage of pearlite structure is 5-15%, the volume percentage of ferrite is 85-95%, and the grain size of ferrite is 10-12 grade.
4. A method for manufacturing a Sn-and Sb-containing sulfuric acid and chloride ion corrosion resistant steel sheet according to any one of claims 1 to 3, comprising the steps of: molten iron pretreatment → converter smelting → refining → continuous casting → slab heating → hot continuous rolling → laminar cooling → coiling.
5. The manufacturing method according to claim 4, wherein after the continuous casting, the slab is subjected to hot charging rolling, and the time interval between the cutting and the charging of the slab is less than or equal to 4 hours.
6. The manufacturing method according to claim 4, wherein the air excess coefficient of the rear two sections of the heating furnace is less than 1.0 during the slab heating process.
7. The manufacturing method according to claim 4 or 6, characterized in that the slab tapping temperature is controlled at 1170-1210 ℃ and the slab on-furnace time is controlled to be less than 150 min.
8. The manufacturing method according to claim 4, wherein the temperature of the rough rolling final pass slab in the hot continuous rolling is not less than 1030 ℃.
9. The manufacturing method according to claim 4 or 8, wherein in the hot continuous rolling, the finish rolling temperature 840-890 ℃.
10. The method as claimed in claim 4 or 8, wherein the coiling temperature is 550 ℃ and 640 ℃.
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