CN111621699A - Corrosion-resistant low alloy steel for high-humidity-heat marine atmospheric environment bridge structure and preparation method thereof - Google Patents
Corrosion-resistant low alloy steel for high-humidity-heat marine atmospheric environment bridge structure and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
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- 238000003723 Smelting Methods 0.000 claims description 2
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- 230000000171 quenching effect Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 22
- 239000000956 alloy Substances 0.000 abstract description 22
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 13
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 abstract 1
- 229910000746 Structural steel Inorganic materials 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 13
- 229910000870 Weathering steel Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
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- 229910052742 iron Inorganic materials 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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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
- C21D8/0226—Hot rolling
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- 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
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- 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
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
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Abstract
A corrosion-resistant low alloy steel for a bridge structure in a high-humidity and high-heat marine atmospheric environment and a preparation method thereof belong to the technical field of corrosion-resistant steel. Chemical composition (wt.%) of the corrosion resistant steel: c: 0.02 to 0.05, Si: 0.20 to 0.60, Mn: 0.70-1.20, P is less than or equal to 0.02, S is less than or equal to 0.003, Cu: 0.20 to 0.90, Ni: 0.50 to 1.60, Mo: 0.10 to 0.50, Ti: 0.010-0.030 percent, Nb is less than or equal to 0.030 percent, and the balance is Fe and inevitable impurities. The invention reasonably adjusts the contents of alloy elements Cu, Ni and Mo on the basis of a Cu-Ni-Mo low alloy steel alloy system by combining the economy of low alloy steel, and obtains the ferrite-pearlite structure corrosion-resistant low alloy steel. The corrosion-resistant steel has certain economical efficiency and good corrosion resistance under the condition of high cost brought by properly controlling alloy elements Ni and Mo, is particularly applied to the hot-zone high-humidity hot marine atmospheric environment, is remarkably superior to plain carbon steel in corrosion resistance of low alloy steel with proper Cu/Ni/Mo composition components, and meets the requirement of bridge structural steel on mechanical property in the high-humidity hot marine atmospheric environment.
Description
Technical Field
The invention belongs to the technical field of corrosion-resistant steel, and particularly relates to economical corrosion-resistant low alloy steel for a high-humidity and high-heat marine atmospheric environment bridge structure.
Background
The hot-zone high-humidity hot marine atmospheric environment has the characteristics of high temperature, high humidity, high chloride ions and high irradiation intensity, belongs to a severe marine atmospheric corrosion environment, and seriously threatens the construction, operation and maintenance of bridge and other infrastructure under the environment. For example, thailand dalle areas (100 ° 58'E, 12 ° 5' N) in tropical marine atmospheric environments have an annual average temperature of about 28 ℃, an average relative humidity of about 80%, up to 98%, a total annual rainfall of about 1000mm, are typical tropical high-humidity and hot marine atmospheric environments, and have a corrosion loss of more than 136 billion dollars in thailand. The corrosion of the tropical high-humidity and high-heat ocean atmosphere seriously threatens the service safety of important infrastructures such as bridge structures and the like, and restricts the safe and reliable operation of transportation means. At present, infrastructure construction of bridges and the like in tropical high-humidity and high-heat marine atmospheric environments has urgent need for low-cost economic corrosion-resistant steel, so that the development of low-cost economic corrosion-resistant low-alloy steel suitable for bridge structures in high-humidity and high-heat marine atmospheric environments is needed.
At present, more and more domestic and foreign scholars are focusing on the research and development of the steel for resisting marine atmospheric corrosion. For example, the Japan NKK company has developed a corrosion-resistant steel sheet for the coast which contains 1.5% Ni to 0.3% Mo as a main alloy component. Aiming at the ocean atmospheric environment, Japan JFE iron and steel company develops novel corrosion-resistant steel with the main alloy components of 2.7 percent of Ni, 0.38 percent of Cu and 0.02 percent of P, and greatly improves the seawater corrosion resistance of Cu-P series corrosion-resistant steel. Steel company, u.s.steel in the united states, first developed high strength corrosion resistant low alloy steel-Corten steel that could be applied directly to buildings and bridges in the 60's of the 20 th century without painting, among which Corten a series of high P, Cu, Cr and Ni and Corten b series of steel mainly alloyed with Cr, Mn and Cu were most commonly used and widely used in japan and some european countries. The Sailcor-a series of corrosion resistant steels was developed following india to simulate the U.S. CortenA series of corrosion resistant steels. A series of marine atmosphere corrosion resistant low alloy steels added with Ni element and Ca element were also developed by korean Pohang science and technology university. In China, many steel mills also develop corrosion-resistant steel, such as 08CuPVRE series and 3Ni steel of the saddle steel group, 09MnNb steel of the Jinan iron and steel company, and the like.
Some patents have been published for the development of low alloy steel with high corrosion resistance in marine atmospheric environment, for example, patent publication No. CN101376953A discloses "a high corrosion resistance high strength weathering steel and a manufacturing method thereof", patent application No. 201710502466.5 discloses "a weathering steel used in marine environment", patent application No. 201710075154.0 "a high corrosion resistance low alloy steel suitable for high temperature coastal environment", and U.S. Pat. No. US6315946 discloses "ultra low carbon bainite weathering steel". Most of these patents are centered around changes in the alloying elements Cu, Ni, Cr or emphasis on the rolling process, and less on actual field exposure corrosion experiments in hot-zone high-humidity hot marine atmospheric environments; the patent application number 201611097512.X discloses a high-strength weathering steel for high-humidity and high-heat-resistance ocean atmosphere, the steel of the invention has good corrosion resistance after field insolation experiments are carried out in the south China sea area, the Ni content in the invention is as high as 2.90-3.10%, and the cost of the steel is obviously improved.
In conclusion, the corrosion-resistant steels in various countries have different developments, but are researched, developed and applied according to the use environment and climate characteristics of the country. In general, although corrosion-resistant steel is rapidly developed in various countries, no economic corrosion-resistant low alloy steel which meets certain corrosion resistance requirements, has low cost and can meet large-scale engineering application and is suitable for the high-humidity and high-heat harsh marine atmospheric environment of a heat band is available.
Disclosure of Invention
The invention aims to solve the existing problems and provide economical corrosion-resistant low alloy steel for a high-humidity and high-heat marine atmospheric environment bridge structure, which can improve the corrosion resistance of the heat-resistant high-humidity and high-heat severe marine atmosphere of a steel grade under the condition of certain economical and reasonable manufacturing cost so as to meet the urgent need of the high-humidity and high-heat marine atmospheric environment of a heat zone on the low alloy steel for the high-corrosion-resistance bridge structure.
The corrosion-resistant low alloy steel for the bridge structure in the high-humidity and high-heat marine atmospheric environment comprises the following chemical components in percentage by weight: c: 0.02 to 0.05, Si: 0.20 to 0.60, Mn: 0.70-1.20, P is less than or equal to 0.02, S is less than or equal to 0.003, Cu: 0.20 to 0.90, Ni: 0.50 to 1.60, Mo: 0.10 to 0.50, Ti: 0.010-0.030, Nb is less than or equal to 0.030, and the balance is Fe and inevitable impurities.
Further, the chemical composition (wt.%) of the steel is preferably: c: 0.025-0.035%, Si: 0.29 to 0.32%, Mn: 0.72-0.76%, P is less than or equal to 0.01%, S is less than or equal to 0.003%, Cu: 0.23-0.90, Ni: 0.70 to 1.50, Mo: 0.20 to 0.40, Ti: 0.018-0.021, Nb is less than or equal to 0.020, and the balance of Fe and other unavoidable impurity elements.
The rolling process of the corrosion-resistant low alloy steel for the bridge structure in the high-humidity and high-heat marine atmospheric environment comprises the following steps:
smelting in a 200kg vacuum induction furnace at the heating temperature of 1150-1200 ℃ with the pass deformation of 10-20%, controlling rolling in two stages of a recrystallization zone and a non-recrystallization zone, and finally quickly quenching to room temperature, wherein the thickness specification of the finished plate is 5-40 mm.
Further, the corrosion-resistant steel structure is ferrite + pearlite.
Further, the yield strength of the corrosion resistant steel: 345-490 MPa, tensile strength: 530 to 580MPa, elongation after fracture: 22-30%, total elongation: 10 to 15 percent.
The following description of the design of the steel chemical composition of the present invention is as follows:
c: the steel is important for improving the strength of steel, the content of C in the weathering steel is controlled below 0.12 percent, meanwhile, the content of C has certain influence on the heat treatment of the structure, and the structure of the steel is ferrite plus pearlite after being rolled, so the content of the steel is controlled to be 0.02 to 0.05 percent.
Si: the Si-rich protective film can be formed on the surface of the steel, so that the marine atmosphere corrosion resistance of the steel is improved, but the excessive Si content is harmful to the weldability of the steel, and therefore, the Si content is controlled to be 0.20-0.60%.
Mn: a proper amount of Mn in the steel can improve the corrosion resistance of the steel in the ocean atmosphere, but the over-high content can increase the hardenability of the steel and influence the toughness, so the content of Mn is controlled to be 0.70-1.20%.
P: the atmospheric corrosion resistance of the steel can be effectively improved, but the toughness and the weldability of the steel are damaged due to the excessively high content of the steel, so that the content of the steel is controlled to be less than or equal to 0.02 percent.
S: easily form sulfide inclusions, damage the toughness of steel and seriously reduce the corrosion resistance of the steel, so the content of the sulfide inclusions is controlled to be less than or equal to 0.003 percent.
Cu: the corrosion-resistant steel is one of the alloy elements with the best corrosion-resistant effect, the corrosion resistance of the corrosion-resistant steel can be several times higher than that of plain carbon steel by adding less than 0.5% in the marine atmospheric environment, but the hot brittleness is easily caused by the excessively high content of the corrosion-resistant steel, so the content of the corrosion-resistant steel is controlled to be 0.20-0.90%.
Ni: the Ni content is one of the most commonly used effective corrosion resisting elements in corrosion resisting steel, the increase of the content is more effective for improving the corrosion resistance of the material in the ocean atmosphere environment, but the Ni content is properly increased in consideration of economic cost, so the content is controlled to be 0.50-1.60%.
Mo: the ocean atmospheric corrosion resistance of the steel can be effectively improved by properly increasing the content of the alloy element Mo, but the hardenability of the steel is increased and the welding is not facilitated due to the excessively high content of the alloy element Mo, so that the content of the alloy element Mo is controlled to be 0.10-0.50%.
Ti: the method is beneficial to grain refinement, strength improvement and welding performance improvement, so that the content of the alloy is controlled to be 0.010-0.030%.
Nb: the addition of a small amount of the alloy contributes to the grain refinement of steel, and the content of the alloy is controlled to be less than or equal to 0.030 percent from the view point of microalloying cost.
Design instructions based on the above components:
the invention has the advantages that:
1. the corrosion-resistant steel obtained according to the alloy design components has excellent corrosion resistance, and a 12-month field exposure experiment is carried out at an atmospheric corrosion experiment station of the thailand dalle tropical sea, and the result shows that the corrosion resistance of the low alloy steel with reasonable component design can be improved by 50% compared with that of ordinary carbon steel (see example 1);
2. the corrosion-resistant steel has yield strength of 345-490 MPa, tensile strength of 530-580 MPa, elongation after fracture of 22-30% and total elongation of 10-15%, and meets the requirements of corrosion-resistant low-alloy steel for bridge structures in marine atmospheric environments on mechanical properties.
Drawings
FIG. 1 macroscopic Corrosion morphology of the sample after Corrosion (a:0# plain carbon Steel; b:1# Low alloy Steel; c:2# Low alloy Steel)
Detailed Description
Example 1 on-site insolation experiment at atmospheric corrosion experiment station in thailand ocean environment
The test steel is subjected to 12-month field exposure experiment at the atmospheric corrosion experiment station in the marine environment in Thailand. The atmosphere exposure experiment is carried out according to the general requirements of GB/T14165-2008 'metal and alloy atmospheric corrosion experiment field experiment', the front surface of an exposure sample faces south, and the exposure sample is exposed at 45 degrees with the ground. The samples were mounted on an exposure rack. And taking back the sample after 12 months of exposure, observing the surface macroscopic morphology of the sample before and after pickling by using a digital camera, and testing the corrosion weight loss after pickling. The mechanical properties of the steel are shown in Table 2.
Recording the original mass of the corrosion weightlessness sample before the exposure experiment, removing a surface rust layer by using a rust removing liquid after sampling on site, wherein the preparation of the rust removing liquid is carried out according to the relevant requirements in GB/T16545-.
Wherein V represents the corrosion rate, mm/y;
w is corrosion weight loss g after exposure for different time;
s-surface area of sample, cm2；
t-exposure time, h;
rho-sample Density, g/cm3。
The chemical compositions of the three test steels are shown in table 1, wherein the 1# and 2# steels are novel corrosion-resistant steels obtained by optimizing the content of alloy elements on the basis of plain carbon steel. Table 2 shows the mechanical property test results of the low alloy steel of the present invention.
TABLE 1 chemical composition (wt%) of carbon steel for experiments and corrosion resistant low alloy steel of the present invention
TABLE 2 mechanical Properties of the corrosion-resistant Low alloy steels of the invention
The corrosion resistance of the low alloy steel of the invention is calculated by formula (2):
wherein, CiIs corrosion resistance of steel, ViRespectively 0# (i is 0), 1# (i is 1) and 2# (i is 2), wherein V is0Is the corrosion rate of plain carbon steel.
The corrosion resistance improvement rate α of the corrosion resistant steel relative to plain carbon steel is calculated by the formula (3)i：
The corrosion resistance improvement rates obtained from the field test data of example 1 are shown in table 3.
TABLE 3 Corrosion resistance improvement of the low alloy steel of the present invention over plain carbon steel
As can be seen from table 3, the 2# steel of the present invention exhibited good corrosion resistance, which was improved by 50% compared to plain carbon steel. FIG. 1 is a macroscopic photograph of the corrosion of the plain carbon steel and the corrosion-resistant low alloy steel of the invention in the actual tropical marine environment in example 1, and it can be seen that the rust layer on the plain carbon steel surface is relatively completely covered but has no obvious protective property, and the rust layer on the No. 2 steel surface is relatively dense and has the best protective property. The corrosion resistance of steel can be effectively enhanced by increasing the content of the single alloy element Mo, but the effect of increasing the content of the single alloy element Cu on the improvement of the corrosion resistance is not obvious, so that the cost of the low alloy steel element can be more economic and reasonable by properly increasing the content of the alloy element Mo on the premise of reducing the content of the alloy elements Cu and Ni, and the low alloy steel has good corrosion resistance to a high-humidity hot ocean atmosphere environment with a heat-resistant zone.
In conclusion, the corrosion resistance of the low alloy steel is obviously improved compared with that of plain carbon steel. The corrosion resistance improvement rate of the corrosion-resistant low alloy steel can reach 50 percent, and the corrosion resistance of the high-humidity hot marine atmospheric environment of the heat-resistant zone is good. The corrosion-resistant low alloy steel has the yield strength of 345-490 MPa, the tensile strength of 530-580 MPa, the elongation after fracture of 22-30% and the total elongation of 10-15%, meets the requirements of the corrosion-resistant low alloy steel for bridge structures on mechanical properties in marine atmospheric environments, can be used as a structural material in the hot-zone high-humidity and high-heat marine atmospheric environments such as southeast Asia and the like, and prolongs the service life of facilities.
Claims (5)
1. The corrosion-resistant low alloy steel for the high-humidity and high-heat marine atmospheric environment bridge structure is characterized by comprising the following chemical components in percentage by weight: c: 0.02 to 0.05, Si: 0.20 to 0.60, Mn: 0.70-1.20, P is less than or equal to 0.02, S is less than or equal to 0.003, Cu: 0.20 to 0.90, Ni: 0.50 to 1.60, Mo: 0.10 to 0.50, Ti: 0.010-0.030 percent, Nb is less than or equal to 0.030 percent, and the balance is Fe and inevitable impurities.
2. The corrosion-resistant low alloy steel for the high-humidity marine atmospheric environment bridge structure according to claim 1, which is characterized in that: the chemical composition (wt.%) of the corrosion-resistant steel is preferably: c: 0.025-0.035, Si: 0.29 to 0.32, Mn: 0.72-0.76, P is less than or equal to 0.01, S is less than or equal to 0.003, Cu: 0.23-0.90, Ni: 0.70 to 1.50, Mo: 0.20 to 0.40, Ti: 0.018-0.021, Nb is less than or equal to 0.02, and the balance is Fe and inevitable impurities.
3. A preparation method of the corrosion-resistant low alloy steel for the high-humidity and high-heat marine atmospheric environment bridge structure as claimed in claim 1 or 2, characterized by comprising the following steps: smelting in a vacuum induction furnace at the heating temperature of 1150-1200 ℃ with the pass deformation of 10-20%, rolling into a plate with the required thickness by adopting two stages of a recrystallization zone and a non-recrystallization zone, and finally rapidly quenching to room temperature at the final rolling temperature of 780-860 ℃.
4. The preparation method of the corrosion-resistant low alloy steel for the high-humidity marine atmospheric environment bridge structure according to claim 3, characterized by comprising the following steps: the microstructure of the rolled steel is ferrite plus pearlite.
5. The preparation method of the corrosion-resistant low alloy steel for the high-humidity marine atmospheric environment bridge structure according to claim 3, characterized by comprising the following steps: the yield strength of the low alloy steel reaches 345-490 MPa, the tensile strength reaches 530-580 MPa, the elongation after fracture is 22-30%, and the total elongation is 10-15%.
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|---|---|---|---|---|
| JPH06264176A (en) * | 1993-03-12 | 1994-09-20 | Sumitomo Metal Ind Ltd | Low alloy steel excellent in seawater corrosion resistance |
| CN102650018A (en) * | 2012-05-29 | 2012-08-29 | 江苏省沙钢钢铁研究院有限公司 | Seawater corrosion resistant steel plate and production method thereof |
| CN103194679A (en) * | 2013-04-07 | 2013-07-10 | 南京钢铁股份有限公司 | Steel plate for structure with excellent marine atmospheric corrosion resistance and production method thereof |
| CN106223190A (en) * | 2016-08-31 | 2016-12-14 | 中铁第四勘察设计院集团有限公司 | A kind of bridge steel support without the resistance to sea atmosphere corrosion of application |
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2020
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| CN113755751A (en) * | 2021-08-20 | 2021-12-07 | 首钢集团有限公司 | 235 MPa-level low-alloy corrosion-resistant steel for coating in marine atmospheric environment and manufacturing process thereof |
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Application publication date: 20200904 |