CN103014549A - High-performance duplex stainless steel and processing method thereof - Google Patents
High-performance duplex stainless steel and processing method thereof Download PDFInfo
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Abstract
The invention further relates to a processing method for high-performance duplex stainless steel. The processing method comprises the following steps: 1), controlling the components of mother liquor in an electric furnace as follows in percentage by weight: more than 1.0% of C, less than 0.5% of Si, 1-15% of Cr, 8.2-9.0% of Ni and less than 0.02% of P; controlling the steel tapping temperature to 1580 DEG C to 1630 DEG C; 2), transferring the mother liquor from the electric furnace to an AOD (Argon Oxygen Decarburization) furnace, carrying out oxygen-blowing and decarbonizing, nitrogen-blowing and component adjusting; refining in a steel ladle refining furnace and adding components to micro alloy to carry out final adjusting, wherein the equivalent ratio of the chromium to the nickel after adjustment is not less than 2.55. The equivalent ratio of the chromium to the nickel is properly controlled for forming high-temperature ferrite favorably, so that thermal processing is carried out in a single-phase region to the greatest extent and the high temperature plasticity of the duplex stainless steel is improved favorably.
Description
Technical field
The present invention relates to a kind of high-performance diphase stainless steel, the invention still further relates to a kind of working method of high-performance diphase stainless steel, belong to field of metallurgy.
Background technology
Duplex stainless steel has good mechanical property and corrosion resistance nature, can be widely used in the industries such as oil, chemical industry, building, but the two-phase stainless structure of steel is to be made of austenite and ferrite, because austenite and ferritic structure composition, intensity, unit elongation are had nothing in common with each other, easily produce stress concentration during thermal processing distortion at the phase boundary place, cause limit section or surface to crack, had a strong impact on its plate face quality and lumber recovery, limited its wide popularization and application.The surface quality of duplex stainless steel limit section and main component, chromium nickel equivalent ratio, microalloy element, impurity element phosphorus, sulphur, the content of oxygen, heat processing technique are relevant.
A kind of its moiety of strong corrosion resistant duplex stainless steel is disclosed in the Chinese invention patent specification sheets such as CN 102102166 A and each composition weight percent (Wt%) is as follows:
C :≤0.03; Si:0.4～0.7; Mn:1.4～1.7; P :≤0.03; S :≤0.001; Cr:22.3～22.7; Ni:5.6～5.9; Mo:3.0～3.2; Cu :≤0.5; Al :≤0.15; B:0.0028～0.0043; N:0.145～0.175; Ti :≤0.005; Pb :≤0.99; Surplus is Fe.Although this strong corrosion resistant duplex stainless steel erosion resistance is strong, owing to wherein do not add the B element, so that hot workability, the intergranular corrosion resistance poor performance; Wherein do not add REM, so that the hot-working plastic performance is poor yet.
A kind of strong corrosion resistant duplex stainless steel production technique of also openly knowing clearly in this patent specification: in 1705 ± 20 ℃ the high-temperature molten steel, be blown into O2 and nitrogen, reduce C content in the composition by principle of oxidation and reduction, simultaneously, add Mo, Mn, Cr, V, the elements such as Nb, Ti, to improve the N content in the composition; Rolling sequence, furnace temp are controlled at 1320～1350 ℃ of scopes, in the operation of rolling, avoid opening high pressure water dephosphorization system; The annealing temperature general control is at 1100～1150 ℃; Acid cleaning process adopts H2SO4:220～240g/L, NaCl:30～38g/L, and additive: 10～14g/L is at 60 ℃ of average pickling 55～60min.But because this production technique do not control chromium nickel equivalent ratio, strengthened wherein between the two-phase strength difference, reduced overall performance.
Summary of the invention
The object of the invention is to overcome above shortcomings in the prior art, and all very good high-performance diphase stainless steels of a kind of hot workability and intergranular corrosion resistance performance are provided.The present invention also provides a kind of working method that can effectively control the high-performance diphase stainless steel of chromium nickel equivalent ratio.
The present invention addresses the above problem the technical scheme that adopts: the working method of this high-performance diphase stainless steel is characterized in that may further comprise the steps:
1) mother liquor composition is controlled at C＞1.0% in electric furnace, Si＜0.5%, Cr:1-15%, Ni:8.2-9.0%; P＜0.02%, tapping temperature are controlled at 1580-1630 ℃;
2) mother liquor in the electric furnace is transferred to oxygen decarburization in the AOD stove, nitrogen flushing and composition adjustment; Refining and microalloy adding composition is finally adjusted in ladle refining furnace again, chromium nickel equivalent ratio 〉=2.55 after adjusting.
The present invention is further comprising the steps of: 3) carry out successively continuous casting, slab reconditioning, heating, rolling and batch.
Step 3 of the present invention) temperature of heating is 1240-1280 ℃ in, and is incubated 45-55min after heating.
Step 3 of the present invention) rollingly comprise roughing and finish rolling, described roughing 7-13 passage, thickness is rolling to 30mm, rolling temperature is at 950-1280 ℃, the relative draft of each roughing is controlled at 8-25%, and wherein the relative draft of breaking down is less than 10%, and roll speed is controlled at 3-12m/s; The number of times of described finish rolling is 5-11 time, each rolling relative draft control 10-25%, and roll speed is controlled at 2-12m/s, finishing temperature 〉=950 ℃, coiling temperature≤800 ℃.
The temperature of step 3 of the present invention) batching≤800 ℃.
The rolling temperature of roughing of the present invention is 1100-1220 ℃.
The present invention also provides a kind of high-performance diphase stainless steel, it is characterized in that comprising the component of following mass percent:
Cr:21-23%; Ni:5-5.6%; C :≤0.03%; Si:0.45-0.6%; Mn:1.1-1.5%; N:0.14-0.18%; Cu :≤0.5%; O :≤0.005%; P :≤0.02%; S :≤0.001%; Ca:0.005-0.05%; B:0.005-0.03%; REM:0.01-0.1%; Surplus is iron.
Cr content of the present invention is 22%-23%.
C content of the present invention≤0.02%.
O content of the present invention≤0.003%.
The present invention compared with prior art has the following advantages and effect:
The Cr ferrite former can improve the erosion resistance of material, puies forward heavy alloyed intensity, and the content of suitably controlling the Cr element is conducive to control chromium nickel equivalent ratio, and then is conducive to control the hot-workability of this duplex stainless steel.
Ni is austenite former.
C is austenite former, replaces to a certain extent nickel, promotes austenite and stable austenite, when carbon content is too high, with the chromium Chromium Carbide Formation, stainless erosion resistance and toughness worsen, in order to ensure stainless erosion resistance.
Si is ferrite former and plays and stablize ferritic effect, also plays the deoxidation additive, improves welding mobile, and having when silicone content is too high increases the middle trend of separating out mutually and reduce N concentration.
Mn is the effect of austenite former and stable austenite, can replace nickel to a certain extent, obtain austenite structure, improve simultaneously the nitrogen solid solubility, and then the content of raising nitrogen, too high manganese is unfavorable to the corrosion-resistant shape of material, and promotes the formation of metallographic phase, affects impelling strength and corrosion resistance nature.
N is stable austenite element, improves the erosion resistance of steel, improves the intensity of steel.Improve the welding property of material, but cross the hot-workability that high nitrogen-containing reduces material, excessively low nitrogen content can reduce again the content of chromium, molybdenum, and is unfavorable to the corrosion resistance nature of material.
Cu is weak austenite stable element, improves the erosion resistance of material, improves resistance to atmospheric corrosion, have 40% austenitic effect, improve the cold-workability of material, improve the corrosive nature in sulfuric acid, when being higher than 0.5%, easily produce fragility phase ε phase, unfavorable to hot-work.
O is harmful element, is the representative element that consists of non metallic oxide inclusion, and too much oxygen level is unfavorable to the toughness of dual phase steel, when generating in addition thick bunch of shape oxide compound, just becomes the reason of surface imperfection.
P is harmful element, is segregated in crystal boundary or the phase boundary, and is unfavorable to erosion resistance and the hot workability of material.
S is harmful element, and easy and manganese forms the hot workability that manganese sulfide reduces material, and calcium formation calcium sulfide, and is harmful to corrosion resistance.
The machine that Ca can improve steel adds performance and the character of improving oxide inclusion, and too much easy and sulphur forms calcium sulfide, and is unfavorable to the erosion resistance of material.
B is the less intermittence atom of radius, easily at phase boundary and Grain Boundary Segregation, crystal grain thinning improves the hot workability of material, improves the intergranular corrosion resistance performance of material, general control is between 0.0005 ~ 0.003%, when being higher than 0.003%, the risk of cracking is arranged when continuous casting and welding, too much boron easily forms low-melting BN at grain boundaries, unfavorable on the contrary to the materials hot working performance, general B content is less than or equal to 0.003%.
REM(cerium/lanthanum) rare earth element mainly plays the effect of the hot-workability of cleaning molten steel, purification crystal boundary, modification impurity, the distribution that improves impurity, raising crystal boundary energy, thinning microstructure, raising duplex stainless steel.The avidity of rare earth and oxygen, sulphur is high, main and O and S have formed Ce2O3, the material such as CeS and LaS, be combined into the oxide compound of aluminium and do not have angular hard inclusions thing, in the steel strip MnS be mingled with shorten, quantity tails off, simultaneously rare earth has and purifies crystal boundary, improves crystal boundary energy and reduce the regional segregation effect of phosphorus, makes phosphorus no longer concentrate on crystal boundary and then improves the hot-workability of duplex stainless steel and improve the limit section of duplex stainless steel and the effect of surface quality.But too much rare earth can form the oxide compound dross when being added on cast, worsens production performance, and what while and sulfide formed is mingled with than great, is not easy to floating, general and calcium compound use.REM represents cerium and/or lanthanum among the present invention.
Usually improve the hot-workability of duplex stainless steel by adding calcium, boron and rare earth (cerium/lanthanum) unit, these elements mainly play cleaning molten steel, purification crystal boundary, modification impurity, improve the distribution of impurity, improve the effects such as crystal boundary energy, thinning microstructure.The avidity of calcium or rare earth and oxygen, sulphur is high, main and O and S have formed CaO and Ce2O3, CaS, the material such as CeS and LaS, be combined into the oxide compound of aluminium and do not have angular hard inclusions thing, in the steel strip MnS be mingled with shorten, quantity tails off, and finds simultaneously that rare earth (cerium/lanthanum) has to purify crystal boundary, improve crystal boundary energy and reduce the regional segregation effect of phosphorus, makes phosphorus no longer concentrate on crystal boundary.And add the tissue that boron can the refinement duplex stainless steel, improve crystal boundary energy and then improve its hot workability.
After this two-phase stainless composition of steel and tissue were determined, rolling temperature, draft and roll speed were the key factors that affects the hot workability of duplex stainless steel.Raising along with rolling temperature, ferrite content also raises, being beneficial to duplex stainless steel processes in the single phase region, the duplex stainless steel hot-workability reduces on the contrary when hot processing temperature is too high simultaneously, this is to grow up because organize sharply when temperature reach a certain height, burn-off phenomenon appears, have a strong impact on the hot-workability of this duplex stainless steel, along with a large amount of nitrogen element of the rising of temperature concentrate on austenite mutually in, causing the rapid increase of two-phase intensity difference also is one of reason of plasticity variation when causing high temperature, the danger that has σ to separate out mutually when if hot processing temperature is lower than 950 ℃ certainly, σ is a kind of fragility phase mutually, hot-workability to this duplex stainless steel is unfavorable, thus this dual-phase stainless steel hot processing interval temperature generally be selected in 950-1280 ℃ carry out comparatively suitable.For preventing that limit section and surperficial temperature drop are too fast when rolling, cause its limit section and surface heat working plasticity to be worse than the hot-workability opposite side section of heart section and the disadvantageous effect that the surface cracks, should adopt fast speed rolling when rolling, roughing roll speed 3-12m/s, finish rolling roll speed 2-12m/s as far as possible.Because this two-phase stainless steel microscopic structure is made of austenite and ferrite, the difference of its two-phase structure, composition, intensity, unit elongation, easily produce stress concentration during thermal processing distortion at the phase boundary place, cause limit section or surface to crack, so this duplex stainless steel should adopt down draft multi-pass rolling technique, roughing is generally rolled the 7-13 passage to about the 30mm concerning thickness 160-220mm strand, the relative draft of breaking down≤10%, and finishing rolling control is rolled down to finished product thickness in the 5-11 passage.
Suitably control chromium nickel equivalent ratio is conducive to the ferritic formation of high temperature, makes as far as possible hot-work in the single phase region, the high-temp plastic of favourable raising duplex stainless steel.Improve the chromium nickel equivalent than the ratio that can suitably adjust ferrite former and austenite former, the content of control nitrogen element is more obvious than to improving the chromium nickel equivalent in austenite former, approximately is 30 times of nickel element because the nitrogen element forms austenitic ability.Simultaneously nitrogen with the interstitial solid solution mode mainly exist austenite mutually in, raising along with nitrogen content, the austenite phase content is also increasing, two alternate intensity differences also have increase tendency, make strain be more prone to produce at ferritic phase, reduced the strain distribution of austenite phase, cause thermoplastic decline, during hot-work, along with the rising of temperature, austenite also is being transformed into ferrite gradually in the duplex stainless steel, nitrogen content in the austenite has caused the difference between the two-phase intensity more also in rapid increase simultaneously, so after hot-work surpasses certain temperature, be beneficial to the production of this two-phase stainless roll of steel plate when control chromium nickel equivalent ratio 〉=2.55, nitrogen content≤0.18% left and right sides.
The calculation formula of the chromium nickel equivalent ratio described in the present invention is:
Creq/Nieq≥2.2；
Wherein Creq is the Cr equivalent, Creq=%Cr+%Mo+1.5*%Si+0.73%W+0.5%Nb;
Wherein Nieq is the Ni equivalent, Nieq=%Ni+30*%C+0.5*%Mn+0.33*%Cu+30 (%N-0.045);
In the above formula, %Cr, %Mo, %Si, %W, %Nb represent respectively the numerical value of the weight percentage of Cr, Mo, Si, W, Nb; %Ni, %C, %Mn, %Cu, %N represent respectively the numerical value of the weight percentage of Ni, C, Mn, Cu, N.
Description of drawings
Fig. 1 is the stainless steel that the working method of high-performance diphase stainless steel among the embodiment 1 is produced.
Fig. 2 is the stainless steel microscopic inspection that the working method of high-performance diphase stainless steel among the embodiment 1 is produced.
Fig. 3 is plate face quality behind the acid-washing stainless steel produced of the working method of high-performance diphase stainless steel among the embodiment 1.
Fig. 4 is the stainless steel that the working method of high-performance diphase stainless steel among the embodiment 2 is produced.
Fig. 5 is the stainless steel microscopic inspection that the working method of high-performance diphase stainless steel among the embodiment 2 is produced.
Fig. 6 is plate face quality behind the acid-washing stainless steel produced of the working method of high-performance diphase stainless steel among the embodiment 2.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing and by embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1.
The working method of the high-performance diphase stainless steel of the present embodiment is characterized in that may further comprise the steps.
1) mother liquor composition is controlled at C 1.39% in the Consteel electric furnace, and Si 0.04%, and Cr 1.25%, and Ni 6.42%, and P 0.015%, and tapping temperature is controlled at 1580-1630 ℃;
2) mother liquor in the electric furnace is transferred to oxygen decarburization in the AOD stove, nitrogen flushing and composition adjustment; Refining and microalloy adding composition finally is adjusted in ladle refining furnace again:
C：0.02%；Cr：22.6%；Si：0.55；Ni：5.3%；Mn：1.35%；Mo：3.2%；N：0.16%；P：0.018%；O：0.0035%；S：0.0075%；Al：0.003%；Ca：0.015%；B：0.018%；REM：0.015%。Chromium nickel equivalent ratio is 2.64.
3) carry out successively continuous casting, slab reconditioning, heating, rolling and batch.
Continuous casting: casting speed is 1.1m/min, and slab thickness is 198mm, and the strand holding temperature is that 1260 ℃, the slab upper and lower plates face temperature difference are-10 ℃.
Slab reconditioning: then carry out the slab reconditioning.
Heating: slab reconditioning post-heating to 1260 ℃, insulation 45min.
Rolling: roughing 7 passages, rolling temperature are at 1100 ℃, the relative draft of breaking down less than 10%, 20%, roll speed is controlled at 3-12m/s to draft for rolling maximal phase, roughing finish to gauge thickness is at 30mm.
Rolling 7 passages of finish rolling, draft is controlled 13-25% relatively, and roll speed is controlled at 2-12m/s, and rolling thickness is 10mm, and finishing temperature is at 960 ℃.Mill product is without the raw edges phenomenon, and plate face quality is good, finds no obvious precipitated phase by detection.
Batch: coiling temperature is at 650 ℃.
The present embodiment can use stainless steel waste material, high-quality steel scrap, ferronickel, ferrochrome as raw material.
What Fig. 1 showed is this duplex stainless steel finished product volume, can find out that limit section is without the raw edges phenomenon.What Fig. 2 showed is this duplex stainless steel microscopic inspection, and grey is ferritic structure, and brilliant white is austenite structure, can find out that phase boundary is smooth, without obvious precipitated phase.Plate face quality condition after this duplex stainless steel pickling that Fig. 3 shows can see that ejecting plate face quality is good.
Embodiment 2.
1) be controlled at C:1.65%, Si:0.03%, P:0.013%, Cr:1.56%, Ni:6.35% at Consteel electric furnace mother liquor composition, tapping temperature is controlled at 1580-1630 ℃;
2) mother liquor in the electric furnace is transferred to oxygen decarburization in the AOD stove, nitrogen flushing and composition adjustment; Refining and microalloy adding composition finally is adjusted in ladle refining furnace again:
C:0.015%, Cr:22.5%, Si:0.50, Ni:5.2%, Mn:1.30%, Mo:3.15%, N:0.17%, P:0.017%, O:0.0030%, S:0.008%, Al:0.004%, Ca:0.02%, B:0.015%, REM:0.013%, chromium nickel equivalent ratio is 2.63.The time of blowing is 30min a little less than the LF stove.
3) carry out successively continuous casting, slab reconditioning, heating, rolling and batch.
Continuous casting: casting speed is that 1.0m/min, slab thickness are 200mm.The strand holding temperature is that 1270 ℃, the slab upper and lower plates face temperature difference are 15 ℃.
Slab reconditioning: then carry out the slab reconditioning.
Heating: slab reconditioning post-heating to 1260 ℃, insulation 50min.
Rolling:
Roughing 7 passages, thickness is rolling to about 30mm, and rolling temperature is at 1100 ℃, and the relative draft of breaking down is less than 10%, and 20%, rolling thickness is 4.95mm to each rolling maximal phase to draft,, roll speed is controlled at 3-12m/s.
Rolling 7 passages of finish rolling, draft is controlled 10-25% relatively, and roll speed is controlled at 2-12m/s, and finishing temperature is at 960 ℃.Mill product is without the raw edges phenomenon, and plate face quality is good, finds no obvious precipitated phase by detection.
Mill product is without the raw edges phenomenon, and plate face quality is good, finds no obvious precipitated phase by detection.
Batch: coiling temperature is at 650 ℃.
What Fig. 4 showed is this duplex stainless steel finished product volume, can find out that limit section is without the raw edges phenomenon.What Fig. 5 showed is this duplex stainless steel microscopic inspection, and grey is ferritic structure, and brilliant white is austenite structure, can find out that phase boundary is smooth, without obvious precipitated phase.Plate face quality condition after this duplex stainless steel pickling that Fig. 6 shows can see that ejecting plate face quality is good.
Embodiment 3.
In the present embodiment, high-performance diphase stainless steel comprises the component of following mass percent:
Cr:21%; Ni:5%; C:0.03%; Si:0.45%; Mn:1.1%; N:0.14%; Cu:0.5%; O:0.005%; P:0.02%; S:0.001%; Ca:0.005%; B:0.005%; REM:0.01%; Surplus is iron.
Embodiment 4.
In the present embodiment, high-performance diphase stainless steel comprises the component of following mass percent:
Cr:23%; Ni:5.6%; C:0.01%; Si:0.6%; Mn:1.5%; N:0.18%; Cu:0.3%; O:0.003%; P:0.01%; S:0.0005%; Ca:0.05%; B:0.03%; REM:0.1%; Surplus is iron.
Embodiment 5.
In the present embodiment, high-performance diphase stainless steel comprises the component of following mass percent:
Cr:22%; Ni:5.3%; C:0.01%; Si:0.5%; Mn:1.3%; N:0.16%; Cu:0.3%; O:0.003%; P:0.01%; S:0.0005%; Ca:0.03%; B:0.01%; REM:0.05%; Surplus is iron.
Among the present invention, relatively draft refers to that thickness before rolling subtracts needs after the rolling target thickness again divided by the thickness before rolling.
Above content described in this specification sheets only is made for the present invention illustrating.Those skilled in the art can make various modifications or replenish or adopt similar mode to substitute described specific embodiment; only otherwise depart from the content of specification sheets of the present invention or surmount this scope as defined in the claims, all should belong to protection scope of the present invention.
Claims (10)
1. the working method of a high-performance diphase stainless steel is characterized in that may further comprise the steps:
1) mother liquor composition is controlled at C in electric furnace:＞1.0%, Si:＜0.5%, Cr:1-15%, and Ni:8.2-9.0%, P:＜0.02%, tapping temperature is controlled at 1580-1630 ℃;
2) mother liquor in the electric furnace is transferred to oxygen decarburization in the AOD stove, nitrogen flushing and composition adjustment; Refining and microalloy adding composition is finally adjusted in ladle refining furnace again, chromium nickel equivalent ratio 〉=2.55 after adjusting.
2. the working method of high-performance diphase stainless steel according to claim 1 characterized by further comprising following steps: 3) carry out successively continuous casting, slab reconditioning, heating, rolling and batch.
3. the working method of high-performance diphase stainless steel according to claim 2 is characterized in that: the temperature of heating is 1240-1280 ℃ described step 3), and is incubated 45-55min after heating.
4. the working method of high-performance diphase stainless steel according to claim 2, it is characterized in that: described step 3) rollingly comprise roughing and finish rolling, described roughing 7-13 passage, thickness is rolling to 30mm, rolling temperature is at 950-1280 ℃, the relative draft of each roughing is controlled at 8-25%, and wherein the relative draft of breaking down is less than 10%, and roll speed is controlled at 3-12m/s; The number of times of described finish rolling is 5-11 time, each rolling relative draft control 10-25%, and roll speed is controlled at 2-12m/s, finishing temperature 〉=950 ℃, coiling temperature≤800 ℃.
5. according to the working method of high-performance diphase stainless steel claimed in claim 2, it is characterized in that: the temperature of described step 3) batching≤800 ℃.
6. the working method of high-performance diphase stainless steel according to claim 4, it is characterized in that: the rolling temperature of described roughing is 1100-1220 ℃.
7. the high-performance diphase stainless steel produced of the working method of described high-performance diphase stainless steel according to claim 1 is characterized in that comprising the component of following mass percent:
Cr:21-23%; Ni:5-5.6%; C :≤0.03%; Si:0.45-0.6%; Mn:1.1-1.5%; N:0.14-0.18%; Cu :≤0.5%; O :≤0.005%; P :≤0.02%; S :≤0.001%; Ca:0.005-0.05%; B:0.005-0.03%; REM:0.01-0.1%; Surplus is iron.
8. according to high-performance diphase stainless steel claimed in claim 7, it is characterized in that: described Cr content is 22%-23%.
9. according to high-performance diphase stainless steel claimed in claim 7, it is characterized in that: described C content≤0.02%.
10. according to high-performance diphase stainless steel claimed in claim 7, it is characterized in that: described O content≤0.003%.
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| CN109594025A (en) * | 2019-01-25 | 2019-04-09 | 无锡市法兰锻造有限公司 | A kind of two-phase steel forgings with anti intercrystalline corrosion performance |
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| CN114214565A (en) * | 2021-12-10 | 2022-03-22 | 山西太钢不锈钢股份有限公司 | High-strength corrosion-resistant 410S stainless steel and optimized preparation process method thereof |
| CN114657335A (en) * | 2022-04-01 | 2022-06-24 | 山西太钢不锈钢股份有限公司 | Super duplex stainless steel and annealing method thereof |
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