CN101092675A - Ca plus RE composite modified high strong weathering steel and preparation method - Google Patents
Ca plus RE composite modified high strong weathering steel and preparation method Download PDFInfo
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Abstract
This invention discloses a method for preparing high-strength weathering steel modified with Ca and RE. The weathering steel is composed of: C 0.04-0.07 wt.%, Si 0.2-0.4 wt.%, Mn 0.5-0.8 wt.%, S less than or equal to 0.01 wt.%, P 0.08-0.10 wt.%, Cu 0.45-0.55 wt.%, Ni 0.3-0.4 wt.%, Nb 0.02-0.03 wt.%, Ti 0.02-0.03 wt.%, Ca 0.002-0.006 wt.%, RE 0.01-0.03 wt.%, and Fe as balance. The method comprises: smelting in an electric furnace or converter, refining, continuously casting the slab, and continuously hot-rolling. The yield strength of the weathering steel modified with Ca and RE is 500 MPa, the tensile strength is 590 MPa, the total elongation rate exceeds 26%, and the weight loss is 35% of SPHC steel. The weathering steel has such advantages as low alloying cost, high strength, and high weathering resistance, and can be used to produce railway carriages, containers and industrial facilities.
Description
Technical field
The invention belongs to the weathering steel technical field, particularly provide a kind of Ca to add high-strength weathering steel that the RE composite inoculating handles and preparation method thereof.
Background technology
Recent years, Korea S and Japanology are found by adding micro-Ca element in the steel, can greatly improve corrosion resisting property (the document source: 1.K.Y.Kim of weathering steel, Y.H.Hwang, and J.Y.Yoo.Effect of SiliconContent on the Corrosion Properties of Calcium-Modified Weathering Steel in a ChlorideEnvironment.CORROSION, 2002, Vol.58, No.7:570-585; 2.K.Y.Kim, Y.H.Chung, Y.H.Hwang, and J.Y.Yoo.Effect of Calcium Modification on the Electrochemical andCorrosion Properties of Weathering Steel.CORROSION, 2002, Vol.58, No.6:479-489).Alloying element Ca mainly contains 2 points to the effect of atmospheric corrosion resistance aspect:
The one, make to be formed with in the steel to be beneficial to the Al that improves corrosion resistance nature
2O
3The complex inclusion of-CaO and CaS-MnS, and in a single day these alkaline inclusiones meet the basicity that water will improve the steel surface, thus stoping of the nearly step corrosion of atmosphere middle acid substance to steel matrix, its mechanism is:
CaO+H
2O→Ca
2++OH
-
CaS+2H
2O→Ca
2++2OH
-+H
++HS
-
On the other hand, adding Ca in the steel helps forming the alpha-feooh that can stop atomospheric corrosion at the rusty scale internal layer, alpha-feooh is a kind of material of stable densification in rusty scale, more stable than β-FeOOH and γ-FeOOH on thermodynamics, so alpha-feooh is because own dense structure stable properties thereby have good resistance to atmospheric corrosion.
From the application present situation of researching and developing about the rotten processing of Ca weathering steel both at home and abroad, basically be that (content of Ca is usually 20～60ppm) for the rotten processing of micro-Ca, the inclusion that carries out steel is rotten, the material that generation is favourable to the weathering resistance of steel, and the rusty scale that helps weathering steel forms the alpha-feooh that can stop atomospheric corrosion.
According to international online retrieval (having used U.S. Dialog system), domestic online information retrieval and network data library searching, 32 relevant data storehouses have been searched, from the domestic and foreign literature of its storage and patent by retrieval, relatively, analyze, do not see that both at home and abroad the document of handling weathering steel relevant for Ca and RE composite inoculating reports with patent.
Summary of the invention
The object of the present invention is to provide a kind of Ca to add the method for the high-strength weathering steel that the RE composite inoculating handles, solved common Cu-P-Cr-Ni and be the weathering steel weather-proof degree that is beyond one's reach, have very high weather resistance.
The present invention is satisfying under intensity, the unit elongation condition, in order to obtain better plasticity and solidity to corrosion, is that weathering steel does not add Cr and adds micro-Nb, Ti for original Cu-P-Cr-Ni, and adds Ca and the processing of RE composite inoculating that its alloying constituent is as shown in table 1.Wherein Nb, Ti mainly play refined crystalline strengthening, precipitation strength work in order to satisfy intensity and toughness, reach the level of high-strength steel; Ca and RE mainly are rotten processing effects, to improve the weather resistance of steel, reach high weatherable purpose.In addition, University of Science ﹠ Technology, Beijing finds that in national 973 projects " research of 800MPa low-carbon bainite weathering steel " Nb is except playing crystal grain thinning, be a kind of good element aspect the raising steel solidity to corrosion, and Ca and RE can improve corrosion resisting property on the one hand, they can also change the shape of steel inclusion on the other hand, improve the low-temperature impact toughness of weathering steel.
Table 1Ca and RE composite inoculating are handled the alloying constituent (wt.%) of weathering steel
| C | Si | Mn | S | P | Cu | Ni | Nb | Ti | Ca | RE |
| 0.04～ 0.07 | 0.2～ 0.4 | 0.5～ 0.8 | ≤0.01 | 0.08～ 0.10 | 0.45～ 0.55 | 0.3～ 0.4 | 0.02～ 0.03 | 0.02～ 0.03 | 0.002～ 0.006 | 0.01～ 0.03 |
Annotate: surplus is Fe, and RE is the mixture of Rare-Earth Ce and La in the table, and wherein, Ce is 50%, and La is 50%
The production technique that Ca and RE composite inoculating are handled weathering steel is as follows:
(1) passes through electric furnace or converter smelting, refining, sheet billet continuous casting.At first in stove, load onto pure iron as raw material, suction to 10
-2Torr, beginning to send electricity to add power smelts, treat that molten clear back 5～10min fills high-purity argon gas, begin to add alloying element afterwards, the addition sequence of alloy is Ni, P, Cu, Si all adds in the pan feeding, add Mn after having changed refining 10～15min, add Nb again, Ti adds Ca and RE behind stirring 10～15min, adds Ca and adopts hello calcium line, RE then adds with thin bag of aluminium, play rotten processing effect, the nodularization inclusion, and make to be formed with in the steel and be beneficial to the complex inclusion that improves corrosion resistance nature, then continuous casting becomes slab behind restir 10～15min, and board briquette is at 1180～1210 ℃.The technical process of smelting as shown in Figure 1.
(2) continuously hot rolling then.Strand heating (soaking) temperature is 1180～1210 ℃, and hot rolling finishing temperature is 880～850 ℃, and the laminar flow cooling rate is controlled at 20～30 ℃/s, and coiling temperature is controlled at 580～650 ℃, at last slow cooling to the room temperature coil of strip that gets product in air.
Each element add-on is Ni:0.3～0.4% in the smelting process, P:0.08～0.10%, Cu:0.45～0.55%, Si:0.2～0.4%, Mn:0.5～0.8%, Nb:0.02～0.03%, Ti:0.02～0.03%, Ca:0.002～0.006%, RE:0.01～0.03%; All be weight percentage.
The processing of Ca+RE composite inoculating is a principal feature of the present invention in the weathering steel of the present invention, Ca change of elements scope is at 20～60ppm, the content of RE element makes that its weather resistance is good about 0.01～0.03%, minimum about 35% of the SPHC steel that arrives of rate of weight loss.In addition, the Ca+RE composite inoculating is handled weathering steel the good mechanical performance, and its yield strength meets or exceeds 500MPa, and breaking elongation surpasses 26%.
Adopt this invention, the yield strength that Ca and RE composite inoculating are handled weathering steel can reach 500MPa, and tensile strength reaches 590MPa, and total elongation surpasses 26%, and rate of weight loss is about 35% of SPHC steel aspect weather resistance.Its alloying cost is lower, can obtain high strength, high-weatherability steel plate, is to be used for the desirable sheet material that production railcar, freight container and industrial plants are built.
Description of drawings
Fig. 1 handles the smelting technology figure of weathering steel for Ca+RE composite inoculating of the present invention.
Fig. 2 handles the rate of weight loss change curve of weathering steel for laboratory trial-production Ca and RE composite inoculating in the cycle infiltration experiment of the present invention.
Laboratory trial-production Ca and RE composite inoculating were handled the rate of weight loss contrast of weathering steel when Fig. 3 soaked into experiment 240h for the cycle of the present invention.
B1 when Fig. 4 soaks into experiment 240h for the cycle of the present invention, B2, the rate of weight loss contrast of B3.
Embodiment
Chamber trial-production Ca and RE composite inoculating are handled weathering steel by experiment.Adopt the vacuum oven of German Bao Lai company to smelt, the addition sequence of alloy is that Ni, P, Cu, Si all add in the pan feeding, has changed refining after 10min add Mn, add Nb, Ti then, not adding Al is to contain sour molten aluminium Al because of in the pure iron as raw material
s0.037%, add Ca and RE behind the stirring 15min, cast is into about the heavy steel ingot of 7Kg after stirring 15min, and the steel ingot temperature is cooled to room temperature at last at 1200 ℃, and speed of cooling is controlled at 2.5 ℃/s.Produce three stove steel by the difference of Ca content, grade of steel is B1, B2, B3, and each element add-on is Ni:25g in the smelting process, P:7g, and Cu:33g, Si:23g, Mn:35g, Nb:2.5g, Ti:1.6g, RE:1.5g, Ca are respectively 0.2g, 0.35g, 0.5g.
Hot rolling then, to consider that when heating weathering steel all contains the Cu element to strand, therefore when formulating heating process, should avoid near 1083 ℃ of crackle sensitive areas the fusing point of copper, consider that again producing actual is heating efficiency and rolling power, in order to realize high temperature rapid firing, must in heat treatment furnace, steel billet be heated to 900 ℃ of insulation 30min, then base is put into furnace temperature and is 1200 ℃ process furnace, be heated to 1200 ℃, and be incubated 1 hour.Finishing temperature is 850 ℃, and speed of cooling is controlled at 25 ℃/S approximately, and final cooling temperature is controlled at 600～650 ℃, and strand is rolled into the thick steel plate of 4mm the most at last.In order to simulate the cooling situation after curling, (begin to cool down 600 ℃ of temperature, slow cooling is 4 hours in 50 ℃ of the cooling rates/h) in slow cooling in University of Science ﹠ Technology, Beijing's heat treatment furnace.
The alloying constituent content of laboratory trial-production steel is as shown in table 2, and the steel plate of laboratory trial-production has been carried out the test of mechanics and weather resistance, and its mechanical property sees Table 3, and its weather resistance sees Table 4, Fig. 2, Fig. 3, Fig. 4.
From alloying constituent, the Composition Control of trial-production steel gets better, all in scope of design.From mechanical property, its yield strength all arrives 500MPa, and unit elongation is preferably arranged, and maximum can reach 30.5%.Aspect weather resistance, minimum 35% of the SPHC steel that is about of its rate of weight loss, and can see that Ca and RE composite inoculating handle the weightlessness of weathering steel and increase along with the increase of Ca content, Ca content are that the rate of weight loss of trial-production weathering steel of 23ppm is minimum.
Table 2 laboratory trial-production Ca and RE composite inoculating are handled the alloying constituent (Wt.%) of weathering steel
| Grade of steel | C | Si | Mn | S | P | Cu | Ni | Nb | Ti | Ca | RE |
| B1 | 0.050 | 0.30 | 0.78 | 0.007 | 0.090 | 0.45 | 0.32 | 0.030 | 0.018 | 0.0022 | 0.023 |
| B2 | 0.060 | 0.30 | 0.55 | 0.010 | 0.085 | 0.55 | 0.30 | 0.028 | 0.024 | 0.0046 | 0.025 |
| B3 | 0.045 | 0.30 | 0.60 | 0.008 | 0.095 | 0.50 | 0.31 | 0.032 | 0.020 | 0.0058 | 0.024 |
Annotate: surplus is Fe, and RE is the mixture of Rare-Earth Ce and La in the table, and wherein, Ce is 50%, and La is 50%
Table 3 laboratory trial-production Ca and RE composite inoculating are handled the Mechanics Performance Testing result of weathering steel
| Grade of steel | Yield strength/MPa | Tensile strength/MPa | Breaking elongation δ s/％ | Yield tensile ratio |
| B1 | 505 | 550 | 22.0 | 0.919 |
| B2 | 525 | 585 | 30.5 | 0.897 |
| B3 | 515 | 575 | 29.0 | 0.896 |
Laboratory trial-production Ca and RE composite inoculating are handled the rate of weight loss of weathering steel in the infiltration experiment of table 4 cycle
| Grade of steel | Rate of weight loss/% (behind the 48h) | Rate of weight loss/% (behind the 96h) | Rate of weight loss/% (behind the 168h) | Rate of weight loss/% (behind the 240h) | Rate of weight loss/% (behind the 480h) |
| B1 | 0.449 | 0.806 | 1.674 | 2.259 | 4.595 |
| B2 | 0.469 | 0.941 | 1.684 | 2.410 | 4.796 |
| B3 | 0.521 | 0.973 | 1.833 | 2.428 | 5.083 |
| SPHC | 0.699 | 1.538 | 3.214 | 6.172 | 10.348 |
Annotate:
The SPHC steel is as correlated straight carbon steel.
Claims (4)
1, a kind of Ca adds the high-strength weathering steel that the RE composite inoculating is handled, and it is characterized in that composition is:
C:0.04～0.07%, Si:0.2～0.4%, Mn:0.5～0.8%, S :≤0.01%, P:0.08～0.10%, Cu:0.45～0.55%, Ni:0.3～0.4%, Nb:0.02～0.03%, Ti:0.02～0.03%, Ca:0.002～0.006%, RE:0.01～0.03%, surplus is Fe; All be weight percentage.
According to the described weathering steel of claim 1, it is characterized in that 2, RE is the mixture of Rare-Earth Ce and La, wherein, Ce is 50%, and La 50% all is weight percentage.
3, the described weathering steel of a kind of preparation claim 1 is characterized in that technology is:
(1) by electric furnace or converter smelting, refining, sheet billet continuous casting: at first in stove, load onto pure iron as raw material, suction to 10
-2Torr begins to send electricity to add power and smelts, and treats that molten clear back 5～10min fills high-purity argon gas, begin to add alloying element afterwards, the addition sequence of alloy is that Ni, P, Cu, Si all add in the pan feeding, adds Mn after having changed refining 10～15min, add Nb, Ti again, add Ca and RE after stirring 10～15min, add Ca and adopt hello calcium line, RE then adds with thin bag of aluminium, play rotten processing effect, the nodularization inclusion, continuous casting becomes slab behind restir 10～15min, and board briquette is at 1180～1210 ℃;
(2) continuously hot rolling: slab heating temperature is 1180～1210 ℃, and hot rolling finishing temperature is 880～850 ℃, and the laminar flow cooling rate is controlled at 20～30 ℃/s, and coiling temperature is controlled at 580～650 ℃, and slow cooling to room temperature is the finished product coil of strip in air at last.
4, in accordance with the method for claim 3, it is characterized in that, the element add-on is Ni:0.3～0.4%, P:0.08～0.10%, Cu:0.45～0.55%, Si:0.2～0.4%, Mn:0.5～0.8%, Nb:0.02～0.03%, Ti:0.02～0.03%, Ca:0.002～0.006%, RE:0.01～0.03%; All be weight percentage.
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| CN102268613A (en) * | 2010-06-07 | 2011-12-07 | 鞍钢股份有限公司 | Atmospheric-corrosion-resistant hot-rolled steel plate for railway freight vehicle and manufacturing method thereof |
| CN109252092A (en) * | 2018-09-30 | 2019-01-22 | 燕山大学 | It is a kind of to exempt from coating weathering steel and preparation method thereof containing rare earth element |
| CN110923572A (en) * | 2019-11-27 | 2020-03-27 | 上海大学 | Rare earth weathering steel rich in alloying rare earth elements and manufacturing method thereof |
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| CN102268613A (en) * | 2010-06-07 | 2011-12-07 | 鞍钢股份有限公司 | Atmospheric-corrosion-resistant hot-rolled steel plate for railway freight vehicle and manufacturing method thereof |
| CN102268613B (en) * | 2010-06-07 | 2013-07-03 | 鞍钢股份有限公司 | Atmospheric-corrosion-resistant hot-rolled steel plate for railway freight vehicle and manufacturing method thereof |
| CN101880820A (en) * | 2010-06-11 | 2010-11-10 | 武汉钢铁(集团)公司 | Steel-aluminum compound hot rolled steel with tensile strength of 310MPa and production method thereof |
| CN101880820B (en) * | 2010-06-11 | 2011-11-16 | 武汉钢铁(集团)公司 | Steel-aluminum compound hot rolled steel with tensile strength of 310MPa and production method thereof |
| CN109252092A (en) * | 2018-09-30 | 2019-01-22 | 燕山大学 | It is a kind of to exempt from coating weathering steel and preparation method thereof containing rare earth element |
| CN110923572A (en) * | 2019-11-27 | 2020-03-27 | 上海大学 | Rare earth weathering steel rich in alloying rare earth elements and manufacturing method thereof |
| CN111057968A (en) * | 2019-12-19 | 2020-04-24 | 钢铁研究总院 | Corrosion-resistant hot-rolled steel plate for street lamp pole and preparation method thereof |
| CN111057968B (en) * | 2019-12-19 | 2021-03-30 | 钢铁研究总院 | Corrosion-resistant hot-rolled steel plate for street lamp pole and preparation method thereof |
| CN111270135A (en) * | 2020-02-17 | 2020-06-12 | 本钢板材股份有限公司 | Economical weathering steel produced by strengthening RE-P and preparation process thereof |
| CN116121663A (en) * | 2022-12-01 | 2023-05-16 | 内蒙古包钢钢联股份有限公司 | Rare earth La weather-resistant steel plate with 355 MPa-grade yield strength for container and preparation method thereof |
| CN116121663B (en) * | 2022-12-01 | 2024-02-09 | 内蒙古包钢钢联股份有限公司 | Rare earth La weather-resistant steel plate with 355 MPa-grade yield strength for container and preparation method thereof |
| CN116855844A (en) * | 2023-07-07 | 2023-10-10 | 广州广钢新材料股份有限公司 | Preparation method of Q345B alloy material with low porosity and high strength |
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