CN101235469A - High-strength easy-formation atmospheric corrosion resisting steel - Google Patents
High-strength easy-formation atmospheric corrosion resisting steel Download PDFInfo
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Abstract
The invention relates to high strength easily forming atmospheric corrosion resistant steel. The invention provides the high strength easily forming atmospheric corrosion resistant steel aiming at the problems in existing steel that the weatherability is bad and the service life is lowered under the condition that the thickness is thinned. The high strength easily forming atmospheric corrosion resistant steel is composed of components of following weight percent: C: 0.04-0.09%, Si: 0.10-0.50%, Mn: 1.20-1.70%, P: <=0.020%, S: < =0.010%, Cu: 0.20-0.60%, Cr: 0.40-0.80%, Ni: 0.20-0.50% and Nb: 0.03-0.07%, and also comprises one or a plurality of Mo: <=0.20%, Ti: <=0.03% and Als: <=0.035%, and allowance is Fe and unavoidable impurity. The yield strength of the steel of the invention is more than or equal to 550MPa, the tensile strength is more than or equal to 650MPa, the percentage elongation is more than or equal to 18%, the corrosion resistance is equivalent to SPA-H steel which is used for previous containers, and the steel has excellent welding performance, cold roll forming performance and low temperature impact toughness, which is beneficial for extending and applying.
Description
Technical field
The present invention relates to a kind of steel.
Background technology
Continuous development along with container industry, the container factory man has adopted the high-strength steel (container semi-trailer of yield strength 〉=550MPa, tensile strength 〉=600MPa) make outlet Europe, the United States, add, to reduce the casing deadweight, strengthen shock resistance, improve loading weight.Present used high strength steel grade does not have weathering resistance, increases in intensity, in the time of the casing reduced thickness, can produce the negative effect of casing in the situation reduction in following work-ing life of reduced thickness.
In order to significantly improve the atmospheric corrosion resistance of steel, usually adopt and add alloying elements such as a certain amount of Cu, P in steel, high phosphorus, the copper developed as the U.S. add nickel, chromium weather resisting steel COR-TENA (ASTM A242) series, and its main chemical compositions is by weight percentage: C≤0.12%, Mn:0.20～0.50%, Si:0.25～0.75%, Cu:0.25～0.60%, S≤0.04%, P≤0.07～0.15%, Cr:0.30～1.25%, Ni≤0.65%, surplus is Fe.Yield strength 〉=the 345MPa of this weather resisting steel, tensile strength 〉=490MPa.Also developed COR-TENB (ASTM A588) serial weather resisting steel and modified form COR-TEN B weather resisting steel in addition based on Cr, Mn, Cu, i.e. COR-TEN B-QT 70 (ASTM A852), this steel carbon content is 0.12～0.20%.
Before the present patent application, " a kind of economy type weathering-resistant steel " patent of publication number CN 1800428A, its composition design has added atmospheric corrosion resistance element Cu and P on the basis of conventional element.Though this steel has been considered the requirement of environment for use, lower to the requirement of intensity rank, yield strength only has 345MPa.For at present concerning the requirement of ferrous materials high intensity levels, the intensity rank of this steel is on the low side, makes it use and also has significant limitation.
Another U.S. Patent number is US6, and 315,946 patent is introduced a kind of ULCB weather resisting steel (Ultra low carbon bainitic weathering steel), and its chemical ingredients is by weight percentage: C:0.015～0.035%; Cu:0.20～0.40%; Cr:0.40～0.70%; Ni:0.20～0.50%; Ti:0.02～0.05%; Nb:0.03～0.06%; B:0.0015～0.003%; Mn≤2.0%; P≤0.012%; S≤0.005%; Si≤0.40%; Mo≤0.50%; V≤0.10%; Al≤0.03%; N≤0.006%; Surplus is Fe and trace impurity.Behind controlled rolling and controlled cooling yield strength only 〉=450MPa, and the concrete scheme that contains Mo in a kind of composition of steel is not disclosed in this patent publication.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, the high-strength easy-formation atmospheric corrosion resisting steel of a kind of low-carbon (LC)-manganese for the Cu-Cr-Ni-Nb series of base is provided, the yield strength of this steel (ReL) 〉=550MPa, tensile strength (Rm) 〉=650MPa, unit elongation (A) 〉=18%, its corrosion resisting property was suitable with the SPA-H steel with former freight container, and had good welding property, cold roll forming performance and low-temperature impact toughness.
The technical scheme that is adopted is as follows for achieving the above object:
A kind of high-strength easy-formation atmospheric corrosion resisting steel, one-tenth by following weight per-cent is grouped into: C:0.04～0.09%, Si:0.10～0.50%, Mn:1.20～1.70%, P: S≤0.020% :≤0.010%, Cu:0.20～0.60%, Cr:0.40～0.80%, Ni:0.20～0.50%, Nb:0.03～0.07%, also contain one or more of following compositions: Mo: Ti≤0.20%: Als≤0.03% :≤0.035%, surplus is Fe and unavoidable impurities.
In the mentioned component, preferably adopt following weight per-cent:
C：0.06～0.09％；
Mn：1.30～1.60％；
Cu+Cr+Ni：0.9％＜Cu+Cr+Ni＜1.6％；
The weight ratio of Ni/Cu is: 0.80～1.20;
Nb：0.04～0.07％。
In the mentioned component, all right preferred following weight per-cent: C:0.04～0.07%; Si:0.20～0.40%; Mn:1.50～1.70%; P :≤0.020%; S :≤0.010%; Cu:0.30～0.40%; Cr:0.50～0.70%; Ni:0.30～0.40%; Nb:0.05～0.06%.
For improving the low-temperature flexibility of steel, can also handle by ton steel≤200 gram feeding RE silks or ton steel 500～800 gram feeding Ca-Si silks.
The setting of main alloy element content of the present invention is based on following principle:
Carbon of the present invention (C) content is 0.04～0.09%, and carbon is one of element of indispensable raising steel strength in the steel, if dissolve in matrix, can play the effect of solution strengthening, increases carbon content and can promote to form carbide and martensite.In order to guarantee high tenacity, good cold formability and welding property, carbon content is limited in below 0.09%, not only can improve the intensity of steel but also be fit to production operation.
Silicon of the present invention (Si) content is 0.10%～0.50%, and Si mainly is the intensity that improves steel with the solution strengthening form, also be simultaneously the deoxidant element in the steel, but content can not be too high, in order to avoid reduce the toughness and the welding property of steel.
Manganese of the present invention (Mn) content is the speed of cooling when rolling, specifications and characteristics and definite according to product, add 1.20%～1.70% manganese, can reduce austenitic transformation and become ferritic transformation temperature, enlarge the austenite region in the iron-carbon diagram, promote the middle temperature structural transformation of steel, obtain uniform microtexture, thereby make steel have good weather resistance, high intensity and excellent low-temperature flexibility.Too high Mn impairs the toughness of steel, and too low Mn then can not guarantee the intensity of steel plate.
Phosphorus of the present invention (P) content≤0.020%, sulphur (S) content≤0.010%.Higher phosphorus content can increase substantially the weathering resistance of steel, but phosphorus causes segregation easily in steel, worsen welding property, significantly reduce steel low-temperature impact toughness, improve brittle transition temperature, so, consider that hardness of steel of the present invention is higher, control phosphorus content≤0.020%.Sulphur easily combines generation MnS and is mingled with manganese, sulphur also influences the low-temperature impact toughness of steel.Therefore, the present invention should reduce as far as possible phosphorus, element sulphur to rigidity can disadvantageous effect, by molten iron being carried out means such as dark desulfurization pre-treatment, vacuum-treat, control phosphorus, sulphur content, thereby alleviate its disadvantageous effect.
Copper of the present invention (Cu) content is 0.20%～0.60%, copper can improve the hardening capacity of steel, in steel, mainly play solid solution and precipitation strength effect, pass through the suitable proportioning of Cu-Cr-Ni simultaneously, can significantly improve the weather resistance of steel, help obtaining good low-temperature flexibility in addition, increase the antifatigue crack propagation ability of steel.Cu content was less than 0.15% o'clock, and its precipitation strength effect is not obvious, and Cu content was greater than 0.60% o'clock, and the steel plate welding heat influence area toughness can reduce, and easily produced check crack in steel billet heat-processed.
Cr, Ni can improve the erosion resistance of steel.Add several raising erosion resistance unit in the steel simultaneously and have good especially effect, contain the Cu steel in corrosion process, enrichment of element such as Cu, Cr, Ni have reduced Fe near in the metal rusty scale of matrix
3O
4Degree of crystallization, form fine and close, approach amorphous stable rusty scale.This kind rusty scale can hinder and have corrosive medium to matrix permeability, and the atmospheric corrosion resistance of steel is improved.Ni can also significantly improve the low-temperature flexibility of steel simultaneously, and base material and welded heat affecting zone low-temperature flexibility are increased substantially.The weight ratio of Ni/Cu is: 0.80～1.20, and Ni can effectively stop the hot-short check crack that causes of Cu.The Ni add-on is less than 0.10%, and Ni does not have effect, but too high levels easily causes the steel plate iron scale to be difficult to come off.The content of Ni of the present invention is 0.20～0.50%, and the content of Cr is 0.40～0.80%.
Nb content of the present invention is 0.03～0.07%, and Nb is strong carbonitride forming element, can improve the austenite recrystallization temperature of steel, is beneficial to steel of the present invention and is rolled under higher rolling temperature.Simultaneously, Nb is crystal grain thinning and improve the tensile strength of steel of the present invention significantly, in the controlled rolling process, and by suppressing recrystallize and stop grain growth, but the refine austenite grain-size.In rolling the postcooling process, the small particle of NbC and NbN is separated out, and can play precipitation strength.
Also contain one or more and RE or Ca-Si among Ti, Mo, the Als in the steel of the present invention.
Ti content of the present invention is≤0.03%, Ti is a kind of intensive carbide and nitride forming element, in reheating, steel stop austenite crystal to be grown up, TiN and TiC separate out when the roughing of high temperature austenite district, the pinning austenite grain boundary suppresses austenite crystal and grows up effectively, and steel plate is in welding process in addition, TiN in the steel and TiC particle can significantly stop the heat affected zone grain growth, thereby improve the steel plate welding property.
The content of Mo of the present invention is≤0.20%.Mo can increase hardening capacity, significantly improves the intensity of steel.Simultaneously, Mo also can effectively improve the corrosion resistance of steel.But too high Mo can make the low-temperature flexibility of steel significantly worsen.Excessive Mo also can form martensite when welding, cause the brittle increase of welding joint.So the suitable upper limit is controlled to be 0.20%.
Als content of the present invention is controlled at≤and 0.035%, Al is the main deoxidant element in the steel.Al content will cause the oxide inclusion of Al to increase greater than 0.035%, reduce the purity of steel, be unfavorable for the toughness and the weather resistance of steel.The fusing point of Al is higher, and aborning, Al can be used for organizing grain growth.
Steel of the present invention carries out rare earth (RE) aborning or silico-calcium (Ca-Si) is handled, and it mainly acts on all is sulfide inclusion in the nodularization steel of the present invention, to improve the lateral performance of steel.And the electrode potential difference by reducing sulfide and matrix on every side is to improve corrosion resistance.When carrying out the rare earth processing, form one deck rare earth protective membrane, improve the weather resistance of steel at surface of steel plate.
Steel of the present invention has the following advantages:
1, steel yield strength of the present invention (ReL) 〉=550MPa, tensile strength (Rm) 〉=650MPa, unit elongation (A) 〉=18% belongs to high-strength easy-formation atmospheric corrosion resisting steel.
2, steel constitution simplicity of design of the present invention, the composition of steel is designed to the no P high-strength weathering steel of low-carbon (LC)-manganese for the Cu-Cr-Ni-Nb series of base, compare with high P weathering steel, steel of the present invention has overcome because intensity improves the influence of processability, has therefore guaranteed that steel has good processability.
3. steel of the present invention has splendid obdurability coupling, and good low-temperature flexibility has good welding property simultaneously, can simplify weldprocedure, improves welding efficiency, and steel of the present invention can be widely used in makes freight container and other engineering corrosion resistant member.
Make the development trend of container semi-trailer according to market with non-weather-resistant and high-strength degree steel, when developing a kind of freight container special-purpose steel with high strength, high-weatherability, excellent formability and weldability, it will replace present non-weather-resistant and high-strength degree steel.Simultaneously, along with the raising and the improvement of moulding, welding, complete processing and equipment, using high-strength weathering steel to make freight container also is development in future trend.Its main purpose meaning is: one, and along with improving, according to formula t with hardness of steel
2=t
1* (Rel1/Rel2)
1/2(t wherein
1-former the material thickness of using, t
2-high-strength material thickness, the former material yield intensity of using of Rel1-, Rel2-high-strength material yield strength), use high yield strength steel obviously to reduce thickness of steel product, alleviate Container Weight, strengthen casing impact resistance in transportation, thereby the reduction transportation cost prolongs the casing life-span.Concerning the user, disposable a small amount of input increases, but the benefit of raising stowage capacity is secular.Its two, being constructed and put into operation and give producing high-strength steel of the high-power hot continuous mill of steel mill provides favourable condition, can give full play to the equipment advantage of high-power hot continuous mill, produces high-level steel grade.Its three, yield strength 〉=550MPa, tensile strength 〉=650MPa high-strength and high-weather-resistance easy-formation container steel have huge market potential, conservative estimation whole nation every year is 80,000 tons of demands at least.Its four, can reduce import.Its five, steel of the present invention also can be applicable to fields such as building, engineering machinery, is beneficial to and applies.
Embodiment
Elaborate the preferred embodiment of the present invention below.
Table 1 has been listed the chemical ingredients that the present invention can be used for several specific embodiments of the high-strength easy-formation atmospheric corrosion resisting steel that freight container and other engineering make with corrosion resistant member.The production method of these several steel is as follows: carry out top bottom blowing in 80 tons of converters of steelworks, adopt the dark desulfurization of molten iron, dephosphorizing technology, make S≤0.01% in the molten iron, carry out the converter top and bottom blowing then, feed the deoxidation of Al silk, the stove final vacuum is handled, make chemical ingredients in the steel satisfy the requirement of table 1, surplus is Fe and inevitably is mingled with.Continuous casting carries out the calcium processing in Feeding Rare Earth Wire in Continuous Casting Mould or at the LF stove.The pouring molten steel that will satisfy table 1 requirement again becomes the slab of 200～300mm * 1300mm section.Then this slab is delivered to hot rolling mill, on the 2250mm milling train, adopt the controlled rolling and controlled cooling technology to carry out hot continuous rolling, be rolled into hot-rolled sheet (volume).
When adopting the controlled rolling and controlled cooling technology to carry out hot continuous rolling production, in order to give full play to the effect of microalloy element in steel, make full use of the capacity of equipment of high-power milling train, reduce rolling pass, improve percentage pass reduction, earlier slab is heated to 1230～1270 ℃, make the abundant solid solution of microalloy element, roughing start rolling temperature 〉=1150 ℃, roughing is carried out in the austenite recrystallization district, because steel of the present invention has added higher Nb, significantly improved the recrystallization temperature of steel, be convenient to realize that austenite recrystallization district high temperature depresses rollingly greatly, every time draft of roughing is 20～30%, the accumulative total draft is 80～90%, and the roughing end temp is 1000～1100 ℃; Finish rolling again, finish rolling start rolling temperature are 950～1030 ℃, and the pony-roughing pass draft is 20～25%, and last two passage drafts are 10～15%, and finishing temperature is 820～890 ℃; Steel plate rolls the back and adopts the laminar flow cooling, and speed of cooling is 15～40 ℃/s, and coiling temperature is 570～640 ℃, makes the hot-rolled sheet that thickness of slab is 2～12mm (volume).
High-strength easy-formation atmospheric corrosion resisting steel hot continuous rolling processing parameter of the present invention and test-results are listed in table 2 and table 3.Embodiment has enumerated the high-strength easy-formation atmospheric corrosion resisting steel of three kinds of compositions of upper, middle and lower limit, corresponds respectively to the composition 1,2,3 in each table, two kinds of thicker and thin specifications that wherein every kind of technology of upper and lower limit composition is rolling.The performance that reflects from table 3, the thick hot-rolled sheet of 2～12mm of each composition can both satisfy yield strength (ReL) 〉=550MPa, tensile strength (Rm) 〉=650MPa, unit elongation (A) 〉=18%, simultaneously, this steel-40 ℃ Charpy-V impact power (AKv) 〉=100J, d=0,180 ° of clod washes are all qualified, show that steel of the present invention has good formability.
The chemical ingredients of table 1 steel of the present invention (Wt%)
| Composition | C | Si | Mn | P | S | Cu | Cr | Ni | Nb | Ti | Mo | Als |
| 1 | 0.05 | 0.45 | 1.20 | 0.015 | 0.006 | 0.50 | 0.40 | 0.50 | 0.035 | 0.015 | 0.120 | 0.023 |
| 2 | 0.07 | 0.35 | 1.40 | 0.014 | 0.005 | 0.35 | 0.58 | 0.34 | 0.045 | 0.018 | 0.080 | 0.028 |
| 3 | 0.083 | 0.25 | 1.65 | 0.014 | 0.006 | 0.25 | 0.75 | 0.30 | 0.065 | 0.025 | 0.15 | 0.025 |
Table 2 steel hot continuous rolling of the present invention processing parameter
| Composition | Embodiment | Heating temperature ℃ | Roughing end temp ℃ | Finish rolling start rolling temperature ℃ | Finishing temperature ℃ | Coiling temperature ℃ | Water-cooled speed ℃/s | Finished product thickness mm |
| 1 | 1 | 1260 | 1100 | 1030 | 870 | 610 | 20 | 3.2 |
| 2 | 1250 | 1080 | 1015 | 860 | 610 | 19 | 4.5 | |
| 2 | 3 | 1250 | 1080 | 1010 | 850 | 630 | 15 | 6 |
| 4 | 1230 | 1070 | 985 | 850 | 620 | 16 | 8 | |
| 3 | 5 | 1235 | 1055 | 1000 | 830 | 590 | 17.5 | 12 |
| 6 | 1230 | 1050 | 970 | 840 | 580 | 20 | 10 |
Table 3 steel mechanical property test-results of the present invention
| Composition | Embodiment | Finished product thickness | ReL | Rm | A | Clod wash | -40℃ AKv |
| mm | MPa | MPa | ％ | (d＝0、180°) | J | ||
| 1 | 1 | 3.2 | 570 | 680 | 26 | Qualified | 120 |
| 2 | 4.5 | 555 | 660 | 24.5 | Qualified | 116 | |
| 2 | 3 | 6 | 600 | 695 | 27 | Qualified | 130 |
| 4 | 8 | 610 | 710 | 25 | Qualified | 120 | |
| 3 | 5 | 12 | 630 | 740 | 23 | Qualified | 118 |
| 6 | 10 | 635 | 750 | 22.5 | Qualified | 118 |
Annotate: table 2,3 composition 1,2,3 and the composition 1,2,3 in the table 1 are corresponding relation; Simultaneously, composition 1 is by ton steel 150 gram feeding RE silks, and composition 2 is by ton steel 600 gram feeding Ca-Si silks, and composition 3 is by ton steel 180 gram feeding RE silks; Charpy-V impact power in the table 3 is for being converted to standard impact specimen (size of sample: the mean value of-40 ℃ of impact toughness value of 10 * 10 * 55mm).
The hot-rolled sheet made from the embodiment of the invention 2,4,5 steel is carried out corrosion rate, relative corrosion proof detection with the SPA-H steel that present domestic manufacturing freight container is used, and detected result sees Table 4, table 5.
Table 4 corrosion rate (g/m
2.h)
| Test period (h) | ||||
| 50 | 75 | 100 | 150 | |
| SPA-H | 3.5344 | 2.9826 | 2.7359 | 1.9635 |
| Embodiment 2 | 3.4458 | 2.7366 | 2.4702 | 1.8989 |
| Embodiment 4 | 3.4009 | 2.6754 | 2.4508 | 1.8583 |
| Embodiment 5 | 3.3789 | 2.6840 | 2.4107 | 1.8011 |
Table 5 is solidity to corrosion (%) relatively
| Test period (h) | ||||
| 50 | 75 | 100 | 150 | |
| SPA-H | 100 | 100 | 100 | 100 |
| Embodiment 2 | 102.60 | 108.99 | 110.76 | 103.40 |
| Embodiment 4 | 103.95 | 111.48 | 111.63 | 105.66 |
| Embodiment 5 | 104.63 | 111.13 | 113.49 | 109.02 |
Test-results shows that the weathering resistance of the embodiment of the invention 2,4,5 steel slightly improves than SPA-H steel, has guaranteed the work-ing life when the steel plate reduced thickness is used effectively.
Claims (4)
1. high-strength easy-formation atmospheric corrosion resisting steel, it is characterized in that being grouped into: C:0.04～0.09%, Si:0.10～0.50%, Mn:1.20～1.70%, P: S≤0.020% :≤0.010%, Cu:0.20～0.60%, Cr:0.40～0.80%, Ni:0.20～0.50%, Nb:0.03～0.07% by the one-tenth of following weight per-cent, also contain one or more of following compositions: Mo: Ti≤0.20%: Als≤0.03% :≤0.035%, surplus is Fe and unavoidable impurities.
2. high-strength easy-formation atmospheric corrosion resisting steel according to claim 1 is characterized in that one or more following compositions are by following weight percent:
C：0.06～0.09％；
Mn：1.30～1.60％；
Cu+Cr+Ni：0.9％＜Cu+Cr+Ni＜1.6％；
The weight ratio of Ni/Cu is: 0.80～1.20;
Nb：0.04～0.07％。
3. high-strength easy-formation atmospheric corrosion resisting steel according to claim 1 is characterized in that one or more following compositions are by following weight percent: C:0.04～0.07%; Si:0.20～0.40%; Mn:1.50～1.70%; P :≤0.020%; S :≤0.010%; Cu:0.30～0.40%; Cr:0.50～0.70%; Ni:0.30～0.40%; Nb:0.05～0.06%.
4. according to claim 1,2 or 3 described high-strength easy-formation atmospheric corrosion resisting steels, it is characterized in that handling, to improve the steel low-temperature flexibility by ton steel≤200 gram feeding RE silks or ton steel 500～800 gram feeding Ca-Si silks.
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