CN103866194A - Abnormally segregated stanniferous low-clearance ferritic stainless steel and preparation method thereof - Google Patents
Abnormally segregated stanniferous low-clearance ferritic stainless steel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses abnormally segregated stanniferous low-clearance ferritic stainless steel and a preparation method thereof, and belongs to the technical field of metallurgy. The stainless steel comprises the following components in percentage by weight: 0.005-0.03% of C, 0.2-0.4% of Si, 0.2-0.5% of Mn, less than or equal to 0.03% of P, less than or equal to 0.02% of S, 14-16% of Cr, less than or equal to 0.01% of N, 0.1-0.4% of Sn, Nb, Ti and/or V and the balance of iron and inevitable impurities; the tensile strength is 445-451MPa; the pitting potential is 202-240mV. The preparation method comprises the following steps: (1) smelting and casting a blank according to set components; (2) heating to be 1150+/-10 DEG C, carrying out heat preservation for 1-3 hours, and subsequently hot-rolling to make a hot-rolled steel plate; (3) annealing at 900+/-10 DEG C for 2-3 hours, cooling to room temperature, pickling and then cold-rolling to make a cold-rolled steel plate; (4) heating to 800+/-10 DEG C and carrying out normalizing treatment to obtain the abnormally segregated stanniferous low-clearance ferritic stainless steel. By adopting the method disclosed by the invention, the production cost of the stainless steel can be greatly lowered, the process is simple, and a product is high in strength, hardness and corrosion resistance.
Description
Technical field
The invention belongs to metallurgical technology field, particularly stanniferous low gap ferritic stainless steel of a kind of unusual segregation and preparation method thereof.
Background technology
Stainless main alloying constituent is nickel, chromium etc., and wherein nickel is more expensive metal, substantially all fluctuations more than tens0000 of LME-Ni, and it is more than 40 ten thousand per ton that a high position reaches.China is the country of a scarce nickel, few molybdenum, poor chromium and stainless steel scrap resources scarcity, the fast lifting of stainless steel output, and raw material supplying has become distinct issues; In order to reduce business risk and to reduce the prices of raw and semifnished materials impact of fluctuate on stainless steel market, force enterprises of producing stainless steel and downstream user to turn to not containing or few nickeliferous chromium is and chrome molybdenum is stainless steel.Along with the further sustainable growth of domestic ferritic stainless steel production capacity and apparent consumption demand, the problem of chromium resource has also emerged and is increasingly outstanding.According to incompletely statistics, domestic approximately 3,200,000 tons of the high carbon ferro-chromes that consume altogether of China in 2010, wherein have 1,800,000 tons of left and right from import, and externally interdependency is up to 56%.
(day for announcing is on November 4th, 2009 in the patent application of China Patent Publication No. CN101573466A, name is called the ferritic stainless steel of the discoloration-resistant with excellent corrosion resistance) a kind of high Cr ferritic stainless steel disclosed, with Cr, Cu, Ti, the high corrosion resistance ferritic stainless steel of the austenitic stainless steel that the replacements such as Nb contain expensive Ni, this ferritic stainless steel consist of C :≤0.01%, Si:0.2 ~ 1.0%, Mn :≤0.3%, Cr:20 ~ 22%, Ni:, N :≤0.01%, Al:0.03 ~ 0.1%, Cu:0.3 ~ 0.5%, Zr:0.02 ~ 0.04%, Ti:0.2 ~ 0.4%, Nb:0.06 ~ 0.45%, all the other are Fe and inevitable impurity, in this invention minimizing stainless steel, Ni's adds, save cost, but still need to add 0.2 ~ 0.4% Ni, and substituted element kind is too much, recovery rate in smelting process is also difficult to guarantee.
Publication number is that (day for announcing is on December 14th, 2011 for the Chinese patent application of 102274937A, name is called a kind of preparation method of stanniferous ferritic stainless steel strip of inverse segregation tin) a kind of preparation method of stanniferous ferritic stainless steel strip of inverse segregation tin disclosed, carry out as follows: the ferritic stainless steel take stanniferous weight percent as 0.1 ~ 0.8 is as raw material, first in the medium-frequency induction furnace under high vacuum environment, smelt and obtain molten steel, then adopt the casting of double roll strip casting rolling plant to obtain the stanniferous ferritic stainless steel band base of the inverse segregation tin that 1.0 ~ 3.2mm is thick, wherein, teeming temperature is 1550 ~ 1640 ℃, roll casting speed is 2 ~ 80m/min, default roll gap is 0.0 ~ 2.2mm, after follow-up rolling and anneal, finally obtain the ferritic stainless steel strip of inverse segregation tin, this invention only provides the rough range of tin in ferritic stainless steel, and other elements in steel are not illustrated, be difficult to the material mechanical performance and the corrosion resistance nature that guarantee that its smelting steel grade can be satisfied the demand.
Summary of the invention
The object of this invention is to provide stanniferous low gap ferritic stainless steel of a kind of unusual segregation and preparation method thereof, by adjusting stainless composition, make stanniferous ferritic stainless steel through hot rolling, annealing, pickling, cold rolling and thermal treatment, in reducing stainless production cost and significantly saving the resource such as chromium, nickel, improve stainless erosion resistance and plasticity.
The composition of the stanniferous low gap ferritic stainless steel of unusual segregation of the present invention contains C 0.005 ~ 0.03%, Si 0.2 ~ 0.4%, Mn 0.2 ~ 0.5% by weight percentage, P≤0.03%, S≤0.02%, Cr 14 ~ 16%, N≤0.01%, Sn 0.1 ~ 0.4%, and contain Nb, Ti and/or V, in the time containing Nb, the content of Nb is 0.05 ~ 0.15%, in the time containing Ti, the content of Ti is 0.05 ~ 0.15%, in the time containing V, the content of V is 0.05 ~ 0.15%, and all the other are iron and inevitable impurity; Tensile strength 445 ~ 451 MPa, pitting potential is 202 ~ 240mV.
The upper yield point of the stanniferous low gap ferritic stainless steel of above-mentioned unusual segregation is 310 ~ 337 MPa, and lower yield point is 306 ~ 325 MPa, and elongation after fracture is 47 ~ 49%.
The preparation method of the stanniferous low gap ferritic stainless steel of unusual segregation of the present invention carries out according to the following steps:
1, smelt by set component and the strand of casting, its composition is by weight percentage containing C 0.005 ~ 0.03%, Si 0.2 ~ 0.4%, Mn 0.2 ~ 0.5%, P≤0.03%, S≤0.02%, Cr 14 ~ 16%, N≤0.01%, Sn 0.1 ~ 0.4%, and contain Nb, Ti and/or V, in the time containing Nb, the content of Nb is 0.05 ~ 0.15%, in the time containing Ti, the content of Ti is 0.05 ~ 0.15%, in the time containing V, the content of V is 0.05 ~ 0.15%, and all the other are iron and inevitable impurity;
2, by slab cooling to room temperature, be heated to 1150 ± 10 ℃, insulation 1 ~ 3h, then carry out 5 ~ 6 passage hot rollings, start rolling temperature is 1080 ~ 1100 ℃, finishing temperature is 800 ~ 850 ℃, rolling reduction is 20 ~ 30%, makes hot-rolled steel sheet;
3, by hot-rolled steel sheet 900 ± 10 ℃ of annealing, the time is 2 ~ 3 h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, cold rolling total reduction is 75 ~ 88%, makes cold-rolled steel sheet;
4, cold-rolled steel sheet is heated to 800 ± 10 ℃, insulation 10 ~ 30min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation.
In aforesaid method, while smelting by set component, Sn wherein derives from zinc-plated waste steel plate.
Low gap: C, N element are because atomic volume is little, in steel, exist with interstitial atom, because C in present method, N content are low, adding a certain amount of Ti, Nb, V that C, N atom in steel are fixed to as carbide and nitride, thereby the number that has reduced in a large number steel intermediate gap atom, has improved intergranular corrosion resistance ability, mechanical property and high-temperature behavior.
Unusual segregation: in process of setting, the each region of foundry goods exists certain temperature head, therefore, synchronization foundry goods everywhere not solidified amount of liquid phase be also different; In general, cold junction setting rate is very fast, and solidification liquid is mutually not less, and not the average solute concentration of lime set in mutually compared with hot junction high (K<1); In the time that there is liquid-flow in interdendritic, if liquid flows to cold junction from hot junction, from the lower higher region of field flow orientation solutes content of solutes content, the solute average assay in Shi Gai district reduces, and produces unusual segregation; The mechanism of unusual segregation is: along with the carrying out of melt solidifying, solute enrichment in residual liquid, due to the gaseous tension of separating out in the contraction of solidified shell or residual liquid, make limb and the branch gap of solute enrichment phase through the dentrite of formation scull, mobile to ingot casting surface, make ingot casting limit portion solute higher than ingot casting center.
Because casting billet surface is loose compared with crystal inner structure, there is larger space, can make interior can minimizing, promote in crystal that solute atoms is from being sent to surface of steel ingot migration, so there is tin segregation in surface of steel ingot chill, along with the appearance of segregation line, form the barrier that stops heat to be dispersed, center, column crystal orientation development in crystallisation process, tin solute atoms is affected by barrier to crystal boundary migration time, migration amount reduces to some extent, showing as segregation degree declines gradually, in the operation of rolling, produce the unusual segregation of tin, near top layer, produce the enrichment region of tin, form stanniferous, the fine and close passivation layer of chromium.
For general steel grade, tin is that the impurity element being harmful to exists in steel, and the processing characteristics of steel is had to disadvantageous effect, simultaneously because the fusing point of tin is very low, when tin content causes hot-shortly compared with Gao Shihui, the thermoplasticity of steel is declined, and worsens the performance of steel.
But the few high purity ferritic stainless steel with excellent formability of carbon content in the stanniferous low gap ferritic stainless steel of the unusual segregation of the present invention's design can form the body centered structure that defect is few; The stainless steel that is originally added with chromium is compared with carbon steel, even if mixing tin is also difficult for breaking, add that to have reduced the high purity ferritic stainless steel with excellent formability subsurface defect of carbon and nitrogen content few, body centered structure can make tin be scattered in equably among material, has just overcome tin completely in the dispersed rear crackly problem of material internal; Thereby the present invention adds tin and replaces nickel in ferritic stainless steel, can be guaranteeing in its processing characteristics, to improve stainless erosion resistance.The interpolation of tin makes ferritic stainless steel that certain lattice distortion occur, increase the tensile strength of steel by solution strengthening, slightly reduce stainless steel plasticity, improve its plastic strain ratio (r value) simultaneously, and the rising of temperature when stretching, stanniferous stainless moulding groove temperature reduces, the interpolation of tin has increased stainless moulding on the contrary, it is a large amount of dimples that stanniferous stainless steel is broken rear fracture at 400 ~ 800 ℃, this temperature range steel moulding better, when stretching, there is ductile rupture.
Tin also can exist certain segregation phenomena in ferrite, can separate out in crystal boundary with simple substance form, tin also has the trend of enrichment around inclusion simultaneously, for example sulfide inclusion, sulfur compound is mingled with than oxide inclusion and more easily brings out spot corrosion, in spot corrosion expansion process, the inclusion optimum solvation formation corrosion pit that comes off, has promoter action to spot corrosion expansion.Stainless steel is in the time of corrosive medium; point-like inclusion is often as spot corrosion core, thereby steel is destroyed, so tin can form the protective layer of tin around inclusion at the enrichment around inclusion and parcel; meet Oxidant and form fine and close oxide film, thereby improve pitting resistance of stainless steel.
In addition, tin is the modifying function to passive film in stainless steel, the characteristic that can cause surface corrosion-resistant erosion property rete changes, make passive film finer and close, reduce the blunt current density of dimension, tin plays a part activated cathode in atmosphere, can impel steel to produce anode passivation under certain condition, thereby reduces the erosion rate of steel; Stanniferous ferritic stainless steel is in the situation that running into corrosive medium, and the tin on steel surface, chromium optimum solvation become the metal oxide of tin and chromium, under its synergy, generates finer and close passive film, and tin can improve the corrosion resistance nature of steel in the enrichment of rusty scale.
In Composition Design of the present invention:
Carbon: carbon in steel as interstitial element, in ferritic stainless steel, carbon content is generally less than 0.15%, in super-purity ferrite stainless steel, carbon content is less than 0.02%, if carbon content is too high, carbon can form compound at crystal boundary and chromium, reduces the erosion resistance of grain boundaries, and therefore in steel, the content of carbon is set in below 0.03%;
Nitrogen: the effect of nitrogen in ferritic stainless steel is similar to carbon, nitrogen is austenite former, also be that a kind of interstitial atom has solution strengthening effect, nitrogen is separated out with chromium and is formed compound at crystal boundary, reduce erosion resistance and the processing characteristics of grain boundaries, nitrogen in steel content is mainly derived from airborne nitrogen, and nitrogen in steel content is set in below 0.01%;
Silicon: silicon can improve hardness and the intensity of steel in ferritic stainless steel, and its effect is only second to phosphorus, when siliceous steel heats in oxidizing atmosphere, surface forms one deck SiO
2film, thus the oxidation-resistance of steel in the time of high temperature improved.But silicone content is high, ductility and welding property variation, the silicon in steel mainly comes from the deoxidation of ferro-silicon and bringing into of steelmaking feed, and in steel, silicone content should be not more than 0.4%;
Manganese: manganese is good reductor and sweetening agent.In steel, generally all contain a certain amount of manganese, it can eliminate or weaken the red brittleness of the steel causing due to sulphur, thereby improves the hot workability of steel.The sosoloid that manganese and iron form, improves ferritic hardness and intensity in steel.Manganese and sulphur form the MnS that fusing point is higher, can prevent the hot-short phenomenon causing because of FeS.But manganese has the tendency and the temper brittleness susceptibility that increase crystalline grain of steel alligatoring, and therefore in steel, manganese content should be not more than 0.5%;
Phosphorus: although phosphorus can improve intensity and the hardness of steel, maximum harm is that segregation is serious, increases temper brittleness, causes steel also so-called " cold short " phenomenon of easy embrittlement in the time of cold working.Phosphorus also has disadvantageous effect to weldability.Phosphorus is harmful element, and in steel, phosphorus content is controlled at below 0.03%;
Sulphur: sulphur segregation in steel is serious, the quality of deterioration steel, under reduction high temperature, the plasticity of steel, is a kind of harmful element, conventionally sulphur content is controlled at below 0.02%;
Chromium: chromium is stainless main alloy element, in order to guarantee stainless erosion resistance, in steel of the present invention, chromium content is controlled at 14 ~ 16%, and chromium too high levels can make cost increase;
Copper: copper can be used as the supplementary interpolation element of tin, effectively improves the solidity to corrosion effect of tin in steel, improves cold-formed property, but unfavorable to the hot workability of steel when copper too high levels, therefore the copper in steel is controlled at below 1.5%;
Tin: tin improves top layer passivation film structure and is confirmed to propose heavy alloyed resistance to spot corrosion effect in stainless steel, cast iron, copper alloy, now joined in ferritic stainless steel, add 0.1% can improve stainless erosion resistance effect, but when its content is greater than after 0.4%, unfavorable and the cost increase to hot workability, therefore in steel of the present invention, tin content is controlled at 0.1 ~ 0.4%;
Molybdenum: molybdenum is ferrite former, and can improve the ability of stainless corrosion-resistant ability and reducing resistance corrosive medium, but molybdenum is precious metal, therefore molybdenum is controlled at below 2%;
Titanium: titanium and nitrogen, oxygen, carbon have extremely strong avidity; It is the effective element of a kind of good deoxidation getter and fixed nitrogen and carbon.Because the avidity between titanium and carbon is much larger than the avidity between chromium and carbon, in stainless steel, conventional titanium fixes carbon dilution at grain boundaries with elimination chromium wherein, thus the intergranular corrosion of eliminating or alleviating steel.In high chromium-stainless steel, conventionally need add the titanium of approximately 5 times of carbon contents, not only can improve corrosion stability (being mainly anti intercrystalline corrosion) and the toughness of steel; Can also the Grain growth trend of organization steel in the time of high temperature and improve the welding property of steel; In steel, titanium content is controlled at 0.05 ~ 0.15%;
Niobium: niobium part is dissolved in sosoloid, plays solution strengthening effect.Trace niobium can be in the case of not affecting the intensity that improves steel the plasticity of steel or toughness.In the time that content is greater than 8 times of carbon, almost can fix carbon all in steel, thus the intergranular corrosion of eliminating or alleviating steel; In steel, content of niobium is controlled at 0.05 ~ 0.15%;
Vanadium: similar to niobium, titanium, vanadium and carbon, oxygen, nitrogen have extremely strong avidity, form with it corresponding stable compound.Vanadium mainly exists with the form of carbide in steel.Its Main Function is tissue and the crystal grain of refinement steel, the intergranular corrosion of eliminating or alleviating steel; In steel, content of niobium is controlled at 0.05 ~ 0.15%;
The synergy of tin, copper and chromium: chromium is the main alloy element in ferritic stainless steel, and stainless steel solidity to corrosion also changes with the variation of chromium content; Not adding nickel, reducing under the prerequisite of chromium content, by adding trace tin, reach corrosion proof requirement.0.1% tin, 0.1% copper and 14% chromium can guarantee that tensile strength reaches 450MPa on the one hand, unit elongation >=46%, tin and chromium can form at stainless steel surface the copper tin chromium composite oxides of one deck densification on the other hand, under its synergy, further improve erosion resistance, more than its pitting potential reaches 202mV; When smelting by adding zinc-plated steel scrap or tin iron binary alloy guarantees tin content.
Compared with the corrosion-resistant stainless steel of the present invention and prior art, there is following remarkable advantage:
(1) present method can significantly reduce stainless production cost, stanniferous stainless steel has reduced adding of noble metal nickel, molybdenum, the production cost that greatly reduces steel under the prerequisite that guarantees its good erosion resistance, has improved the competitive power of enterprise, and has saved resource;
(2) product has good erosion resistance and plasticity, when the tin in steel is greater than 0.05%, just has good machinability; Because tin is distributed in crystal boundary and intracrystalline, improve stainless resistance to spot corrosion and intergranular corrosion resistance performance, thereby make stainless steel in dilute sulphuric acid and organic chloracid, have good corrosion-resistant effect;
(3) tensile strength of product gets a promotion, and the tensile strength of stanniferous ferritic stainless steel increases about 30MPa than 430 not stanniferous ferritic stainless steel steel grades;
(4) technical process is simple, and the recovery rate of the Sn in smelting process can reach 80%, and is easy to control, and after heat treatment has higher intensity, hardness and corrosion resistance nature.
Accompanying drawing explanation
Fig. 1 is the stanniferous low gap ferritic stainless steel of the unusual segregation in the embodiment of the present invention 1 microtexture metallograph under Carl Zeiss metaloscope;
Fig. 2 is the stanniferous low gap ferritic stainless steel of the unusual segregation in the embodiment of the present invention 1 scanning electron microscope (SEM) photograph under the Japanese Shimadzu SSX-550 of company scanning electron microscope, is illustrated as the segregation phenomena of tin around sulfide;
Fig. 3 is the stanniferous low gap ferritic stainless steel of the unusual segregation in the embodiment of the present invention 1 scanning electron microscope (SEM) photograph under the Japanese Shimadzu SSX-550 of company scanning electron microscope, is illustrated as the face scanning result of tin element in the visual field;
Fig. 4 be to the stanniferous low gap ferritic stainless steel of the unusual segregation in the embodiment of the present invention 1 under the Japanese Shimadzu SSX-550 of company scanning electron microscope and X-ray energy spectrometer to its inclusion around composition get analytical results ready; In figure, the weight content of Cr is 14.28%, and atomic percent is 15.21%; The weight content of Fe is 85.21%, and atomic percent is 84.55%; The weight content of Sn is 0.51%, and atomic percent is 0.24%;
Fig. 5 is the sample position distribution plan under the Japanese Shimadzu SSX-550 of company scanning electron microscope to the stanniferous low gap ferritic stainless steel of the unusual segregation in the embodiment of the present invention 1; In figure, A is top layer sampling, and B is 1 group of sample position, and 2,3,4 are respectively 2,3,4 groups of sample position;
Fig. 6 is the top layer sampling of stanniferous low gap ferritic stainless steel and the quantitative analysis graphic representation of 1,2,3,4 group of sampling tin element, carbon under the Japanese Shimadzu SSX-550 of company scanning electron microscope and X-ray energy spectrometer analysis of the unusual segregation in the embodiment of the present invention 1; In figure, ■ is carbon, and ▼ is tin element;
Fig. 7 is that the stanniferous low gap ferritic stainless steel of the unusual segregation in the embodiment of the present invention 1 is at the lower inclusion defects scintigram of the Japanese Shimadzu SSX-550 of company scanning electron microscope.
Embodiment
Smelting and the strand of casting by set component in the embodiment of the present invention, smelting is to adopt electric furnace or converter smelting, VOD refining, the refining of LF stove, casting is to adopt sheet billet continuous casting; Or directly by vacuum induction furnace smelting, casting is die casting or sheet billet continuous casting.
The pickle solution that in the embodiment of the present invention, pickling adopts is by 100 mL HF, 50 mL HNO
3with 1 L H
2o preparation.
In the embodiment of the present invention, tested for tensile strength is that accepted standard is GB/T228-2002, rolled sample after thermal treatment is cut into gauge length 50mm with nc wire-cutting line, wide is the room temperature tensile sample of 12.5mm, carries out tensile tests at room on INSTRON-4206 almighty test machine.
In the embodiment of the present invention, testing pitting potential is that the stainless-steel sheet line of preparation is cut into 10.1mm × 10.1mm steel sample, falls surface scale with No. 100 sand paperings, reserves the working area 1cm of sample
2a surface, epoxy resin is coated with envelope for remaining surface; Sample grinds with No. 200, No. 400, No. 600, No. 800 sand paper successively, will note avoiding sample heating (wet-milling to 800 sand paper) when grinding; In order to prevent crevice corrosion, after grinding, carry out Passivation Treatment (soaking 1h in 50 ℃, 20 ~ 30% nitric acid), select electrochemical method, according to GB/T17899-19999 stainless steel pitting potential measuring method, the negative anodic polarization curve of measuring sample to be tested by potentiodynamic technique, obtains stainless pitting potential.
In the embodiment of the present invention, testing upper and lower yield-point is that accepted standard is GB/T228-2002, the stainless steel of preparation is cut into gauge length 50mm with nc wire-cutting line, wide is the room temperature tensile sample of 12.5mm, carries out tensile tests at room on INSTRON-4206 almighty test machine.
In the embodiment of the present invention, testing elongation after fracture is that accepted standard is GB/T228-2002, the stainless steel of preparation is cut into gauge length 50mm with nc wire-cutting line, wide is the room temperature tensile sample of 12.5mm, carries out tensile tests at room on INSTRON-4206 almighty test machine.
In the embodiment of the present invention, testing plastix strain is that accepted standard is GB/T228-2002, the stainless steel of preparation is cut into gauge length 50mm with nc wire-cutting line, wide is the room temperature tensile sample of 12.5mm, carries out tensile tests at room on INSTRON-4206 almighty test machine.
Embodiment 1
Smelt and the strand of casting by set component, its composition contains C 0.005% by weight percentage, Si 0.4%, and Mn 0.2%, P 0.016%, S 0.018%, Cr 14%, N 0.005%, Sn 0.24%, Nb 0.05%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 1h, then carries out 5 passage hot rollings, and start rolling temperature is 1080 ℃, and finishing temperature is 800 ℃, and rolling reduction is 30%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 2 h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 75%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 10min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Its tensile strength 451 MPa, pitting potential is 202mV, and upper yield point is 310MPa, and lower yield point is 306MPa, and elongation after fracture is 47%; Carry out moulding strain testing, r value is that 1.46, n value is that 0.24, △ r value is 0.77, and Erichsen number is 9.84; The forming property of compound material, can meet the requirement of deep drawability energy aspect;
Microtexture metallograph under Carl Zeiss metaloscope as shown in Figure 1, the scanning electron microscope (SEM) photograph of the segregation phenomena of tin around sulfide as shown in Figure 2, the face scanning result of tin element as shown in Figure 3, inclusion around composition get analytical results (the Japanese Shimadzu SSX-550 of company scanning electron microscope and X-ray energy spectrometer) as shown in Figure 4 ready, the stainless steel sample position after thermal treatment distributes as shown in Figure 5; According to the quantitative analysis curve of the tin element of the sample location from stainless steel top layer to central core shown in Fig. 5, carbon as shown in Figure 6; Inclusion defects scanning result as shown in Figure 7;
Carry out simultaneous test, smelt and the composition of the ingot casting of casting by weight percentage containing C 0.020%, Si 0.229%, Mn 0.381%, Cr 15.0%, P 0.021%, S 0.017%, surplus is iron and inevitable impurity; Make ferritic stainless steel by above-mentioned mode of the same race, its tensile strength 432MPa, pitting potential is 105mV, upper yield point is 310MPa, lower yield point is 302MPa, and elongation after fracture is 49%, carries out moulding strain testing, and r value is 1.49, n value is that 0.23, △ r value is 0.85, and Erichsen number is 9.28.
Smelt and the strand of casting by set component, its composition contains C 0.01% by weight percentage, Si 0.35%, and Mn 0.25%, P 0.017%, S 0.014%, Cr 14.5%, N 0.007%, Sn 0.31%, Ti 0.05%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 2h, then carries out 6 passage hot rollings, and start rolling temperature is 1100 ℃, and finishing temperature is 850 ℃, and rolling reduction is 20%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 2.5h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 88%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 20min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 451 MPa, pitting potential is 220mV, and upper yield point is 311MPa, and lower yield point is 308 MPa, and elongation after fracture is 48%; Carry out moulding strain testing, r value is that 1.44, n value is that 0.22, △ r value is 1.15, and Erichsen number is 9.63; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Smelt and the strand of casting by set component, its composition contains C 0.015% by weight percentage, Si 0.33%, and Mn 0.28%, P 0.019%, S 0.015%, Cr 14.8%, N 0.009%, Sn 0.19%, V 0.05%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 3h, then carries out 5 passage hot rollings, and start rolling temperature is 1090 ℃, and finishing temperature is 830 ℃, and rolling reduction is 25%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 3 h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 85%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 30min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 445MPa, pitting potential is 240mV, and upper yield point is 337 MPa, and lower yield point is 325 MPa, and elongation after fracture is 49%; Carry out moulding strain testing, r value is that 1.53, n value is that 0.23, △ r value is 1.21, and Erichsen number is 9.78; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Smelt and the strand of casting by set component, its composition contains C 0.02% by weight percentage, Si 0.31%, and Mn 0.3%, P 0.022%, S 0.014%, Cr 15.1%, N 0.003%, Sn 0.36%, Nb 0.15%, Ti 0.15%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 1h, then carries out 6 passage hot rollings, and start rolling temperature is 1080 ℃, and finishing temperature is 800 ℃, and rolling reduction is 25%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 2h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 82%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 15min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 451 MPa, pitting potential is 240mV, and upper yield point is 331MPa, and lower yield point is 321 MPa, and elongation after fracture is 49%; Carry out moulding strain testing, r value is that 1.44, n value is that 0.23, △ r value is 1.12, and Erichsen number is 10.25; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Smelt and the strand of casting by set component, its composition contains C 0.025% by weight percentage, Si 0.27%, and Mn 0.33%, P 0.021%, S 0.017%, Cr 15.5%, N 0.002%, Sn 0.22%, Ti 0.15%, V 0.15%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 2h, then carries out 5 passage hot rollings, and start rolling temperature is 1100 ℃, and finishing temperature is 850 ℃, and rolling reduction is 30%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 2.5h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 78%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 25min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 448MPa, pitting potential is 216mV, and upper yield point is 329MPa, and lower yield point is 314MPa, and elongation after fracture is 48%; Carry out moulding strain testing, r value is that 1.50, n value is that 0.24, △ r value is 1.10, and Erichsen number is 9.93; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Embodiment 6
Smelt and the strand of casting by set component, its composition contains C 0.03% by weight percentage, Si 0.24%, and Mn 0.38%, P 0.021%, S 0.016%, Cr 16%, N 0.004%, Sn 0.4%, Nb 0.15%, V 0.15%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 3h, then carries out 6 passage hot rollings, and start rolling temperature is 1090 ℃, and finishing temperature is 830 ℃, and rolling reduction is 20%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 3 h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 84%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 10min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 450 MPa, pitting potential is 228mV, and upper yield point is 332MPa, and lower yield point is 320 MPa, and elongation after fracture is 47%; Carry out moulding strain testing, r value is that 1.48, n value is that 0.23, △ r value is 1.01, and Erichsen number is 9., 92; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Embodiment 7
Smelt and the strand of casting by set component, its composition contains C 0.008%, Si 0.22%, Mn 0.41%, P 0.026% by weight percentage, S 0.015%, Cr 15.7%, N 0.06%, Sn 0.3%, Nb 0.08%, Ti 0.11%, V 0.09%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 1h, then carries out 5 passage hot rollings, and start rolling temperature is 1080 ℃, and finishing temperature is 800 ℃, and rolling reduction is 20,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 2.5h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 80%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 20min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 446 MPa, pitting potential is 233mV, and upper yield point is 319MPa, and lower yield point is 315 MPa, and elongation after fracture is 47%; Carry out moulding strain testing, r value is that 1.49, n value is that 0.22, △ r value is 1.14, and Erichsen number is 9.96; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Embodiment 8
Smelt and the strand of casting by set component, its composition contains C 0.019%, Si 0.2%, Mn 0.45%, P 0.019% by weight percentage, S 0.018%, Cr 14.3%, N 0.008%, Sn 0.2%, Nb 0.06%, Ti 0.12%, V 0.12%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 2h, then carries out 6 passage hot rollings, and start rolling temperature is 1100 ℃, and finishing temperature is 850 ℃, and rolling reduction is 25%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 3 h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 88%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 30min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 446MPa, pitting potential is 219mV, and upper yield point is 322MPa, and lower yield point is 311 MPa, and elongation after fracture is 49%; Carry out moulding strain testing, r value is that 1.45, n value is that 0.24, △ r value is 0.94, and Erichsen number is 9.57; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Embodiment 9
Smelt and the strand of casting by set component, its composition contains C 0.024%, Si 0.21%, Mn 0.5%, P 0.029% by weight percentage, S 0.011%, Cr 14.6%, N 0.08%, Sn 0.1%, Nb 0.13%, Ti 0.09%, the content of V is 0.06%, all the other are iron and inevitable impurity; The Sn adopting when smelting derives from zinc-plated waste steel plate;
Slab cooling, to room temperature, is heated to 1150 ± 10 ℃, and insulation 3h, then carries out 5 passage hot rollings, and start rolling temperature is 1090 ℃, and finishing temperature is 830 ℃, and rolling reduction is 30%,, make hot-rolled steel sheet;
By hot-rolled steel sheet, 900 ± 10 ℃ of annealing, the time is 2h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, and cold rolling total reduction is 75%, makes cold-rolled steel sheet;
Cold-rolled steel sheet is heated to 800 ± 10 ℃, and insulation 15min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation; Tensile strength 448MPa, pitting potential is 236mV, and upper yield point is 321 MPa, and lower yield point is 310 MPa, and elongation after fracture is 47%; Carry out moulding strain testing, r value is that 1.48, n value is that 0.22, △ r value is 0.88, and Erichsen number is 9.73; The forming property of compound material, can meet the requirement of deep drawability energy aspect.
Claims (3)
1. a stanniferous low gap ferritic stainless steel for unusual segregation, is characterized in that composition is by weight percentage containing C 0.005 ~ 0.03%, Si 0.2 ~ 0.4%, Mn 0.2 ~ 0.5%, P≤0.03%, S≤0.02%, Cr 14 ~ 16%, N≤0.01%, Sn 0.1 ~ 0.4%, and contain Nb, Ti and/or V, in the time containing Nb, the content of Nb is 0.05 ~ 0.15%, in the time containing Ti, the content of Ti is 0.05 ~ 0.15%, in the time containing V, the content of V is 0.05 ~ 0.15%, and all the other are iron and inevitable impurity; Tensile strength 445 ~ 451 MPa, pitting potential is 202 ~ 240mV.
2. the stanniferous low gap ferritic stainless steel of a kind of unusual segregation according to claim 1, the upper yield point that it is characterized in that this ferritic stainless steel is 310 ~ 337 MPa, and lower yield point is 306 ~ 325 MPa, and elongation after fracture is 47 ~ 49%.
3. a preparation method for the stanniferous low gap ferritic stainless steel of unusual segregation claimed in claim 1, is characterized in that carrying out according to the following steps:
(1) smelt by set component and the strand of casting, its composition is by weight percentage containing C 0.005 ~ 0.03%, Si 0.2 ~ 0.4%, Mn 0.2 ~ 0.5%, P≤0.03%, S≤0.02%, Cr 14 ~ 16%, N≤0.01%, Sn 0.1 ~ 0.4%, and contain Nb, Ti and/or V, in the time containing Nb, the content of Nb is 0.05 ~ 0.15%, in the time containing Ti, the content of Ti is 0.05 ~ 0.15%, in the time containing V, the content of V is 0.05 ~ 0.15%, and all the other are iron and inevitable impurity;
(2) by slab cooling to room temperature, be heated to 1150 ± 10 ℃, insulation 1 ~ 3h, then carry out 5 ~ 6 passage hot rollings, start rolling temperature is 1080 ~ 1100 ℃, finishing temperature is 800 ~ 850 ℃, rolling reduction is 20 ~ 30%, makes hot-rolled steel sheet;
(3) by hot-rolled steel sheet 900 ± 10 ℃ of annealing, the time is 2 ~ 3 h, is cooled to room temperature, then pickling removes surface oxide layer, then carries out cold rollingly, cold rolling total reduction is 75 ~ 88%, makes cold-rolled steel sheet;
(4) cold-rolled steel sheet is heated to 800 ± 10 ℃, insulation 10 ~ 30min carries out normalizing treatment, obtains the stanniferous low gap ferritic stainless steel of unusual segregation.
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