CN103014549B - A kind of high-performance diphase stainless steel and working method thereof - Google Patents
A kind of high-performance diphase stainless steel and working method thereof Download PDFInfo
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Abstract
The invention still further relates to a kind of working method of high-performance diphase stainless steel, it comprises the following steps: 1) in electric furnace, mother liquor composition controls at C:> 1.0%, Si:< 0.5%, Cr:1-15%, Ni:8.2-9.0%, P:< 0.02%, tapping temperature controls at 1580-1630 DEG C; 2) mother liquor in electric furnace is transferred to oxygen decarburization in AOD furnace, nitrogen flushing and composition adjustment; In ladle refining furnace, refining and microalloy add composition and finally adjust again, and after adjustment, chromium nickel equivalent is than >=2.55.Suitable control chromium nickel equivalent ratio is conducive to the ferritic formation of high temperature, makes hot-work in single phase region as far as possible, the high-temp plastic of favourable raising duplex stainless steel.
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 excellent mechanical property and corrosion resistance nature, the industries such as oil, chemical industry, building can be widely used in, but two-phase stainless structure of steel is made up of austenite and ferrite, because austenite and ferritic structure composition, intensity, unit elongation are had nothing in common with each other, easily stress concentration is produced at phase boundary place during thermal processing distortion, cause edge or surface to crack, had a strong impact on its board surface quality and lumber recovery, limit its wide popularization and application.The surface quality of duplex stainless steel edge and main component, chromium nickel equivalent ratio, microalloy element, impurity element phosphorus, sulphur, the content of oxygen, heat processing technique are relevant.
As disclosed a kind of its moiety of strong corrosion resistant duplex stainless steel in the Chinese invention patent specification sheets of CN102102166A and each composition by 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 not adding B element, make hot workability, intergranular corrosion resistance performance is poor; Wherein also do not add REM, make hot-working plastic performance poor.
A kind of strong corrosion resistant duplex stainless steel production technique has been also disclosed: in the high-temperature molten steel of 1705 ± 20 DEG C in this patent specification, be blown into O2 and nitrogen, C content in composition is reduced by principle of oxidation and reduction, simultaneously, add the elements such as Mo, Mn, Cr, V, Nb, Ti, to improve the N content in composition; Rolling sequence, furnace temp controls 1320 ~ 1350 DEG C of scopes, in the operation of rolling, avoids opening dephosphorize by high pressure water system; Annealing temperature general control is at 1100 ~ 1150 DEG C; Acid cleaning process adopts H2SO4:220 ~ 240g/L, NaCl:30 ~ 38g/L, and additive: 10 ~ 14g/L, at 60 DEG C of average pickling 55 ~ 60min.But because this production technique does not control chromium nickel equivalent ratio, strengthen wherein between two-phase strength difference, reduce overall performance.
Summary of the invention
The object of the invention is to overcome above shortcomings in prior art, and a kind of hot workability and all very excellent high-performance diphase stainless steel of intergranular corrosion resistance performance are provided.Present invention also offers a kind of working method that effectively can control the high-performance diphase stainless steel of chromium nickel equivalent ratio.
The present invention's adopted technical scheme that solves the problem is: the working method of this high-performance diphase stainless steel, is characterized in that comprising the following steps:
1) in electric furnace, mother liquor composition controls at C > 1.0%, Si < 0.5%, Cr:1-15%, Ni:8.2-9.0%; P < 0.02%, tapping temperature controls at 1580-1630 DEG C;
2) mother liquor in electric furnace is transferred to oxygen decarburization in AOD furnace, nitrogen flushing and composition adjustment; In ladle refining furnace, refining and microalloy add composition and finally adjust again, and after adjustment, chromium nickel equivalent is than >=2.55.
The present invention is further comprising the steps of: 3) carry out continuous casting, slab reconditioning, heating, rolling successively and batch.
Step 3 of the present invention) in the temperature of heating be 1240-1280 DEG C, and be incubated 45-55min after the heating.
Step 3 of the present invention) rolling comprises roughing and finish rolling, described roughing 7-13 passage, and thickness is rolling to 30mm, rolling temperature is at 950-1280 DEG C, the relative draft of each roughing controls at 8-25%, and wherein the relative draft of breaking down is less than 10%, and roll speed controls at 3-12m/s; The number of times of described finish rolling is 5-11 time, and each rolling relative draft control 10-25%, roll speed controls at 2-12m/s, finishing temperature >=950 DEG C, coiling temperature≤800 DEG C.
Step 3 of the present invention) temperature≤800 DEG C of batching.
The rolling temperature of roughing of the present invention is 1100-1220 DEG C.
Present invention also offers a kind of high-performance diphase stainless steel, it is characterized in that the component comprising 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≤0.02% of the present invention.
O content≤0.003% of the present invention.
The present invention compared with prior art, has the following advantages and effect:
Cr ferrite former, can improve the erosion resistance of material, puies forward heavy alloyed intensity, and suitably the content of control Cr element is conducive to controlling chromium nickel equivalent ratio, and then is conducive to the hot-workability controlling this duplex stainless steel.
Ni is austenite former.
C is austenite former, replaces nickel to a certain extent, promotes austenite stable austenite, when carbon content is too high, with chromium Chromium Carbide Formation, stainless erosion resistance and toughness deteriorate, in order to ensure stainless erosion resistance.
Si is ferrite former and plays to stablize ferritic effect, also plays deoxidation additive, improves welding mobility, has the trend of increase mesophase spherule precipitation and reduce N concentration when silicone content is too high.
Mn is the effect of austenite former and stable austenite, nickel can be replaced to a certain extent, obtain austenite structure, improve nitrogen solid solubility simultaneously, and then improve the content of nitrogen, the corrosion-resistant shape of too high manganese to material is unfavorable, 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, too low nitrogen content can reduce again the content of chromium, molybdenum, 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, there is 40% austenitic effect, improve the cold-workability of material, improve the corrosive nature in sulfuric acid, higher than 0.5% time, easily produce brittlement phase ε phase, unfavorable to hot-work.
O is harmful element, and be the representative element forming non metallic oxide inclusion, the toughness of too much oxygen level to dual phase steel is unfavorable, when generating thick tufted oxide compound in addition, just becomes the reason of surface imperfection.
P is harmful element, is segregated in crystal boundary or phase boundary, to the erosion resistance of material and hot workability unfavorable.
S is harmful element, and easy and manganese forms the hot workability that manganese sulfide reduces material, and calcium forms calcium sulfide, is harmful to corrosion resistance.
The machine that Ca can improve steel adds performance and improves the character of oxide inclusion, and too much easy and sulphur forms calcium sulfide, unfavorable to the erosion resistance of material.
B is the intermittence atom that radius is less, 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%, higher than 0.003% time, have the risk of cracking when continuous casting and welding, too much boron easily forms low-melting BN at grain boundaries, unfavorable on the contrary to materials hot working performance, general B content is less than or equal to 0.003%.
REM(cerium/lanthanum) rare earth element mainly plays cleaning molten steel, purification crystal boundary, modification impurity, improves the distribution of impurity, improves the effect of hot-workability of crystal boundary energy, thinning microstructure, raising duplex stainless steel.The avidity of rare earth and oxygen, sulphur is high, main and O and S defines Ce2O3, the materials such as CeS and LaS, carry out being combined into the oxide compound of aluminium and do not have angular hard inclusions thing, in steel strip MnS be mingled with shorten, quantity tails off, rare earth has purification crystal boundary, improves the regional segregation effect of crystal boundary energy and minimizing phosphorus simultaneously, makes phosphorus no longer concentrate on crystal boundary and then improve the hot-workability of duplex stainless steel and improve the edge of duplex stainless steel and the effect of surface quality.But too much rare earth can form oxide compound dross when being added on cast, worsen production performance, simultaneously and being mingled with than great of being formed of sulfide, be not easy to float, generally and calcium compound use.In the present invention, REM represents cerium and/or lanthanum.
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, the distribution improving impurity, effect such as raising crystal boundary energy, thinning microstructure etc.The avidity of calcium or rare earth and oxygen, sulphur is high, main and O and S defines CaO and Ce2O3, CaS, the materials such as CeS and LaS, carry out being combined into the oxide compound of aluminium and do not have angular hard inclusions thing, in steel strip MnS be mingled with shorten, quantity tails off, find that rare earth (cerium/lanthanum) has purification crystal boundary, improves crystal boundary energy and reduces the regional segregation effect of phosphorus simultaneously, make phosphorus no longer concentrate on crystal boundary.And add boron can the tissue of refinement duplex stainless steel, improve crystal boundary energy and then improve its hot workability.
After this duplex stainless steel Composition and structure is determined, rolling temperature, draft and roll speed are the key factors of the hot workability affecting duplex stainless steel.Along with the raising of rolling temperature, ferrite content also raises, be beneficial to duplex stainless steel to process in single phase region, when hot processing temperature is too high, duplex stainless steel hot-workability reduces on the contrary simultaneously, sharply grow up this is because organize when temperature reach a certain height, there is burn-off phenomenon, have a strong impact on the hot-workability of this duplex stainless steel, along with the nitrogen element that the rising of temperature is a large amount of concentrate on austenite mutually in, causing two-phase intensity difference sharply to increase also is one of reason that when causing high temperature, plasticity is deteriorated, if hot processing temperature is lower than the danger having σ phase to separate out when 950 DEG C certainly, σ phase is a kind of brittlement phase, unfavorable to the hot-workability of this duplex stainless steel, so this dual-phase stainless steel hot processing interval temperature be generally selected in 950-1280 DEG C carry out comparatively suitable.During for preventing rolling edge and surperficial temperature drop too fast, the disadvantageous effect that the hot-workability causing its edge and surface heat working plasticity to be worse than heart portion cracks edge and surface, fast speed rolling should be adopted, roughing roll speed 3-12m/s, finish rolling roll speed 2-12m/s during rolling as far as possible.Because this two-phase stainless steel microscopic structure is made up of austenite and ferrite, the difference of its two-phase structure, composition, intensity, unit elongation, easily stress concentration is produced at phase boundary place during thermal processing distortion, edge or surface is caused to crack, so this duplex stainless steel should adopt lower draft multi-pass rolling technique, 7-13 passage is generally rolled to about 30mm, relative draft≤10% of breaking down to roughing thickness 160-220mm strand, finishing rolling control at 5-11 passes to finished product thickness.
Suitable control chromium nickel equivalent ratio is conducive to the ferritic formation of high temperature, makes hot-work in single phase region as far as possible, the high-temp plastic of favourable raising duplex stainless steel.Improve chromium nickel equivalent than the ratio that suitably can adjust ferrite former and austenite former, the content controlling nitrogen element in austenite former is the most obvious to raising chromium nickel equivalent ratio, because nitrogen element forms 30 times that austenitic ability is approximately nickel element.Simultaneously nitrogen with interstitial solid solution mode mainly exist austenite mutually in, along with the raising of nitrogen content, austenite phase content is also in increase, two alternate intensity differences also have increase tendency, strain is made to be more prone to produce at ferritic phase, reduce the strain distribution of austenite phase, cause thermoplastic decline, during hot-work, along with the rising of temperature, in duplex stainless steel, austenite is also being transformed into ferrite gradually, nitrogen content simultaneously in austenite is also sharply increasing, more result in the difference between two-phase intensity, so after hot-work exceedes certain temperature, control chromium nickel equivalent than >=2.55, the production of this two-phase stainless roll of steel plate is beneficial to time about nitrogen content≤0.18%.
The calculation formula of the chromium nickel equivalent ratio described in the present invention is:
Creq/Nieq≥2.2；
Wherein Creq is Cr equivalent, Creq=%Cr+%Mo+1.5*%Si+0.73%W+0.5%Nb;
Wherein Nieq is Ni equivalent, Nieq=%Ni+30*%C+0.5*%Mn+0.33*%Cu+30 (%N-0.045);
In above formula, %Cr, %Mo, %Si, %W, %Nb represent the numerical value of the weight percentage of Cr, Mo, Si, W, Nb respectively; %Ni, %C, %Mn, %Cu, %N represent the numerical value of the weight percentage of Ni, C, Mn, Cu, N respectively.
Accompanying drawing explanation
Fig. 1 is the stainless steel that the working method of high-performance diphase stainless steel in embodiment 1 is produced.
Fig. 2 is the stainless steel microscopic inspection that the working method of high-performance diphase stainless steel in embodiment 1 is produced.
Fig. 3 is board surface quality after the acid-washing stainless steel produced of the working method of high-performance diphase stainless steel in embodiment 1.
Fig. 4 is the stainless steel that the working method of high-performance diphase stainless steel in embodiment 2 is produced.
Fig. 5 is the stainless steel microscopic inspection that the working method of high-performance diphase stainless steel in embodiment 2 is produced.
Fig. 6 is board surface quality after the acid-washing stainless steel produced of the working method of high-performance diphase stainless steel in embodiment 2.
Embodiment
Below in conjunction with accompanying drawing, also by embodiment, the present invention is described in further detail, 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 comprising the following steps.
1) in Consteel electric furnace, mother liquor composition controls at C1.39%, Si0.04%, Cr1.25%, Ni6.42%, P0.015%, and tapping temperature controls at 1580-1630 DEG C;
2) mother liquor in electric furnace is transferred to oxygen decarburization in AOD furnace, nitrogen flushing and composition adjustment; In ladle refining furnace, refining and microalloy add composition and are finally adjusted to 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 continuous casting, slab reconditioning, heating, rolling successively and batch.
Continuous casting: casting speed is 1.1m/min, slab thickness is 198mm, and strand holding temperature is 1260 DEG C, the slab upper and lower plates face temperature difference is-10 DEG C.
Slab reconditioning: then carry out slab reconditioning.
Heating: slab reconditioning post-heating to 1260 DEG C, insulation 45min.
Rolling: roughing 7 passage, rolling temperature at 1100 DEG C, the relative draft of breaking down is less than 10%, the maximal phase of rolling to draft 20%, roll speed controls at 3-12m/s, and roughing finish to gauge thickness is at 30mm.
Finish rolling rolling 7 passage, relative draft control 13-25%, roll speed controls at 2-12m/s, and rolling thickness is 10mm, and finishing temperature is at 960 DEG C.Mill product is without raw edges phenomenon, and board surface quality is good, finds no obvious precipitated phase by detecting.
Batch: coiling temperature is at 650 DEG C.
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 edge is without 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.Board surface quality situation after this duplex stainless steel pickling of Fig. 3 display, can find out that board surface quality is good.
Embodiment 2.
1) control 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 controls at 1580-1630 DEG C;
2) mother liquor in electric furnace is transferred to oxygen decarburization in AOD furnace, nitrogen flushing and composition adjustment; In ladle refining furnace, refining and microalloy add composition and are finally adjusted to 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 LF stove weak time of blowing is 30min.
3) carry out continuous casting, slab reconditioning, heating, rolling successively and batch.
Continuous casting: casting speed is 1.0m/min, slab thickness is 200mm.Strand holding temperature is 1270 DEG C, the slab upper and lower plates face temperature difference is 15 DEG C.
Slab reconditioning: then carry out slab reconditioning.
Heating: slab reconditioning post-heating to 1260 DEG C, insulation 50min.
Rolling:
Roughing 7 passage, thickness is rolling to about 30mm, and rolling temperature is at 1100 DEG C, and the relative draft of breaking down is less than 10%, and the maximal phase of each rolling is to draft 20%, and rolling thickness is 4.95mm, roll speed controls at 3-12m/s.
Finish rolling rolling 7 passage, relative draft control 10-25%, roll speed controls at 2-12m/s, and finishing temperature is at 960 DEG C.Mill product is without raw edges phenomenon, and board surface quality is good, finds no obvious precipitated phase by detecting.
Mill product is without raw edges phenomenon, and board surface quality is good, finds no obvious precipitated phase by detecting.
Batch: coiling temperature is at 650 DEG C.
What Fig. 4 showed is this duplex stainless steel finished product volume, can find out that edge is without 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.Board surface quality situation after this duplex stainless steel pickling of Fig. 6 display, can find out that board surface 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.
In the present invention, the thickness before relative draft refers to rolling subtract need the target thickness of rolling after again divided by the thickness before rolling.
Above content described in this specification sheets is only made for the present invention illustrating.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to 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, protection scope of the present invention all should be belonged to.
Claims (1)
1. a working method for high-performance diphase stainless steel, is characterized in that comprising the following steps:
1) in electric furnace, mother liquor composition controls at C1.39%, Si0.04%, Cr1.25%, Ni6.42%, P0.015%, and tapping temperature controls at 1580-1630 DEG C;
2) mother liquor in electric furnace is transferred to oxygen decarburization in AOD furnace, nitrogen flushing and composition adjustment; In ladle refining furnace, refining and microalloy add composition and are finally adjusted to 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 continuous casting, slab reconditioning, heating, rolling successively and batch;
Continuous casting: casting speed is 1.1m/min, slab thickness is 198mm, and strand holding temperature is 1260 DEG C, the slab upper and lower plates face temperature difference is-10 DEG C;
Slab reconditioning: then carry out slab reconditioning;
Heating: slab reconditioning post-heating to 1260 DEG C, insulation 45min;
Rolling:
Roughing 7 passage, rolling temperature at 1100 DEG C, the relative draft of breaking down is less than 10%, the maximal phase of rolling to draft 20%, roll speed controls at 3-12m/s, and roughing finish to gauge thickness is at 30mm;
Finish rolling rolling 7 passage, relative draft control 13-25%, roll speed controls at 2-12m/s, and rolling thickness is 10mm, and finishing temperature is at 960 DEG C;
Batch: coiling temperature is at 650 DEG C.
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| CN103667589A (en) * | 2013-12-04 | 2014-03-26 | 蚌埠华泰特种钢有限公司 | Two-step method for producing austenitic stainless steel by using stainless steel scrap |
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| CN106734195A (en) * | 2016-12-16 | 2017-05-31 | 山西太钢不锈钢股份有限公司 | The milling method of two phase stainless steel roll bending is carried out using continuous hot-rolling mill |
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Address after: 314000 New Economic Development Zone, Nanhu District, Jiaxing, Zhejiang, China Patentee after: East special steel company limited of Zhen Shi group Address before: 314000 New Economic Development Zone, Nanhu District, Jiaxing, Zhejiang, China Patentee before: Zhenshi Group Eastern Special Steel Co., Ltd. |