CN101880835B - Seawater corrosion resistant ultra-low carbon bainite steel and preparation method thereof - Google Patents
Seawater corrosion resistant ultra-low carbon bainite steel and preparation method thereof Download PDFInfo
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- 238000005266 casting Methods 0.000 claims abstract description 13
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- 239000000203 mixture Substances 0.000 claims description 9
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Abstract
The invention discloses seawater corrosion resistant ultra-low carbon bainite steel and a preparation method thereof. The bainite steel comprises the following components in percentage by weight: 0.02 to 0.05 percent of C, 1.0 to 1.5 percent of Mn, less than 0.006 percent of S, 0.24 to 0.40 percent of Si, 0.04 to 0.09 percent of P, 0.05 to 0.2 percent of Ni, 0.3 to 0.5 percent of Cu, 0.03 to 0.04percent of Nb, 0.2 to 0.4 percent of Mo, 0.002 to 0.005 percent of B, less than 0.08 percent of Al, less than or equal to 0.06 percent of Cr and the balance of Fe; and the tissue is granular bainite. The preparation method comprises the following steps of: smelting molten steel with vacuum and casting the molten steel to form ingots, roughly rolling the ingots in an austenite recrystallization area after soaking treatment, then finely rolling the ingots in an austenite non-recrystallization area, cooling the rolled ingots to between 450 and 500 DEG C with water after rolling, and cooling the rolled ingots in the air to room temperature. The seawater corrosion resistant ultra-low carbon bainite steel has good comprehensive mechanical property, low raw material cost, simple production process and good seawater corrosion resistance based on excellent mechanical property and welding property.
Description
Technical field
The invention belongs to and relate to corrosion-resistant steel and preparation method thereof, particularly a kind of seawater corrosion resistant ultra-low carbon bainite steel and preparation method thereof.
Background technology
Development along with sea and coastal economy, be used for fields such as bridge spanning the sea, boats and ships, offshore drilling platforms and require steel construction to have excellent comprehensive performances such as high strength, high low-temperature flexibility, high weldability, ultra-low-carbon bainite steel is the ideal material that can satisfy this mechanical property demand.But the applied environment of these steel construction is that long-term exposure is in the seashore atmosphere or seawater of chloride ion-containing; the erosion of corrosive medium make steel construction safety in utilization and be subjected to serious threat work-ing life, take usually to paint or cathode protection measure prevents the harm to structure iron of seawater or chloride ion-containing atmosphere.If can improve the corrosion resistance nature of ultra-low-carbon bainite steel self, make it exempt japanning or cathode protection measure in use, can reduce the maintenance and the maintenance cost of steel construction greatly, guarantee the safety in utilization and the long lifetime of steel construction.
In disclosed corrosion-resistant Hi-Stren steel pertinent literature technology at present, the patent of Japanese publication (publication number JP61012849) has been introduced a kind of seawater corrosion resistance soft steel, mainly be by improving Ni content to 2～4%, and cold soon after the hot rolling+self-tempering technology makes that reinforcing bar is outer and is martensite or bainite that internal layer is low-temperature flexibility and the resistance to corrosion seawater that ferrite and perlite guarantee steel.This method material cost height, complex manufacturing is organized restively, and the intensity of steel does not reach high intensity standard.The patent of asking in another Japan (publication number JP9067619) has been introduced a kind of alloying and production technique of high tensile hot rolled steel sheet.The alloying level of this steel grade is higher, has particularly improved the content than noble metal such as Mo, Ni, Cu, has also increased the manufacturing cost of steel when improving the erosion resistance of steel.The patent (publication number US6315946) of disclosed U. S. application introduced a kind of ULCB weathering steel and added Mn, Cu, Nb, V, Ti, P, Mo, Ni, B alloying element calendar year 2001, its quantity reaches 9 kinds more than, this is difficult to the accurately chemical ingredients of each alloying element of control for suitability for industrialized production, particularly the micro alloying element kind is too much for alloying element, not only increase the manufacturing cost of steel, and can produce complex interactions between each element, the effect of element is separately brought into play in influence.2007 disclosed Chinese patents (publication number CN200610125365.2) introduced the low-carbon bainite weathering steel and adopted quenching+tempering process production after the hot rolling, though improved the intensity of steel, but make complex manufacturingization, production cycle prolongs, and is not easy to realize for large-sized sheet material and long profiles.The patent (publication number CN200810047488.8) of enclosing application in 2008 in disclosed relates to a kind of non-carbide bainitic steel, the weak point of this invention is that chemical ingredients and rolling technology only are provided, but fail to provide the mechanical performance index of steel, the low steel of erosion rate mostly contains high-load Mn in the simulated seawater experiment, Cu, Ni, this has not only increased material cost, and all totally unfavorable to the thermoplasticity and the toughness of steel.
Summary of the invention
Problems such as, preparation cost height bad at existing Seawate-corrosive-resisting steel over-all properties the invention provides a kind of seawater corrosion resistant ultra-low carbon bainite steel and preparation method thereof.
Seawater corrosion resistant ultra-low carbon bainite steel of the present invention be organized as granular bainite, its composition is C0.02～0.05% by weight percentage, Mn 1.0～1.5%, S＜0.006%, Si0.24～0.40%, P 0.04～0.09%, Ni0.05～0.2%, Cu0.3～0.5%, Nb 0.03～0.04%, and Mo 0.2～0.4%, B 0.002～0.005%, Al＜0.08%, Cr≤0.06%, surplus is Fe.
The yield strength of above-mentioned low-carbon bainite steel is 540MPa at least, and tensile strength is 690MPa at least, elongation after fracture 32～35%, relative reduction in area 69～76%, room temperature impact absorbing energy 134～145J ,-40 ℃ of impact absorbing energy 97～129J.
The welding cold cracking sensitivity coefficient Pcm of above-mentioned bainitic steel is 0.13～0.15, and weather-proof index (I) is 6.29～6.95.
The setting principle of composition of the present invention is:
Carbon is very big to intensity, toughness, the weldability influence of steel, for avoiding occurring cementite in the steel, reduces toughness, and be unfavorable for weldability, carbon content should be lower than 0.06, if but carbon content is low excessively, smelt relatively difficulty for big production, therefore, the scope of carbon content is limited to 0.02～0.05%.
Manganese helps improving intensity and toughness, and bainite transformation is had very big promoter action, and is with low cost, and Mn-Cu is compounded with and is beneficial to the raising atmospheric corrosion resistance.Manganese and sulphur form high-melting-point MnS, and it is hot-short to prevent that FeS from causing, and offset sulphur to corrosion proof deleterious effect.Manganese content surpasses at 2% o'clock will make hot-rolled steel produce lower bainite in process of cooling, infringement plasticity and toughness when improving intensity; Manganese content is limited to 1.0～1.5% among the present invention.
Phosphorus is often limited as detrimental impurity in steel, but the compound formation that can promote to have the oxyhydroxide of provide protection of P and Cu, and make oxide film have the self-regeneration function, suppress corrosive and further take place.Phosphorus also has the intensive solid solution strengthening effect.Phosphorus content is too high poly-partially at crystal boundary easily, forms phosphide, and the low-temperature flexibility of steel is had a negative impact, and therefore, phosphorus content is limited in 0.04～0.09%.
Nickel has low-temperature flexibility and the anticorrosive effect that improves steel, can prevent hot-shortly in Copper Bearing Steel, but nickel is noble metal, and therefore, add-on is limited in 0.05～0.2%.
Copper can improve intensity, low-temperature flexibility and the solidity to corrosion of steel, but copper too high levels continuously cast bloom is in heating or be easy to crack during hot rolling, and the price of copper is limited in 0.3～0.5% also than higher with copper content.
Niobium is important micro alloying element, can effectively postpone the dynamic recrystallization of deformed austenite, stop austenite crystal to be grown up, continuously cast bloom has pinning effect by deformation induced carbonitride particle of separating out niobium to dislocation when finish rolling, promote bainite transformation, improve the intensity and the toughness of steel.Content of niobium is limited in 0.03～0.04%.
Molybdenum can be postponed ferritic transformation strongly, promotes bainite to form, and molybdenum and copper, phosphorus, nickel acting in conjunction can improve the solidity to corrosion of steel, particularly improves anti-pitting ability under the chloride ion-containing environment.Molybdenum is a noble metal, and addition is difficult for too much being limited in 0.2～0.4%.
Boron can improve hardening capacity, promotes bainite transformation.Boron preferentially gathers partially at austenite grain boundary can suppress the poly-partially of phosphorus, thereby offsets the disadvantageous effect of phosphorus to low-temperature flexibility.Boron content is limited in 0.002～0.005%.
Preparation method's step of seawater corrosion resistant ultra-low carbon bainite steel of the present invention is:
By the mentioned component smelting molten steel and pour into ingot casting, carry out two stage rolling after ingot casting is warming up to 1200～1230 ℃ of equal thermal treatment 2～3h, wherein the roughing start rolling temperature that carries out in the austenite recrystallization district is 1100～1130 ℃, the roughing finishing temperature is 990～1000 ℃, roughing accumulative total deflection 42～44%; 920～940 ℃ of the finish rolling start rolling temperatures that carries out in austenite non-recrystallization district, the finish rolling finishing temperature is 830～850 ℃, finish rolling total deformation 69～71%, finish rolling finishes the back with rate of cooling water-cooled to 450～500 of 7～10 ℃/s ℃, and air cooling is to room temperature again.
Among the preparation method of the present invention, the roughing process is come the original thick austenite crystal of effective refinement by the static recrystallize of austenite dynamic recrystallization and passage interim; The finish rolling process can increase defect concentration in the deformed austenite by controlled rolling of low temperature aximal deformation value and controlled chilling, induce separating out of the second phase particle, improve the nucleation rate of austenite to bainitic transformation, suppress ferritic formation, at room temperature obtain tiny and uniform granular bainite tissue.
The comprehensive mechanical property of seawater corrosion resistant ultra-low carbon bainite steel of the present invention is good, and raw materials cost is low, production technique is simple, by reducing carbon content and rationally adding elements such as copper, phosphorus, molybdenum, boron, adopt the TMCP rolling technology, obtain uniform granular bainite tissue, add the formation that P can promote fine and close interior rusty scale in the ultra-low-carbon bainite steel, thereby effectively reduce the erosion rate in seawater, therefore having on excellent mechanical property and the weldability basis, also has good seawater corrosion resistance.
Description of drawings
Fig. 1 is the low-carbon bainite product made from steel and the polarization curve of traditional low-carbon bainite steel in 3.5%NaCl solution of the embodiment of the invention 1,2;
Fig. 2 is the low-carbon (LC) Jian Shi body steel band rusty scale sample and the polarization curve of traditional low-carbon bainite steel band rusty scale sample in 3.5%NaCl solution of the embodiment of the invention 1,2;
Fig. 3 is traditional low-carbon bainite steel microstructure picture figure;
Fig. 4 is the low-carbon bainite steel microstructure picture figure of the embodiment of the invention 1;
Fig. 5 is the low-carbon bainite steel microstructure picture figure of the embodiment of the invention 2;
Fig. 6 is that traditional low-carbon bainite steel soak 20 days rear surface rusty scale shape appearance figures in 3.5%NaCl solution;
Fig. 7 is that the low-carbon bainite steel of the embodiment of the invention 1 soaks 20 days rear surface rusty scale shape appearance figures in 3.5%NaCl solution;
Fig. 8 soaks rusty scale section shape appearance figure after 20 days respectively for the low-carbon bainite product made from steel among traditional low-carbon bainite steel and the embodiment 1 in 3.5%NaCl solution;
(a) is traditional low-carbon bainite steel among the figure, (b) be low-carbon bainite product made from steel among the embodiment 1, X is the low phosphoretic steel of similar component, Y is the product of embodiment 1, and Z is the product of embodiment 2, and B is the rusty scale of traditional low-carbon bainite steel, C is traditional low-carbon bainite steel matrix, D is the outer rusty scale of the low-carbon bainite steel of embodiment 1, and E is the interior rusty scale of the low-carbon bainite steel of embodiment 1, and F is the low-carbon bainite steel matrix.
Embodiment
Embodiment 1
Composition is C 0.03% by weight percentage, and Mn 1.17%, and S 0.005%, and Si 0.27%, and P 0.048%, Ni 0.15%, and Cu 0.3%, and Nb 0.038%, and Mo 0.21%, and B 0.0038%, Al 0.078%, and Cr 0.06%, and surplus is Fe, is organized as bainite.
The yield strength of above-mentioned low-carbon bainite steel is 540MPa, and tensile strength is 690MPa, elongation after fracture 32%, and relative reduction in area 69.4%, the room temperature impact of collision absorbs merit 140.1J, and-40 ℃ of impacts of collision absorb merit 127.8J.
The welding cold cracking sensitivity coefficient of above-mentioned low-carbon bainite steel is 0.15, and weather-proof index is 6.29～6.95.
The preparation method is: by the mentioned component smelting molten steel and pour into ingot casting, carry out two stage rolling after ingot casting is warming up to 1200 ℃ of equal thermal treatment 3h, wherein, 1100 ℃ of the roughing start rolling temperatures that carries out in the austenite recrystallization district, the roughing finishing temperature is 990 ℃, roughing accumulative total deflection 42%; 920 ℃ of the finish rolling start rolling temperatures that carries out in austenite non-recrystallization district, the finish rolling finishing temperature is 830 ℃, finish rolling total deformation 69%, finish rolling finishes the back with the rate of cooling water-cooled to 500 of 7 ℃/s ℃, and air cooling is to room temperature again; Microstructure as shown in Figure 4.
With the etch 5 days in 3.5%NaCl solution of above-mentioned low-carbon bainite steel, recording annual corrosion rate is 0.120mm/a, and it is 0.095mm/a that etch recorded annual corrosion rate in 20 days; Soak 20 days rear surface rusty scale patterns as shown in Figure 7, rusty scale section pattern as shown in Figure 8.
Adopt traditional low-carbon bainite steel to compare experiment, the composition of traditional low-carbon bainite steel of selecting for use is C 0.050%, and Mn 1.28%, S 0.008%, and Si 0.40%, and P 0.008%, Ni 0.08%, Cu 0.36%, and Nb 0.040%, and Mo 0.31%, B 0.007%, Al 0.06%, and Cr 0.05%, and surplus is Fe; The welding cold cracking sensitivity coefficient is 0.20, and weather-proof index is 5.83; The yield strength of low-carbon bainite steel is 725MPa, and tensile strength is 810MPa, elongation after fracture 32.8%, and relative reduction in area 50.0%, the room temperature impact of collision absorbs merit 111.6J, and-40 ℃ of impacts of collision absorb merit 50.0J.Etch is 5 days in 3.5%NaCl solution, and recording annual corrosion rate is 0.134mm/a, and it is 0.104mm/a that etch recorded annual corrosion rate in 20 days; Microstructure picture is soaked 20 days rear surface rusty scales as shown in Figure 6 as shown in Figure 3, and rusty scale section pattern as shown in Figure 8.
The polarization curve of above-mentioned two kinds of steel in 3.5%NaCl solution is with the polarization curve of rusty scale sample in 3.5%NaCl solution as shown in Figure 2 as shown in Figure 1.
Embodiment 2
Composition is C 0.03% by weight percentage, and Mn 1.14%, and S 0.005%, and Si 0.28%, and P 0.09%, Ni 0.15%, Cu0.3%, and Nb 0.036%, and Mo 0.22%, and B 0.0038%, Al 0.067%, and Cr 0.06%, and surplus is Fe, is organized as bainite.
The yield strength of above-mentioned low-carbon bainite steel is 575MPa, and tensile strength is 720 MPa, elongation after fracture 32.8%, and relative reduction in area 70.0%, the room temperature impact of collision absorbs merit 134.6J, and-40 ℃ of impacts of collision absorb merit 97.8J.
The welding cold cracking sensitivity coefficient of above-mentioned low-carbon bainite steel is 0.15, and weather-proof index is 6.95.
The preparation method is: by the mentioned component smelting molten steel and pour into ingot casting, carry out two stage rolling after ingot casting is warming up to 1230 ℃ of equal thermal treatment 2.5h, wherein, 1130 ℃ of the roughing start rolling temperatures that carries out in the austenite recrystallization district, the roughing finishing temperature is 1000 ℃, roughing accumulative total deflection 44%; 940 ℃ of the finish rolling start rolling temperatures that carries out in austenite non-recrystallization district, the finish rolling finishing temperature is 850 ℃, finish rolling total deformation 71%, finish rolling finishes the back with the rate of cooling water-cooled to 480 of 8 ℃/s ℃, and air cooling is to room temperature again; Microstructure as shown in Figure 5.
With the etch 5 days in 3.5%NaCl solution of above-mentioned low-carbon bainite steel, recording annual corrosion rate is 0.107mm/a, and it is 0.090mm/a that etch recorded annual corrosion rate in 20 days.
Embodiment 3
Composition is C 0.02% by weight percentage, and Mn 1.05%, and S 0.004%, and Si 0.40%, and P 0.08%, and Ni 0.05%, Cu0.4%, and Nb 0.03%, and Mo 0.31%, and B 0.0022%, and Al 0.071%, and Cr 0.05%, and surplus is Fe, is organized as bainite.
The yield strength of above-mentioned low-carbon bainite steel is 563MPa, and tensile strength is 705MPa, elongation after fracture 32.5%, and relative reduction in area 73%, the room temperature impact of collision absorbs merit 131J, and-40 ℃ of impacts of collision absorb merit 101.3J.
The welding cold cracking sensitivity coefficient of above-mentioned low-carbon bainite steel is 0.13, and weather-proof index is 6.56.
The preparation method is: by the mentioned component smelting molten steel and pour into ingot casting, carry out two stage rolling after ingot casting is warming up to 1220 ℃ of equal thermal treatment 2h, wherein, 1110 ℃ of the roughing start rolling temperatures that carries out in the austenite recrystallization district, the roughing finishing temperature is 990 ℃, roughing accumulative total deflection 43%; 930 ℃ of the finish rolling start rolling temperatures that carries out in austenite non-recrystallization district, the finish rolling finishing temperature is 840 ℃, finish rolling total deformation 70%, finish rolling finishes the back with the rate of cooling water-cooled to 460 of 9 ℃/s ℃, and air cooling is to room temperature again.
Embodiment 4
Composition is C 0.05% by weight percentage, and Mn 1.5%, and S 0.005%, and Si 0.33%, and P 0.055%, and Ni 0.19%, and Cu 0.5%, and Nb 0.04%, and Mo 0.4%, and B 0.005%, and Al 0.064%, and Cr 0.05%, and surplus is Fe, is organized as bainite.
The yield strength of above-mentioned low-carbon bainite steel is 570MPa, and tensile strength is 710MPa, elongation after fracture 33%, and relative reduction in area 71%, the room temperature impact of collision absorbs merit 139J, and-40 ℃ of impacts of collision absorb merit 112.3J.
The welding cold cracking sensitivity coefficient of above-mentioned low-carbon bainite steel is 0.14, and weather-proof index is 6.73.
The preparation method is: by the mentioned component smelting molten steel and pour into ingot casting, carry out two stage rolling after ingot casting is warming up to 1220 ℃ of equal thermal treatment 3h, wherein, 1120 ℃ of the roughing start rolling temperatures that carries out in the austenite recrystallization district, the roughing finishing temperature is 1000 ℃, roughing accumulative total deflection 44%; 920 ℃ of the finish rolling start rolling temperatures that carries out in austenite non-recrystallization district, the finish rolling finishing temperature is 850 ℃, finish rolling total deformation 70%, finish rolling finishes the back with the rate of cooling water-cooled to 450 of 10 ℃/s ℃, and air cooling is to room temperature again.
Claims (2)
1. a seawater corrosion resistant ultra-low carbon bainite steel is characterized in that composition is C 0.02～0.05% by weight percentage, and Mn 1.0～1.5%, S＜0.006%, Si0.24～0.40%, P 0.04～0.09%, Ni0.05～0.2%, Cu 0.3～0.5%, Nb0.03～0.04%, and Mo 0.2～0.4%, B 0.002～0.005%, Al＜0.08%, Cr≤0.06%, surplus is Fe; Be organized as granular bainite; The yield strength of this low-carbon bainite steel is 540MPa at least, and tensile strength is 690MPa at least, elongation after fracture 32～35%, and relative reduction in area 69～76%, the room temperature impact of collision absorbs merit 134～145J, and-40 ℃ of impacts of collision absorb merit 97～129J; This low-carbon bainite steel welding cold cracking sensitivity coefficient is 0.13～0.15, and weather-proof index is 6.29～6.95.
2. the preparation method of the described seawater corrosion resistant ultra-low carbon bainite steel of claim 1, it is characterized in that step is: the vacuum metling molten steel also pours into ingot casting, and its composition is C 0.02～0.05% by weight percentage, Mn 1.0～1.5%, S＜0.006%, Si0.24～0.40%, P 0.04～0.09%, Ni0.05～0.2%, and Cu 0.3～0.5%, Nb 0.03～0.04%, Mo 0.2～0.4%, and B 0.002～0.005%, Al＜0.08%, Cr≤0.06%, surplus are Fe; Carry out two stage rolling after ingot casting is warming up to 1200～1230 ℃ of equal thermal treatment 2～3h, wherein, 1100～1130 ℃ of the roughing start rolling temperatures that carries out in the austenite recrystallization district, the roughing finishing temperature is 990～1000 ℃, roughing accumulative total deflection 42～44%; 920～940 ℃ of the finish rolling start rolling temperatures that carries out in austenite non-recrystallization district, the finish rolling finishing temperature is 830～850 ℃, finish rolling total deformation 69～71%, finish rolling finishes the back with rate of cooling water-cooled to 450～500 of 7～10 ℃/s ℃, and air cooling is to room temperature again.
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| CN102127710B (en) * | 2011-04-07 | 2013-06-12 | 莱芜钢铁集团有限公司 | Chromium-free weather-resistant steel |
| CN102605255A (en) * | 2012-01-19 | 2012-07-25 | 武汉钢铁(集团)公司 | 400Mpa grade corrosion resistant reinforcing steel bar |
| CN102586686B (en) * | 2012-03-05 | 2013-09-18 | 武汉钢铁(集团)公司 | Clean corrosion-resistant steel for ocean engineering and manufacturing method thereof |
| CN104152808B (en) * | 2014-08-24 | 2017-02-15 | 长兴德田工程机械股份有限公司 | Boron-containing high-silicon bainite wear-resistant corrosion-resistant alloy and manufacturing method thereof |
| CN105349888B (en) * | 2015-11-30 | 2017-06-23 | 钢铁研究总院 | One kind can high heat input welding vanadium nitrogen titanium high-strength steel sheet and preparation method |
| CN113755679A (en) * | 2021-09-09 | 2021-12-07 | 新疆八一钢铁股份有限公司 | Manufacturing method of weather-resistant bridge steel with uniform granular bainite structure |
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