CN115466902A - Niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance and manufacturing method thereof - Google Patents
Niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance and manufacturing method thereof Download PDFInfo
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Abstract
Niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance and a manufacturing method thereof comprise the following components in percentage by mass: 0.01 to 0.06 percent of C, 0.2 to 0.9 percent of Si, 3.0 to 5.0 percent of Mn, 0.8 to 2.0 percent of Ni, 20.6 to 22.5 percent of Cr, less than or equal to 1.0 percent of Mo, less than or equal to 1.0 percent of Cu, 0.08 to 0.15 percent of N, less than 0.07 percent of V, less than 0.04 percent of P, less than 0.0015 percent of S, 0.02 to 0.30 percent of Nb, 0.001 to 0.003 percent of B, 0.01 to 0.03 percent of RE, and the balance of Fe and other inevitable impurities. The stainless steel has low cost, the intergranular corrosion resistance and the pitting corrosion resistance are superior to those of 304 stainless steel, the stress corrosion performance is superior to that of 304 austenitic stainless steel and 2205 duplex steel stainless steel at the same time, and the yield strength Rp at room temperature 0.2 More than 500MPa, elongation A 50 More than 40 percent, no edge crack of the hot rolled coil and good surface quality; the composite material is more suitable for being applied to dual environments of Cl ions and bearing stress, such as bearing parts of stainless steel bridges, stainless steel high-rise building beam columns, subway pipe galleries and the like.
Description
Technical Field
The invention relates to duplex stainless steel and a manufacturing method thereof, in particular to niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance and a manufacturing method thereof.
Background
Stainless steel is an important choice for materials in the modern industrial field due to certain strength and corrosion resistance. However, the conventional austenitic stainless steels 304 and 316 have low strength and poor intergranular corrosion resistance and stress corrosion resistance, cannot well meet the requirements of the bearing field with high strength and needing welding, and the products contain higher noble metal nickel and have higher cost. In recent years, people obtain nickel-saving or even nickel-free austenitic stainless steel by using an N alloying means, so that the cost is greatly reduced, the strength is improved to a certain extent, and the products are well applied to the fields of household electrical products, building enclosures and the like. However, the yield strength of the currently developed nickel-saving austenitic stainless steel is only about 400MPa, the strength cannot completely meet the requirements of high-strength stainless steel, and more importantly, the austenitic stainless steel has very poor stress corrosion resistance and is not suitable for the field of high-strength load-bearing structures.
The duplex stainless steel has a high strength characteristic compared with the austenitic stainless steel. However, conventional duplex stainless steel contains high alloy content of Cr, mo, N, etc., and is liable to precipitate brittle phases such as intermetallic compounds and nitrides, and hot working in the temperature range where brittle phases precipitate is liable to cause defects such as severe edge cracking and surface crack peeling. And the brittle phase precipitation temperature is usually above 1000 ℃ and higher than the finishing temperature. In addition, the precipitates are difficult to remove even in the solution treatment at a temperature of 1000 ℃ to brittle precipitation temperature, and particularly chromium nitrides precipitate in ferrite or at a ferrite-austenite phase boundary, so that the elongation is greatly reduced, and a chromium poor layer is formed by the precipitation, whereby the corrosion resistance is also seriously reduced.
Chinese patent publication No. CN101215674 discloses an economical duplex stainless steel alloy material and a preparation method thereof, wherein the alloy material comprises the following components in percentage by mass: c is more than 0 and less than or equal to 0.04 percent, S is more than 0 and less than or equal to 0.01 percent, si is more than 0 and less than or equal to 1.0 percent, P is more than 0 and less than or equal to 0.015 percent, cr:18.0 to 20.0%, mn:5.0 to 7.0%, N:0.15 to 0.25%, B: 0.001-0.01%, rare earth Ce or Y: 0.005-0.20 percent, and the balance of Fe. The steel is a typical economical duplex stainless steel which replaces Ni by Mn and N, the N content is high, the casting process is easy to cause N pore quality problems, and the PREN value of the duplex stainless steel is less than 19.3 and less than 20.0.
Chinese patent publication No. CN 112522642A discloses a tungsten-containing rare earth-free economical duplex stainless steel and a preparation method thereof, wherein the tungsten-containing rare earth-free economical duplex stainless steel comprises the following chemical components in percentage by mass: c is less than or equal to 0.03%, si is less than or equal to 0.75%, mn: 2-4%, S is less than or equal to 0.02%, P is less than or equal to 0.04%, ni: 1.5-2.5%, cr: 20.5-22.5%, mo is less than or equal to 0.6%, cu:0.5 to 1.5%, N:0.15 to 0.20%, W:0.5 to 1.5 percent, and the balance of Fe and other inevitable impurities. The steel adopts a die casting process, continuous casting manufacturability, particularly hot processing performance of a continuous casting slab is not mentioned, and continuous casting-hot rolling mass industrial production is difficult to realize.
Chinese patent publication No. CN 105200341A discloses an economical duplex stainless steel with tensile strength more than 1000MPa and a manufacturing method thereof, and the economic duplex stainless steel comprises the following chemical components in percentage by mass: c:0.01 to 0.08%, si:0.1 to 0.8%, mn:0.8 to 5.0%, cr:18.0 to 20.5%, ni:0.5 to 2.5%, N:0.07 to 0.15%, mo:0 to 0.5%, cu:0 to 1.0%, and the balance of Fe and other unavoidable impurities. The material controls the Md30 to 145 ℃ at the temperature of 115 ℃ or more, and mainly improves the tensile strength to over 1000 MPa. However, the corrosion resistance, particularly the intergranular corrosion resistance, is not concerned, and the PREN value is 19.1, which is relatively low. In addition, hot processing manufacturability is not mentioned.
Disclosure of Invention
The invention aims to provide niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance and a manufacturing method thereof, the stainless steel has low cost, the intergranular corrosion resistance and pitting corrosion resistance are superior to those of 304 stainless steel, the stress corrosion performance is simultaneously superior to those of 304 austenitic stainless steel and 2205 duplex steel, and the room-temperature yield strength Rp is 0.2 More than 500MPa, elongation A 50 More than 40 percent, no edge crack of the hot rolled coil and good surface quality; the method is more suitable for being applied to dual environments of Cl ions and bearing stress, such as bearing parts of stainless steel bridges, stainless steel high-rise building beam columns, subway pipe galleries and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance comprises the following components in percentage by mass:
C：0.01～0.06％，
Si：0.2～0.9％，
Mn：3.0～5.0％，
Ni：0.8～2.0％，
Cr：20.6～22.5％，
Mo：≤1.0％，
Cu：≤1.0％，
N：0.08～0.15％，
V：＜0.07％，
P：＜0.04％，
S：＜0.0015％，
Nb：0.02～0.30％，
B：0.001～0.003％
RE：0.01～0.03％，
the balance contains Fe and other inevitable impurities, and the following relationship is satisfied:
ferrite ratio F: 40-60%, wherein F =51.3 (Cr +1.5 Si + Mo + 5V +2 Nb)/(Ni + 30C +30N +0.11 Mn-0.009 Mn +0.1T-220, T is the final rolling temperature, DEG C;
pitting corrosion resistance equivalent weight PREN is more than or equal to 20.0, wherein PREN = Cr +3.3Mo +30N-Mn;
M 23 C 6 the precipitation temperature is less than or equal to 800 ℃, wherein M 23 C 6 Precipitation temperature = 3389C +3.5 Si +9.4 Cr +6.4 Mo + 85V-214N-720Nb +516;
Cr 2 the precipitation temperature of N is less than or equal to 1000 ℃, wherein, cr 2 N precipitation temperature =67 × Si-9 × Mn +1.1 × Cr-18 × Ni +10 × Mo +24 × Cu +781 × V +531 × N-480 × C +882;
a martensite content M (. Epsilon.40) produced by a tensile strain of 40%, 10% < M (. Epsilon.40) < 30%, wherein,
M(ε40)＝246-231*(C+N)-4.6*Si-4*Mn-14*(Ni+Cu)-6.7*Cr-9.2*Mo。
the balance being Fe and other unavoidable impurities.
The stainless steel of the present invention is mixed with acid (10% HNO) 3 +3% of corrosion rate of < 60 g/(m) in HF 2 * h) The time for cracks to appear in the 42 percent boiling magnesium chloride solution is more than 20 hours, and the time for crack penetration is more than 90 hours; room temperature yield strength Rp 0.2 More than 500MPa, elongation A 50 ＞40％。
In the composition design of the duplex stainless steel of the present invention:
c is an austenite forming element, can balance the austenite and ferrite phase ratio in the stainless steel, and can also stabilize the austenite and regulate and control the content of deformed martensite. Meanwhile, C is used as interstitial atoms and can play a role in solid solution strengthening. However, the C content is too high to form a series of complex carbides with chromium, which can reduce the corrosion resistance of steel and particularly can obviously improve M 23 C 6 Precipitation temperature, acceleration M 23 C 6 Precipitation occurs to impair intergranular corrosion resistance. Therefore, the role of carbon in stainless steel is contradictory from the comprehensive viewpoints of tissue regulation, strength improvement, corrosion resistance and the like. By combining the effects, the carbon content is controlled to be 0.01-0.06%.
Si plays a role of deoxidation in molten steel, and has a certain promotion effect on Cr2N precipitation, the toughness of the steel is obviously reduced due to the excessively high content of Si, and the production and processing are difficult, so that the content of Si is controlled to be 0.2-0.9%.
Mn can improve the solubility of N in the molten steel, so that more N is dissolved in the molten steel. Mn-N is commonly used to replace noble metal Ni, so that the stability of an austenite phase is improved, the generation tendency of deformed martensite is regulated and controlled, and the two-phase structure in the two-phase stainless steel is balanced. Too high Mn is disadvantageous to corrosion resistance, so that the Mn content is controlled to 3.0 to 5.0%.
Cr, the most important additive element for ensuring high corrosion resistance of the duplex stainless steel of the invention, is a ferrite forming element, reduces the austenite phase region and stabilizes the austenite structure. When the chromium content is low, the corrosion resistance will be significantly reduced. Meanwhile, the chromium content is reduced, the stability of austenite is obviously reduced, and excessive martensite is easily generated during cold deformation to damage the plasticity of the material. Therefore, the chromium content of the invention is controlled to be 20.6 percent at the lowest. However, when the chromium content is too high, the austenite forming element content needs to be increased in order to obtain a dual-phase structure, thereby increasing the cost. Also, too high a chromium content significantly increases the risk of chromium-rich brittle precipitated phases, which also makes the austenite more difficult to martensitic. Therefore, the chromium content in the steel of the invention is controlled to be 22.5 percent at most.
Ni and an austenite forming element, expands an austenite phase region, simultaneously improves the stability of austenite, regulates one of main elements of the strain martensite content, and ensures that the proportion of two phases is within a reasonable range at room temperature by matching with a ferrite performance element Cr. The effect of Ni on the stress corrosion resistance of stainless steel is in a U-shaped trend, wherein the stress corrosion resistance in the range of 3-8% is the worst, and the Ni is positioned at the bottom of the U-shaped. In addition, the Ni content is too high, the proportion of two phases is unbalanced, the alloy cost is greatly increased, and the cost and the performance (particularly the stress corrosion resistance) are considered, so the Ni content is controlled to be 0.8-2.0%.
N and nitrogen can improve the strength of steel and obviously improve pitting corrosion resistance, and the effect of N and nitrogen on improving the pitting corrosion resistance is 30 times that of Cr. Nitrogen is also a strong austenite stabilizing element, and if the nitrogen content is too high, the austenite stability is too high, and the transformation of austenite into martensite is inhibited. Meanwhile, high nitrogen can increase the risk of nitrogen pores and greatly improve Cr 2 N precipitation temperature, remarkably promoting Cr 2 Formation of the N brittle phase. Thereby increasing the difficulty of smelting and hot working and causing difficult industrial scale production. Therefore, the content of N in the steel of the invention is controlled to be 0.08-0.15%.
P, which is a harmful element in steel in general, increases cold brittleness of steel and deteriorates welding and cold bending properties, so that the P content is controlled to be less than 0.040%.
S, sulfur is a harmful element in general, and causes hot brittleness, reduces ductility and toughness, and forms cracks during rolling. Particularly, the hot workability of the duplex stainless steel is extremely sensitive to the element S, and the content of the element S is controlled within 0.0015% in order to reduce the adverse effect of S on the hot workability.
V, ferrite-forming element, more importantly, V is Cr strongly promoted 2 N (a brittle phase with a hexagonal close-packed structure) in each pair of the alloying elements, cr 2 The N precipitation temperature effect is most pronounced. Seriously impairing the hot workability of the duplex stainless steel, and Cr 2 N can greatly reduce the toughness and plasticity of the material in a room temperature structure, and V is a harmful element in the invention, and the low level is controlled as soon as possible, and the content of V is required to be less than 0.07%.
Mo, an element for remarkably improving corrosion resistance, particularly improving the pitting corrosion resistance in a chloride ion environment, has the corrosion resistance effect about 3.3 times that of Cr. However, it is very expensive, and too high Mo easily forms brittle phases, greatly impairing hot workability, so that the Mo content is controlled to be not more than 1.0%.
Cu and a small amount of Cu can improve the toughness and plasticity and cold processing performance of the material in stainless steel, and meanwhile, the method helps to stabilize austenite phase and regulate and control the content of deformed martensite. Too high Cu may cause material processing difficulties. Therefore, the Cu content is controlled to be less than or equal to 1.0 percent.
Nb, a small amount of Nb can be combined with elements such as C, N and the like in the steel to precipitate second phase particles which are dispersed and distributed, the second phase particles can block the growth of crystal grains and tissues, so that the effect of refining the crystal grains and the tissues is achieved, and meanwhile, the combination with C can reduce the dissolving amount of carbon in the steel and improve the intergranular corrosion resistance of the steel; or solid-dissolved in the matrix, the growth of crystal grains is hindered due to the solid-solution dragging effect, the strength is improved, and the Nb content is controlled to be 0.02-0.3%.
B, trace B element can play a role in improving the high-temperature plasticity of the material in the stainless steel, and is beneficial to hot working, but the excessive content of B can cause a large amount of boride harmful phases to appear in the structure, thereby seriously reducing the corrosion resistance and the plasticity, and controlling the content of B to be 0.001-0.003%.
Rare earth RE: the trace rare earth elements can also play a role in improving the high-temperature plasticity of the material in the stainless steel, and are particularly important for the dual-phase steel with high hot working difficulty.
In addition, the composition design of the duplex stainless steel of the present invention also needs to satisfy:
1. austenite forming elements such as C, N, ni and Mn are matched with ferrite forming elements such as Cr, mo, si and V, so that the austenite equivalent and the ferrite equivalent are both in a reasonable range, and a solid solution structure is an austenite-ferrite two-phase structure, wherein the proportion of a ferrite phase is 40-60%; the cold deformation structure is an austenite, ferrite and deformation martensite three-phase structure, wherein the proportion of the deformation martensite phase is 10-30%.
A large number of experimental researches show that the ferrite content F in the hot working process meets the relation:
f =51.3 (Cr +1.5 Si + Mo + 5V +2 Nb)/(Ni + 30C +30N +0.11 Mn-0.009 Mn + Mn) +0.1T-220, T is the final rolling temperature, DEG C.
The ferrite phase proportion F is 40-60%, so that the lowest ferrite content of the steel is over 40% in the hot rolling process, and the higher the high-temperature ferrite content is, the steel can be used as a soft phase to bear more deformation force so as not to crack caused by the incongruity of the two phases. However, when the content of the high-temperature ferrite exceeds 60%, the mechanical properties, welding properties and the like of the finished steel coil are greatly reduced.
2. The duplex stainless steel ensures that the pitting corrosion resistance equivalent PREN = Cr +3.3Mo +30N-Mn is more than or equal to 20.0 through high Cr design, and the material has better pitting corrosion resistance than 304 austenitic stainless steel. The Nb microalloy with a proper amount can obtain a dispersed NbC precipitated phase, greatly reduce the combination of C and Cr, reduce the tendency of poor chromium and obviously improve the intergranular corrosion resistance of the material. Tendency of C to bind Cr, M may be used 23 C 6 Precipitation temperature = 3389C +3.5 Si +11.4 Cr +6.4 Mo + 85V-214N-720Nb +516 (. Degree. C.), the higher the precipitation, the indication of M 23 C 6 The greater the tendency to precipitate, the greater the negative influence on intergranular corrosion. In the formula, C, cr, mo and Si promote M 23 C 6 Is precipitated due to M 23 C 6 Has the main component of Cr 23 C 6 And Mo often partially replaces chromium therein to form (Cr, mo) 23 C 6 Si decreases the solid solubility of C in austenite and promotes Cr 23 C 6 And (4) precipitation. N, nb inhibition of M 23 C 6 Since N and Cr are easily bonded to form Cr 2 N precipitate phase, and M 23 C 6 Thereby inhibiting M 23 C 6 On the other hand, cr 2 The incubation period of N precipitation is very long, in M 23 C 6 The precipitation process does not generally precipitate under the conditions of precipitation. Nb has a significantly higher bonding force with C than Cr, and thus inhibits M 23 C 6 And (4) precipitating. Low V and micro B alloying to ensure that the structure is basically free of Cr 2 N brittle phase, no precipitation of grain boundary B compoundFurther ensuring the corrosion resistance better than 304.
3. The duplex stainless steel has ferrite content of more than 40 percent and is matched with a nickel-saving design of 0.8-2.0 percent, so that the stress corrosion resistance is greatly improved, and the duplex stainless steel is far superior to the conventional duplex stainless steel 2205 and is further superior to austenitic stainless steels such as 304 and the like. This is because Ni tends to have a U-shape in its stress corrosion resistance to stainless steel, and the stress corrosion resistance is the worst in the range of 3 to 8%, which is located at the bottom of the U-shape.
4. The influence on the mechanical property, C and N have obvious solid solution strengthening effect, the C + N content is greater than 1000ppm, the deformed martensite M (epsilon 40) is controlled within the range of 10-30%, the elongation of the material with too high deformed martensite content is greatly reduced, and the plasticity is poor; the phase change strengthening mechanism of the material with too low content can not fully play a role, and the strength is insufficient. The quantitative relationship of M (. Epsilon.40) subject to compositional constraints is M (. Epsilon.40) =246-231 (C + N) -4.6 Si-4 Mn-14 (Ni + Cu) -6.7 Cr-9.2 Mo, where each alloying element increases the stability of austenite, which is consistent with their ability to shift the TTT curve of the steel to the right, extending the incubation period for austenite transformation.
The kinetic reasons for the influence of the alloying elements on the stability of austenite are generally considered:
(1) cr, mo, ni, mn and Cu are replaced and dissolved in the iron matrix, so that lattice distortion is increased, C and N atom energy of interstitial solid solution is reduced, the stability of austenite is increased, and deformed martensite is not easily generated;
(2) the alloy elements drag the movement of the A/M interface, and atoms such as Cr, mo, ni, mn and the like are gathered on the A/M interface, so that the dragging effect of preventing the movement of the interface is achieved, and the growth speed of the deformed martensite is reduced. Proper TRIP effect (metastable austenite in steel induces martensite nucleation under the action of cold deformation, phase transformation strengthening and plastic growth mechanism is introduced to improve the strength and toughness of the steel) is controlled, so that the strength and elongation of the material are greatly improved, and the yield strength Rp 0.2 Compared with 304 austenitic stainless steel, the steel is improved by more than 80 percent and reaches more than 500 MPa. Elongation A 50 Is more than 40 percent and is far better than 30 percent of the conventional duplex stainless steel 2205.
5. The method adopts laterite-nickel ore to directly smelt molten iron containing nickel, wherein the content of Ni is 0.8-2.0%, and no extra ferronickel alloy is needed. Therefore, compared with 304 austenitic stainless steel, the material cost can be reduced by more than 50%.
The invention relates to a method for manufacturing niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance, which comprises the following steps:
1) Smelting and casting
Smelting, AOD, LF refining and casting into a casting blank according to the components;
2) Hot rolling
The billet heating adopts three stages of heating: three-stage heating total time T = (1.0-1.5) h, T unit: min; h steel billet thickness, unit: mm; wherein the temperature of the preheating section is 600-800 ℃; the heating temperature of the first stage is 1050-1150 ℃, and the heating time is ensured to be more than 90min; the second stage has soaking temperature of 1220-1280 deg.c and soaking period of 30-50 min.
Then hot rolling is carried out until the required thickness is achieved, and then coiling is carried out, wherein the final rolling temperature is not lower than 1000 ℃;
3) Annealing and pickling
The annealing temperature is 1010-1100 ℃, and the annealing time is 2-8 min; and then acid washing.
Preferably, the laterite-nickel ore is smelted in a blast furnace to obtain nickel molten iron with the Ni content of 0.8-2.0 percent, and the nickel molten iron is subjected to AOD chromium-maintaining decarburization smelting, LF refining and continuous casting to form a casting blank; wherein, the steel tapping alkalinity in the smelting stage is 2.0-3.5, the reduction alkalinity is more than 2.0, and the desulfurization alkalinity is 3.0-3.5.
Preferably, the acid washing in the step 3) adopts a sulfuric acid + mixed acid process; the mixed acid is formed by mixing nitric acid and hydrofluoric acid, wherein the concentration of the sulfuric acid is 250-400g/L, the concentration of the nitric acid in the mixed acid is 140-240g/L, and the concentration of the hydrofluoric acid is 15-55 g/L.
In the method of manufacturing a duplex stainless steel according to the present invention:
and in the hot rolling stage, a three-stage heating mode is adopted for heating the slab, and the total heating time is according to the thickness T of the slab (= (1.0-1.5)) h. Three-stage heating mode, namely preheating stage temperature 600-800 ℃, first stage heating temperature 1050E1150 deg.c and soaking temperature of 1220-1280 deg.c in the second stage. Wherein, the heating time of 1050-1150 ℃ in the first stage is ensured to be more than 90min, and the soaking time of 1220-1280 ℃ in the second stage is 30-50 min, so as to ensure that the Cr2N brittle phase in the original casting blank is completely decomposed and the alloy elements are fully re-dissolved, and the phenomenon that the retention time in the soaking section is too long to cause the thick structure and influence the hot-working performance is avoided. And finally rolling the steel plate on a hot continuous rolling mill group to the required thickness and then coiling the steel plate. Wherein the finishing temperature is more than 1000 ℃ because Cr is newly precipitated from the structure below 1000 DEG C 2 And N is a brittle phase, so that the hot workability is damaged, and the steel coil is seriously cracked.
The hot rolled steel coil is annealed and pickled at 1020-1120 ℃, the pickling process adopts a sulfuric acid section and mixed acid section (nitric acid and hydrofluoric acid) process, the concentration of the sulfuric acid is 250-400g/L, the main function is to remove rust, and the mixed acid (nitric acid is 140-240g/L and hydrofluoric acid is 15-55 g/L) mainly plays a role in passivation.
Preferably, according to the components of the nickel-saving stainless steel, laterite-nickel ore is smelted into nickel molten iron with the Ni content of 0.8-2.0 percent by a blast furnace, AOD chromium-preserving decarburization smelting is carried out, the alkalinity of tapping is controlled to be 2.0-3.5, the alkalinity is an important condition for ensuring desulfurization, the alkalinity is high, the content of free oxygen ions in slag can be improved, and the desulfurization reaction is favorably carried out. In order to reduce the AOD end-point sulfur content as much as possible, the alkalinity of the reduction stage and the early desulfurization stage needs to be reasonably controlled, specifically, the alkalinity of the reduction stage needs to be controlled to be more than 2.0, and the alkalinity of the early desulfurization stage needs to be controlled to be 2.8-3.5. Then the molten steel enters LF refining to control nitrogen, and is continuously cast into a blank after smelting.
The invention has the beneficial effects that:
the invention has the advantages that through reasonable component design, mn-N alloying, high Cr joint Ni, low V and micro Nb and B alloying, the material has good economy, good hot workability, no edge cracking and good surface quality, compared with the conventional 304 stainless steel, the pitting corrosion resistance, the intercrystalline corrosion resistance and the stress corrosion resistance of the invention are greatly improved, and simultaneously, higher strength (yield strength Rp) is obtained 0.2 > 500 MPa) and excellent plasticity (elongation A) 50 ＞40％)。
Pass through components of the inventionAnd a three-stage heating mode is designed and combined, so that the ferrite content of the casting blank in the hot processing process is not lower than 40%. In addition, the finishing temperature is more than 1000 ℃, and the brittleness-free Cr in the hot rolling process can be ensured 2 N is separated out, and the hot rolling process can not crack, so that the invention can realize the industrial process of continuous casting and slab hot rolling.
The invention preferably controls the alkalinity of each stage in the smelting stage, so that the S content in the stainless steel is extremely low, and good conditions are created for avoiding edge cracking in the rolling process.
In addition, the invention preferably adopts laterite-nickel ore to directly produce molten nickel iron, the Ni content is 0.8-2.0%, and the cost is greatly reduced.
Drawings
FIG. 1 is a drawing showing a real object of a rolled stainless steel prepared in comparative example 1.
Fig. 2 is a drawing of a real object of a roll cracked stainless steel prepared in comparative example 2.
FIG. 3 shows Cr in the cracked stainless steel prepared in comparative example 2 2 And N precipitates out an SEM picture.
Fig. 4 is a drawing of an object of a rolled cracked stainless steel prepared in comparative example 3.
FIG. 5 shows SEM morphology of carbide precipitation of steel coils prepared in comparative example 4.
FIG. 6 is the SEM morphology of the normal steel coil prepared in example 1 without carbide precipitation.
FIG. 7 is a graph of the fitted relationship between the calculated martensite content and the measured martensite content of the M (. Epsilon.40) formula.
Detailed Description
The invention is further illustrated by the following examples and figures.
The compositions of the examples of the present invention and the comparative examples are shown in table 1, and the balance contains Fe and other unavoidable impurities; the manufacturing processes and properties of the examples and comparative examples are shown in tables 2 and 3, respectively. Comparative examples 1 to 3 were severe in cracking after hot rolling and no further processing was performed.
The tensile property of the material is tested according to GB/T228.1 part 1 of the tensile test of metal materials: room temperature test method ";
the intercrystalline corrosion rate-D method tests that according to GB/T4334-2008 'stainless steel intercrystalline corrosion test method', a test solution is 10% nitric acid and 3% hydrofluoric acid, and the test temperature is 70 +/-1 ℃;
the stress corrosion test is carried out according to YB/T5362-2006 method for testing the stress corrosion of stainless steel in boiling magnesium chloride solution, and the test condition is 42 percent boiling magnesium chloride solution;
the pitting potential test is carried out according to GB/T17899-1999 stainless steel pitting potential measuring method, the test solution is 3.5 percent NaCl solution, and the test temperature is 30 +/-1 ℃;
spot corrosion Rate test according to GB/T17897-2016 stainless steel ferric trichloride Spot corrosion test method-method B, the test solution is 6% FeCl 3 +0.16% HCl solution, test temperature 35. + -.1 ℃.
In comparative example 1, the minimum content of ferrite in a cast slab is less than 40% in the hot rolling process, so that the deformation of austenite-ferrite two phases is not coordinated, and finally a hot-rolled steel coil is severely cracked (fig. 1).
Cr of comparative example 2 2 The precipitation temperature of N exceeds 1000 ℃, and Cr is inevitable in the hot working process 2 N brittle phase is separated out, the hot working performance of the material is seriously damaged, the prepared stainless steel is seriously cracked in a rolling way (figure 2), and obvious brittle Cr is found in a cracked sample 2 N precipitates (FIG. 3).
The components and ferrite contents of the comparative example 3 are all in the restricted range of the invention, but the hot rolling finishing temperature is 960 ℃ which is lower than the limited range of the invention by more than 1000 ℃, and as can be seen from figure 4, the stainless steel prepared by the comparative example 3 has serious rolling cracking. The stainless steel product with qualified quality and performance can be prepared only by controlling and controlling the component design, the component constraint and the processing technology in a whole way.
M of comparative example 4 23 C 6 The precipitation temperature of the alloy exceeds 800 ℃ restricted by the invention, the intergranular corrosion performance is seriously reduced, other corrosion resistance is also reduced to a certain extent, and the SEM microstructure observes obvious carbides precipitated along the phase boundary (figure 5), while the SEM appearance of the normal comparative example 1 observes no precipitated phase (figure 6).
The deformed martensite M (. Epsilon.40) of comparative example 5 exceeds the upper limit of the present invention by 30%, and both the strength and the elongation are greatly reduced.
FIG. 7 is a graph of the fitted relationship between the calculated martensite content and the measured martensite content of the M (. Epsilon.40) formula.
As can be seen from table 3, the stress corrosion performance of the 304 austenitic stainless steel is much lower than that of the present invention, and cannot satisfy the corrosion conditions such as Cl ions and the like and the field of load-bearing structures accompanied by stress. The intergranular corrosion rate, the pitting corrosion rate and the pitting potential measured by the steel are superior to those of 304 austenitic stainless steel, the stress corrosion resistance is much superior to those of 304 austenitic stainless steel and 2205 duplex stainless steel, and the steel can meet the use requirements under the conditions of bearing and containing S, cl and other corrosive media, such as coastal or underground structural members containing S, cl and needing bearing.
In conclusion, through reasonable component design, mn-N alloying, high Cr Ni-saving, low V and micro Nb, B alloying, the invention leads the nickel-saving duplex stainless steel to have obviously improved crystal corrosion resistance, pitting corrosion resistance and stress corrosion resistance compared with the conventional 304 stainless steel, and obtains higher strength (yield strength Rp) 0.2 > 500 MPa) and good elongation (A) 50 > 40%). In addition, the method directly produces molten nickel iron by adopting the laterite-nickel ore, the Ni content is 0.8-2.0%, and the nickel-iron alloy is not additionally added, so that the cost is greatly reduced.
Compared with 304 austenitic stainless steel, the invention is more suitable for being applied to the bearing field containing S, cl and other corrosive media and needing to be welded, such as bearing parts of stainless steel bridges, stainless steel high-rise building beam columns, subway pipe galleries, bridge supports and the like, in particular to bearing structural parts of coastal industrial areas.
Claims (6)
1. The niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance comprises the following components in percentage by mass:
C：0.01～0.06％，
Si：0.2～0.9％，
Mn：3.0～5.0％，
Ni：0.8～2.0％，
Cr：20.6～22.5％，
Mo：≤1.0％，
Cu：≤1.0％，
N：0.08～0.15％，
V：＜0.07％，
P：＜0.04％，
S：＜0.0015％，
Nb：0.02～0.30％，
B：0.001～0.003％，
RE:0.01 to 0.03%, and the balance of Fe and other unavoidable impurities, and the following relationships are satisfied:
ferrite ratio F: 40-60%, F =51.3 (Cr +1.5 Si + Mo + 5V +2 Nb)/(Ni + 30C +30N +0.11 Mn-0.009 Mn + Mn) +0.1T-220, T is the final rolling temperature, DEG C;
pitting corrosion resistance equivalent weight PREN is more than or equal to 20.0, PREN = Cr +3.3Mo +30N-Mn;
M 23 C 6 the precipitation temperature is less than or equal to 800 ℃, M 23 C 6 Precipitation temperature =3389 c +3.5 si +9.4 cr +6.4 mo +85 v-214 n-720nb +516;
Cr 2 the precipitation temperature of N is less than or equal to 1000 ℃, cr 2 N deposition temperature =67 Si-9 Mn +1.1 Cr-18 Ni +10 Mo +24 Cu + 781V + 531N-480C +882;
the martensite content M (epsilon 40) generated by the tensile strain of 40 percent, 10 percent to less than M (epsilon 40) to less than 30 percent,
M(ε40)＝246-231*(C+N)-4.6*Si-4*Mn-14*(Ni+Cu)-6.7*Cr-9.2*Mo。
2. the economical high-plasticity duplex stainless steel containing niobium and having excellent resistance to intergranular corrosion according to claim 1, wherein the balance is Fe and other unavoidable impurities.
3. The economical high-plasticity duplex stainless steel containing niobium excellent in intergranular corrosion resistance according to claim 1, wherein the duplex stainless steel has a content of 10% by weight of HNO in mixed acid 3 +3% of the corrosion rate of the crystal under HF conditions < 60 g/(m) 2 * h) The time for cracks to appear in the 42 percent boiling magnesium chloride solution is more than 20 hours, and the time for the cracks to penetrate is more than 90 hours; room temperature yield strength Rp 0.2 More than 500MPa, elongation A 50 ＞40％。
4. The method for producing an economical high-plasticity duplex stainless steel containing niobium excellent in intergranular corrosion resistance as set forth in claim 1 or 2, comprising the steps of:
1) Smelting and casting
Smelting, AOD, LF refining and casting into a casting blank according to the components in the claim 1;
2) Hot rolling
The casting blank is heated by three stages, wherein the total heating time T of the three stages is = (1.0-1.5) h, T unit and min; h, casting blank thickness, unit, mm; wherein the temperature of the preheating section is 600-800 ℃; the first stage heating temperature is 1050-1150 ℃, and the heating time is more than 90min; the second stage has soaking temperature of 1220-1280 deg.c and soaking period of 30-50 min;
then hot rolling is carried out, the steel is coiled after being rolled to the required thickness, and the final rolling temperature is not lower than 1000 ℃;
3) Annealing and pickling
The annealing temperature is 1010-1100 ℃, and the annealing time is 2-8 min; and then acid washing.
5. The method of manufacturing the niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance as claimed in claim 4, wherein the step 1) of smelting uses laterite-nickel ore to smelt nickel-iron water with Ni content of 0.8-2.0% by blast furnace, and the nickel-iron water is subjected to AOD chromium-maintaining decarburization smelting, LF refining and continuous casting into a casting blank; wherein, the steel tapping alkalinity in the smelting stage is 2.0-3.5, the reduction alkalinity is more than 2.0, and the desulfurization alkalinity is 3.0-3.5.
6. The method for producing the niobium-containing economical high-plasticity duplex stainless steel with excellent intergranular corrosion resistance as claimed in claim 4, wherein the pickling in the step 3) employs a sulfuric acid + mixed acid process; the mixed acid is formed by mixing nitric acid and hydrofluoric acid, wherein the concentration of the sulfuric acid is 250-400g/L, the concentration of the nitric acid in the mixed acid is 140-240g/L, and the concentration of the hydrofluoric acid is 15-55 g/L.
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