CN102560286A - Non-magnetic hard-section nickel austenitic stainless steel and preparation method thereof - Google Patents
Non-magnetic hard-section nickel austenitic stainless steel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to non-magnetic hard-section nickel austenitic stainless steel. The non-magnetic hard-section nickel austenitic stainless steel comprises the following chemical components by weight percentage: 0.07-0.12 percent of C, 0.2-1.0 percent of Si, 6.5-9.0 percent of Mn, 17.0-18.0 percent of Cr, 3.5-4.5 percent of Ni, 0.16-0.35 percent of N, 0.51-0.95 percent of Mo, 0.5-2.0 percent of Cu, as well as optionally one or two of 0.02-0.1 percent of V and 0.02-0.1 percent of Nb, and Fe and inevitable impurities in balancing amount. the Ni element is replaced by the C element and the N element to prepare an austenite tissue at room temperature, so that the content of the expensive Ni element can be effectively reduced, thereby reducing the cost; through the synergistic effect of Cr, Mo and N, the pitting resistance equivalent PREN of the material is ensured to be more than or equal to 18, and the corrosion resistance is improved and is equivalent to that of 304; by controlling the Md30/50 temperature to be lower than -35 DEG C and the lowest Md30/50 temperature to be -125 DEG C, after reduction of the cold rolling pressure by 0-80 percent, the yield strength of the material is 360-1590 MPa, but no Martensite phase is formed, so that the material keeps a non-magnetic characteristic, can be widely applied to electronics, apparatuses and instruments and other industries; and compared with the cost of 304 and 305, the cost of the material is obviously reduced.
Description
Technical field
The present invention relates to nitrogenous low-nickel austenitic stainless steel and method of manufacture thereof, hard attitude low-nickel austenitic stainless steel of the no magnetic that especially a kind of solidity to corrosion is good and method of manufacture thereof.
Background technology
The hard attitude material of stainless steel is usually used in industries such as electronics, instrument.The hard attitude material of stainless steel commonly used is mainly S30400 (304) and S30100 (301) in the 300 series austenitic stainless steel.So-called hard attitude stainless steel is meant stainless steel plate or steel band is carried out skin-pass, gives steel band certain cold roling reduction, does not do anneal after the cold working, obtains hard attitude stainless steel product.Hard attitude stainless steel is generally high than the same material intensity after the solution treatment (or anneal), hardness is high, so material is more wear-resisting, longer service life.
The hard attitude material of stainless steel commonly used has 304 and 301, and wherein 304 solidity to corrosion is higher, uses more extensive; 301 solidity to corrosion is lower than 304, generally is used to make rail traffic vehicles.According to the ASTMA240 standard, 304 standard analysis is: C≤0.08%, Si≤0.75%, Mn≤2.0%; Cr:18.0-20.0%, Ni:8.0-10.5%, usually 304 typical composition is C:0.06%, Si:0.4%; Mn:1.0%, Cr:18%, Ni:8%.304 through after rolling or the cold deformation, and intensity and hardness will improve, and table 1 has provided the mechanical property of hard attitude 304.The mechanism that 304 intensity and hardness improve has two: (1) work hardening; (2) strain-induced martensitic transformation sclerosis.Work hardening refers to that 304 stainless steels are in deformation process; The generation of dislocation and accumulation cause resistance to deformation to increase; Generation materials processed sclerosis especially is easy to generate twin and fault in 304 austenitic stainless steels, and twin and fault further hinder moving of dislocation; Increase the degree of work hardening, the hardness of material and intensity are improved.The sclerosis of strain-induced martensitic transformation refers to 304 stainless steels in deformation process, and martensitic transformation takes place, and the generation of martensitic phase causes the strength of materials and hardness to increase, thereby produces transformation hardening.Above-mentioned two mechanism are in the hard attitude stainless steel skin-pass process, the main mode that intensity and hardness increase.
Hard attitude 304 mechanical properties of table 1
But, owing to after the generation of strain-induced martensitic transformation, have the body-centered cubic martensitic phase of high level in the material, and martensitic phase has magnetic, therefore causes whole material to have magnetic.For electron trade and instrument and meter industry,, require material not have magnetic usually for fear of the interference of material to equipment.Therefore, hard attitude 304 stainless steels are restricted in the application of these industries.
The reason that occurs the magnetic martensitic phase after austenitic stainless steel 304 cold working is that its austenite structure is metastable, under effects of strain, martensitic transformation will take place, thereby produces magnetic.For suppressing the generation of martensitic transformation, main approach is exactly to strengthen the stability of austenite phase.The method that adopts at present is to improve nickel content, has produced a new stainless steel trade mark S30500 (305), and 305 composition is: C≤0.12%, Si≤0.75%, Mn≤2.0%, Cr:17.0-19.0%, Ni:10.5-13.5%.Typical composition commonly used is: C:0.06%, Si:0.4%, Mn:1.0%, Cr:18%, Ni:10.5%.After nickel content improved, therefore 305 cold rolling back martensitic phase content can satisfy the application requiring under no magnetic or the low magnetic stripe spare well below 304 stainless steels of depressing equally.But because nickel content is up to 10.5% in 305 stainless steels, so its cost improves greatly.The nickel of every increase by 1% in the stainless steel means the material cost that increases 10-15%.The cost of nickel element accounts for stainless steel material cost about 80%.Since two thousand five, during the important alloying element nickel price in the stainless steel is in always and rises and drops suddenly and sharply, cause Stainless Steel Production very big with the risk of using enterprise.This makes reduction stainless steel material cost and risk become the key issue of development of iron and steel enterprises.Therefore 305 application mainly receives the restriction of cost and price.
CN1089308A discloses a kind of austenite nonmagnetic stainless steel, and its chemical ingredients is:＜0.12%C,＜1.0%Si, 10-13%Mn,＜0.03%P,＜0.03%S; 12-14%Cr, 4-6%Ni, 1.5-2.5%Cu,＜0.02%Re, all the other are Fe; Preferential selection＜0.06-0.1%C,＜1.0%Si, 10-11%Mn,＜0.03%P,＜0.03%S; 12-14%Cr, 4-6%Ni, 1.5-2.5%Cu ,≤0.02%Re, all the other are Fe.Its composition characteristic is to contain a certain amount of REE, and Cr content is far below 304.Even this patent is pointed out this alloy and is carried out deep processing, also can not produce magnetic.
CN1050227A discloses a kind of single-phase austenite magnetism-free stainless steel, it is characterized in that the concrete Chemical Composition of this steel is (weight %): C≤0.08%, Si≤1.5%; Mn:1.0-2.0%, Cr:13.2-14.95%, Ni:12.0-13.9%; Cu:2.5-3.5%, P≤0.025%, S≤0.015%; Re:0.005-0.05%, all the other are Fe.This material mainly increases austenitic stability through adding high-content Ni, after the 20-80% distortion, still be single-phase austenite structure, and the permeance performance is stable.This invention steel mainly is applicable to makes the electrical equipment component.But the solidity to corrosion of this material is lower than 304 steel.
Can find out from above-mentioned patent,, add Cu simultaneously, can reduce the Md30/50 temperature to a certain extent, improve the stability of austenite phase, suppress the generation of strain inducing martensitic phase through improving Ni or Mn content.Added 10-13%Mn like CN1089308A, 1.5-2.5%Cu helps reducing the Md30/50 temperature, reduces or avoid the appearance of magnetic martensitic phase in the cold working process.CN1050227A brings up to 12.0-13.9% with Ni content, guarantees that alloy after the 20-80% distortion, still is single-phase austenite structure.But the solidity to corrosion of CN1089308A and CN1050227A will be far below 304 austenitic stainless steels.
CN 1327078A discloses a kind of austenitic stainless steel of good accurate punching property, and composition is (C+1/2N)≤0.060 quality %, Si≤1.0 quality %; Mn≤5 quality %, S≤0.006 quality %, Cr are 15-20 weight %; Ni is 5-12 quality %; Cu≤5 weight %, Mo are 0-3.0 quality % and Fe and impurity, and the Md30/50 value is controlled in-60～-10 ℃.The hardness increase of cold rolling back steel plate is preferably Vickers' hardness 20% or bigger.The metallographic structure of steel plate is preferably adjusted to #8～#11 grain fineness number in whole as-annealed condition, and the die-cutting performance of this material is improved significantly.But solidity to corrosion significantly is lower than 304 austenitic stainless steels.
EP593158A1 has proposed the Cr-Ni-Mn austenitic stainless steel that a kind of Cu of containing at N, wherein contains Cr:16.5-17.5%, Mn:6.4-8.0%; Ni:2.50-5.0%, Cu:2.0-3.0%, C is not more than 0.15%; N is not more than 0.2%; Si is not more than 1%, and the cold hardening of this alloy is lower than 201, and solidity to corrosion is then near 430.
Existing nitrogenous low-nickel austenitic stainless steel product and patent do not contain Mo basically, adopt to reduce Ni and Cr content in the material simultaneously, and reducing cost, but solidity to corrosion (PREN value) is lower than traditional 304.A kind of nitrogenous austenitic stainless steel that can save nickel chromium triangle is disclosed like CN1129259A; Utilize Mn, N to replace part Ni; In the Ni content and 304 8% is compared remarkable reduction; But in order to guarantee that room temperature obtains the full austenite phase, Cr content also significantly is reduced to 10-15% in the composition, and this will cause solidity to corrosion far below 304.
Provide the hard attitude low-nickel austenitic stainless steel of the good no magnetic of a kind of solidity to corrosion very useful.
Summary of the invention
The object of the present invention is to provide the hard attitude low-nickel austenitic stainless steel of a kind of no magnetic.
Be the realization above-mentioned purpose, the hard attitude low-nickel austenitic stainless steel of no magnetic of the present invention, its chemical component weight per-cent is: C:0.07-0.12%; Si:0.2-1.0%, Mn:6.5-9.0%, Cr:17.0-18.0%; Ni:3.5-4.5%, N:0.16-0.35%, Mo:0.51-0.95%; Cu:0.5-2.0%, and optional add among V:0.02-0.1% and the Nb:0.02-0.1% one or both, surplus is Fe and unavoidable impurities.
Another object of the present invention is to provide the method for manufacture of the hard attitude low-nickel austenitic stainless steel of above-mentioned no magnetic, and this method comprises:
Press mentioned component and smelt, die casting or continuous casting form strand, forge then or hot rolling, and annealing and pickling is handled;
To required thickness, it is rolling to be called modulation with cold-rolling of steel plate, perhaps processing such as cold forging; Intensity and hardness that acquisition needs; Because the material martensitic transformation temperature is lower than-35 ℃, roll and can not produce martensitic phase after hard, therefore obtain the high-intensity while; Steel plate does not produce magnetic, has the hard attitude low-nickel austenitic stainless steel of good corrosion proof no magnetic thereby prepare.
Preferably, adding electric furnaces such as ferrochrome, ferronickel and steel scrap are melted, pour molten steel into the AOD stove after molten clear; In the AOD stove, take off C, take off S and increase N, control the blowing of N; When the smelting composition reaches requirement, pour molten steel into tundish, and continuous casting; Wherein the superheating temperature of continuous casting is 30-80 ℃, and the slab pulling rate is 0.6-2m/min;
Then continuous casting steel billet is heated to 1100-1250 ℃, batches after being rolled down to desired thickness again;
Carry out cold rollingly after the continuous pickling annealing, draught is 0-80%.
The present invention utilizes C, N element to replace the Ni element, obtains the austenite structure under the room temperature, can effectively reduce expensive Ni constituent content, thereby reduce cost; Utilize elements such as C, N significantly to reduce the Md30/50 temperature simultaneously, improve the stability of austenite phase, suppress the generation of strain-induced martensitic phase, with the austenitic stainless steel of no magnetic after developing low-cost, the cold deformation.Through adding the Mo of 0.51-0.95%, utilize the synergy of Cr, Mo and N simultaneously, guarantee the equivalent of anti-spot corrosion PREN >=18 of material, improve erosion resistance, with 304 suitable; Be lower than-35 ℃ through control Md30/50 temperature; Minimum reaching-125 ℃, after the 0-80%, material yield intensity reaches 360-1590MPa under the cold rolling; But not having martensitic phase generates; Therefore material still keeps not having the characteristic of magnetic, can be widely used in industries such as electronics, instrument, and cost and 304 is compared obvious reduction with 305.
Description of drawings
Fig. 1 is the alloy metallograph of the embodiment of the invention 2.
Embodiment
Below in conjunction with embodiment characteristics of the present invention and advantage are carried out detailed explanation.
Among the present invention, unless otherwise, content all refers to weight percent content.
For realizing the hard attitude low-nickel austenitic stainless steel of the no magnetic above-mentioned purpose that provides of the present invention, each elemental composition is controlled as follows:
Carbon, carbon are strong austenite formers, can replace nickel to a certain extent, promote austenite to form, and the stable austenite tissue, significantly reduce the Md30/50 temperature, effectively suppress the formation of magnetic martensitic phase in the strain path.But when carbon content was too high, carbon combined the back to form rich chromium carbide at crystal boundary with chromium, cause intergranular corrosion.In addition, the rich chromium carbide of formation also reduces the impelling strength of steel.Cross low carbon content and will increase difficulty and cost in the preparation process.Therefore, the control carbon content is 0.07-0.12% in the steel of the present invention.
Silicon, silicon are the elements that contains usually in the Manufacture Of Iron And Steel By Melting.Silicon is that ferritic forms and stable element.Silicon is used for deoxidation in fusion process, silicon can improve the hot strength of ferritic phase simultaneously, contains the silicon more than 0.2% in the therefore general stainless steel.Will reduce the solubleness of nitrogen when but silicone content is too high, and quicken separating out of intermetallic phase.Therefore, the control silicone content is 0.2-1.0% in the steel of the present invention.
Manganese; Manganese is that a kind of austenite forms and stable element, can utilize manganese to replace nickel to a certain extent, obtains austenite structure; The interpolation of manganese simultaneously can significantly improve the solubleness of nitrogen; The interpolation of manganese also can reduce the Md30/50 temperature in addition, and every interpolation 1%Mn can make the Md30/50 temperature reduce by 8 ℃.But manganese all is negative to the influence of stainless erosion resistance basically.The experimental formula of estimating the anti-pitting attack performance of nitrogen-contained stainless steel is: PREN (equivalent of anti-the spot corrosion)=%Cr+3.3%Mo+30%N-%Mn.For guaranteeing electrocorrosion-resisting property, control Mn content is 6.5-9.0% in the steel of the present invention.
Chromium, chromium are the most important elements that steel obtains corrosion resistance nature.Because chromium is the element that significantly strengthens corrosion resistance nature, for guaranteeing good solidity to corrosion, chromium content is controlled at more than 17.0% in the steel of the present invention.But chromium is main ferrite former, and too high chromium will cause occurring in the material ferritic phase, can not guarantee that acquisition does not have the austenite of magnetic fully under the room temperature state, so need corresponding higher nickel equivalent to cooperate with it, to guarantee to obtain the room temperature austenite structure.Therefore, chromium content is controlled at 17.0-18.0% in the steel of the present invention.
Nickel, nickel are that the intensive austenite forms and stable element, are main austenizers in the 300 series austenitic stainless steel.Nickel is to reduce the Md30/50 temperature simultaneously, improves the important element of austenite phase stability.But nickel costs an arm and a leg; The cost of nickel accounts for more than 80% of material cost in 300 series austenitic stainless steel; The nickel of every reduction by 1% in the stainless steel means the material cost that reduces 10-15%, so nickel content is controlled at 3.5-4.5% in the steel of the present invention; To guarantee that material has lower cost, guarantee the austenite structure of steel simultaneously in room temperature.
Nitrogen, nitrogen are a kind of strong austenite formers.The present invention reduces the Md30/50 temperature through adding, and effectively suppresses the formation of magnetic martensitic phase in the strain path.More advantageously nitrogen solid solubility in austenite is higher, forms carbide easily with carbon and separates out differently, and nitride generally can not separated out in mutually at austenite.The adding of nitrogen simultaneously helps improving intensity and corrosion resistance nature, the especially nitrogen of steel and the synergy of molybdenum can significantly improve anti-pitting attack performance and slit and corrosion resistant performance.When but nitrogen content is too high, the raising that will improve melting and hot worked difficulty, especially nitrogen content will cause serious hot rolling limit to be split, and cause being difficult to producing existing producing on the line.Therefore, nitrogen in steel content of the present invention is controlled at 0.16-0.35%.
Molybdenum, molybdenum are very beneficial for improving the corrosion resistance nature of steel.The present invention significantly promotes the enrichment of chromium in passive film through adding molybdenum, thereby strengthens the stability of passivation film on stainless steel surface, significantly strengthens the anti-corrosion effect of chromium in the steel, thereby improves the solidity to corrosion of stainless rustless property and anti-various media greatly.Simultaneously molybdenum can also improve the passivation ability again of steel in stainless steel, improves the ability of anti-spot corrosion and crevice corrosion, also to preventing with the spot corrosion to be that the stress corrosion that originates from is favourable, improves stainless anticorrosion stress-resistant and crevice corrosion ability.Molybdenum can also act synergistically with nitrogen, further improves pitting resistance.Therefore the molybdenum content in the steel of the present invention is controlled at 0.51-0.95%.
Copper, copper are a kind of austenite formers, and the present invention improves stainless plasticity and the erosion resistance in reductive acid through adding copper, helps improving the slit and corrosion resistant performance simultaneously.But be unfavorable for hot workability during the copper too high levels.Therefore copper content is controlled at 0.5-2.0% in the steel of the present invention.
Vanadium, niobium, as optional element, main effect in the present invention is a thinning microstructure, improves the molten steel purity, improves hot workability, its content all is controlled at below 0.1%.
Austenite is to the martensitic transformation discovery of strain-induced in 304 stainless steels through analyzing for the contriver, and the generation of martensitic transformation is depended on austenite stability mutually with the increase of amount.Generally estimate the trend that austenite changes the strain-induced martensitic phase mutually into, when its implication is strain 50%, produces martensitic phase content and reach 30% temperature with the Md30/50 temperature.In other words, material was out of shape 50% o'clock under this temperature, and martensitic phase content can reach 30%.If the Md30/50 temperature is high more, represent in this material austenite more unstable mutually, the trend of material induced martensite took place martensitic transformation is just obvious more.Can calculate the Md30/50 temperature with following experimental formula, Md30/50=413-9.5Ni%-13.7Cr%-8.1Mn%-9.2Si%-462 (C%+N%).Calculate Md30/50 (304)=50 ℃ of 304 steel according to this experimental formula, 305 stainless Md30/50 (305)=27 ℃.It is thus clear that 304 Md30/50 temperature is higher, therefore induced martensite took place martensitic phase phase transformation easily in cold-rolled process causes material production magnetic; 305 Md30/50 temperature and 304 has relatively reduced by 23 ℃, thus the amount that takes place of its strain-induced martensitic transformation be less than 304,305 under cold rolling, can keep not having magnetic or weak magnetic under the less condition characteristic.But, said as preamble, added more nickel in 305, will cause material cost to raise more than 20%, therefore limited the promotion and application of material.
Can find out that according to the Md30/50 calculation formula interpolation of Cr, Ni and Mn element can reduce the Md30/50 temperature, improves austenitic stability; More significantly add two kinds of elements of C and N, can improve the stability of austenite phase greatly, suppress the generation of magnetic martensitic phase in the cold working process.But; Element proportionings such as Cr, Ni, Mn, C, N not only determine the cost of alloy; Also influence the Cr:Ni equivalence ratio; Determine simultaneously whether room temperature has the formation risk of harmful precipitated phase in fully austenitic structure, the decision alloy, and wherein Cr, N, Mo etc. still determine the key element of characteristic-erosion resistance that it is important, and its influence can be represented according to the equivalent of anti-spot corrosion formula PREN=%Cr+3.3%Mo+30%N-%Mn.
For this reason; In the composition design process of the present invention, consider that Ni, N, C, Mn, Cu etc. are austenite formers, Cr, Mo, Si etc. are ferrite formers; Must guarantee enough austenite formers, guarantee that at first material had the fully austenitic structure of no magnetic before cold working not.
At first; The present invention is that 1.44-1.90 controls phase composite through the equivalence ratio Creq/Nieq of control chromium and nickel; Guarantee that steel of the present invention at room temperature obtains austenite structure, guarantee that material has advantages such as nonmagnetic, unit elongation high and low temperature good toughness and the plasticity of austenite structure be good.
The present invention is through elements such as adjustment Cr, Ni, Mn; Especially the content of C and N element; Impel the Md30/50 temperature of material to be lower than-35 ℃, compare with 305 Md30/50 temperature (27 ℃) all with 304 Md30/50 temperature (50 ℃) and significantly reduce, so the austenite of material is more stable mutually; Can guarantee after strain such as cold rolling grade, still to keep the austenite phase of no magnetic, not produce the martensitic phase of magnetic.
The present invention is lower than 0.95% through control Mo content; Ni content is 3.5-4.5%, and 8% in the material in the Ni content and 304 is compared remarkable reduction, and the Ni of every reduction by 1%; Can make material cost reduce 10-15%, so material cost significantly is lower than 304 austenitic stainless steels.
The present invention reduces cost through replacing Ni with N, Mn simultaneously, and control N content does not influence performances such as moulding simultaneously smelting and difficulty of processing not strengthen below 0.35%.
Steel of the present invention is guaranteed Cr content greater than 17.0%, and control Mn content is lower than 9%, adds a certain amount of Mo and N then.Wherein Mo can significantly promote the enrichment of chromium in passive film, thereby strengthens the stability of passivation film on stainless steel surface, significantly strengthens the anti-corrosion effect of Cr in the steel, thereby improves the solidity to corrosion of stainless rustless property and anti-various media greatly.Simultaneously Mo can also improve the passivation ability again of steel in stainless steel, and the ability of its anti-spot corrosion and crevice corrosion is about 3 times of chromium, and Mo also to preventing with the spot corrosion to be that the stress corrosion that originates from is favourable, improves stainless anticorrosion stress-resistant and crevice corrosion ability.Utilize the interaction between Cr, Mo and the N three, N promotes the enrichment of Cr in Passive Film, improves the passivation ability of steel, and N and Mo can also improve the stability of passive film; N can improve the pH value of microcell, adds a certain amount of Mo, and comprehensively adjusts the content of N, Ni, Mn, guarantees PREN >=18 of material, reaches the erosion resistance suitable with 304 austenitic stainless steels.This also is that the present invention is different from existing low-nickel austenitic stainless steel part, because existing low-nickel austenitic stainless steel is main to reduce cost, solidity to corrosion is lower than austenitic stainless steel 304.
The hard attitude low-nickel austenitic stainless steel of the no magnetic that above-mentioned solidity to corrosion of the present invention is good can be produced through common process.
Preferably, through comprising the method manufacturing of following steps:
Its chemical component weight per-cent is: C:0.07-0.12%, Si:0.2-1.0%, Mn:6.5-9.0%; Cr:17.0-18.0%, Ni:3.5-4.5%, N:0.16-0.35%; Mo:0.51-0.95%, Cu:0.5-2.0%, optional a kind of two kinds of adding among V:0.02-0.1% and the Nb:0.02-0.1%; Surplus Fe and inevitable impurity, the appropriate design through composition makes material Md30/50 temperature be lower than-35 ℃;
Press mentioned component and smelt, die casting or continuous casting form strand, forge then or hot rolling, and annealing and pickling is handled;
To required thickness, it is rolling to be called modulation with cold-rolling of steel plate, perhaps processing such as cold forging; Intensity and hardness that acquisition needs; Because the material martensitic transformation temperature is lower than-35 ℃, roll and can not produce martensitic phase after hard, therefore obtain the high-intensity while; Steel plate does not produce magnetic, has the hard attitude low-nickel austenitic stainless steel of good corrosion proof no magnetic thereby prepare.
The present invention compared with prior art has the following advantages:
Existing austenitic stainless steel 304 cold rolling hard attitude products generally have magnetic, have influenced its application in no magnetic fields such as electronic units.The content of noble element nickel reaches 8% in while 304, and material cost is higher; Austenite is more stable than 304 in the nickelic austenitic stainless steel 305; Can guarantee under certain draught condition, not produce in the hard attitude product strain-induced martensitic phase of magnetic; But the content of your elemental nickel is higher than 10.5% in 305, so cost is higher than 304, has limited its application.
The present invention utilizes the austenitizing effect of elements such as manganese, carbon, nitrogen, replaces noble element nickel on the one hand, guarantees that material has the austenite phase in room temperature, can effectively reduce cost; On the other hand, utilize manganese, carbon, nitrogen, especially carbon and nitrogen element significantly reduce the Md30/50 temperature, improve the stability of austenite phase, guarantee in cold-rolled process, not produce the martensitic phase of magnetic.Guarantee that through adding an amount of chromium, molybdenum and nitrogen material has good solidity to corrosion.
Existing nitrogenous low-nickel austenitic stainless steel product and patent do not contain Mo basically, adopt to reduce Ni and Cr content in the material simultaneously, and reducing cost, but solidity to corrosion (PREN value) is lower than traditional 304.Solidity to corrosion like CN1129259A, CN101338403A, CN1089308A, CN1050227A and the disclosed material of EP593158A1 will be far below 304 austenitic stainless steels.
The present invention replaces noble metal Ni through adding elements such as C, N, Mn, utilizes C, N etc. significantly to reduce the Md30/50 temperature simultaneously; Improve the austenite phase stability; Reduce the generation of magnetic martensitic phase in the cold working process, through Cr content is controlled at 17-18%, add the Mo element of 0.51-0.95% simultaneously; Guarantee the equivalent of anti-spot corrosion PREN value >=18 of alloy, corrosion resistance nature is suitable with 304 austenitic stainless steels.
The hard attitude low-nickel austenitic stainless steel of no magnetic of the present invention existing stainless steel capable of using produces line and produces in batches; Product has excellent mechanical property and corrosion resisting property: after 0-80% is depressed in cold working; Ys Rp0.2 is the martensitic phase that does not produce magnetic in 360-1590MPa, the especially material; Anti-spot corrosion equivalent value PREN=Cr%+3.3%Mo+30N%-Mn% >=18, with 304 austenitic stainless steels quite or be higher than 304 austenitic stainless steels.
Table 2 is depicted as the chemical ingredients of embodiment of the invention steel grade, and table 2 has provided the chemical ingredients of standard 304 austenitic stainless steels of example as a comparison simultaneously.Give Md30/50 temperature, Cr equivalent, Ni equivalent, spot corrosion equivalent PREN etc.
The composition unit of table 2 embodiment of the invention and Comparative Examples: weight percent
| Numbering | C | Si | Mn | Cr | Ni | Mo | Cu | N | V | Nb |
| Embodiment 1 | 0.120 | 0.8 | 6.5 | 17.5 | 4.1 | 0.95 | 1.5 | 0.20 | 0.10 | |
| Embodiment 2 | 0.080 | 0.4 | 6.6 | 17.0 | 3.8 | 0.85 | 1.6 | 0.16 | 0.10 | 0.06 |
| Embodiment 3 | 0.076 | 0.6 | 7.0 | 17.9 | 3.5 | 0.51 | 0.8 | 0.35 | 0.02 | 0.05 |
| Embodiment 4 | 0.100 | 0.2 | 7.8 | 17.6 | 4.5 | 0.70 | 0.5 | 0.25 | 0.10 | |
| Embodiment 5 | 0.070 | 0.5 | 7.0 | 18.0 | 4.4 | 0.68 | 1.3 | 0.32 | 0.07 | |
| Embodiment 6 | 0.085 | 0.4 | 7.2 | 17.2 | 3.6 | 0.85 | 2.0 | 0.18 | 0.05 | |
| Embodiment 7 | 0.075 | 1.0 | 6.8 | 17.8 | 3.9 | 0.71 | 1.6 | 0.30 | 0.07 | |
| Embodiment 8 | 0.072 | 0.6 | 9.0 | 18.0 | 4.0 | 0.90 | 1.5 | 0.30 | 0.02 | 0.02 |
| Comparative Examples | 0.06 | 0.4 | 1.0 | 18.0 | 8.0 | 0 | 0 | 0 |
The performance of table 3 embodiment and Comparative Examples
| Numbering | Md30/50 | PREN | Creq | Nieq | Creq：Nieq |
| Embodiment 1 | -73.6 | 20.14 | 19.65 | 12.423 | 1.582 |
| Embodiment 2 | -35.0 | 18.81 | 19.25 | 10.152 | 1.896 |
| Embodiment 3 | -124.5 | 23.08 | 19.31 | 13.254 | 1.457 |
| Embodiment 4 | -97.6 | 19.61 | 18.6 | 12.837 | 1.449 |
| Embodiment 5 | -116.9 | 22.84 | 19.43 | 13.539 | 1.435 |
| Embodiment 6 | -48.1 | 18.71 | 19.15 | 10.612 | 1.805 |
| Embodiment 7 | -105.4 | 22.34 | 20.01 | 12.896 | 1.552 |
| Embodiment 8 | -121.9 | 20.97 | 19.80 | 12.745 | 1.554 |
| Comparative Examples | 50.9 | 17.00 | 18.60 | 9.890 | 1.881 |
The embodiment of the invention is an example with the Production Flow Chart that electric furnace-AOD smelts: adding electric furnaces such as ferrochrome, ferronickel and steel scrap are melted; Pour molten steel into the AOD stove after melting clearly; In the AOD stove, take off C, take off S and increase N, control the blowing of N; When the smelting composition reaches requirement, pour molten steel into tundish, and on vertical-bending caster, cast.The superheating temperature of continuous casting is 30-80 ℃, and the slab pulling rate is 0.6-2m/min.Continuous casting steel billet is put into roller hearth type heating furnace be heated to 1100-1250 ℃, after being rolled down to desired thickness on the hot continuous rolling unit, batch.Carry out successive pickling annealing then, carry out then under the cold rolling, draught 0-80% specifically confirms according to the hardness and the intensity of user's needs, finally obtains the good hard attitude low-nickel austenitic stainless steel of the no magnetic product of solidity to corrosion.
Test Example 1: metallographic structure
The alloy metallograph of embodiment 2 (room temperature is an austenite structure) as shown in Figure 1, sample is through electrolytic corrosion, and etching reagent is saturated oxalic acid solution, corrosion current 0.2-0.4A/cm
2
Test Example 2: mechanical property
Table 4 has provided the mechanical property after the different distortion amount is depressed in steel of the present invention and contrast steel grade cold working, utilizes the magnetic tester to detect the content that magnetic martensitic phase in the material of back is depressed in different cold working, and with 304 contrast.Mechanical property is all taken from cold-reduced sheet, adopts JIS 13B standards and detection.Its result sees table 3.
The mechanical property of table 4 embodiment of the invention and Comparative Examples
Annotate: Comparative Examples is 304 austenitic stainless steels of standard.
2-4 result is visible by table, and steel of the present invention obtains the room temperature austenite structure owing to utilize C, N to replace the austenitizing effect of noble metal Ni; Utilize C, N, Mn can reduce the characteristic of Md30/50 temperature simultaneously, the Md30/50 temperature of material is reduced to-35 ℃, minimumly can be reduced to-125 ℃; After material is depressed through cold working; Intensity and hardness etc. significantly improve, and can satisfy the needs to material mechanical performance such as electron trade, simultaneously since the stability of austenite phase improve; The sclerosis of material mainly produces through work hardening; I.e. generation and accumulation through dislocation and twin produces, and do not produce the martensitic phase of magnetic, guarantees the no magnetic properties of hard attitude material.On the other hand, guarantee that Cr content is higher than 17% in the material, through adding the Mo of 0.51-0.95%; Utilize the synergy of Mo and N, improve erosion resistance, especially through element proportionings such as adjustment Cr, Mo, N and Mn; Guarantee the equivalent of anti-spot corrosion PREN >=18 of material; With 304 austenitic stainless steels quite or be higher than 304 austenitic stainless steels, thereby prepare a kind of solidity to corrosion good contain the molybdenum low-nickel austenitic stainless steel, have good comprehensive performances and lower cost simultaneously.Have only 4.1% such as Ni content among the embodiment 1, compare Ni with 304 and reduced about 4%, it is about more than 30% to reduce cost; But material still has the austenite structure under the room temperature, and the PREN value reaches more than 20, keeps good solidity to corrosion; Its Md30/50 temperature is reduced to-75 ℃; Behind the cold deformation 30%, do not produce the martensitic phase of magnetic in the material, and 304 after identical depressing martensitic phase content reach 22%.Explain that material of the present invention can keep corrosion resistance nature when reducing material cost; Simultaneously after cold working, can keep not having the characteristic of magnetic, can be widely used in the field of corrosion resistance natures such as electronic machine, equipment, intensity and hardness requirement height and the necessary no magnetic of requirement.
Claims (8)
1. do not have the hard attitude low-nickel austenitic stainless steel of magnetic, its chemical component weight per-cent is: C:0.07-0.12%, Si:0.2-1.0%; Mn:6.5-9.0%, Cr:17.0-18.0%, Ni:3.5-4.5%; N:0.16-0.35%, Mo:0.51-0.95%, Cu:0.5-2.0%; And optional add among V:0.02-0.1% and the Nb:0.02-0.1% one or both, surplus is Fe and unavoidable impurities.
2. the hard attitude low-nickel austenitic stainless steel of no magnetic as claimed in claim 1 is characterized in that V:0.02-0.1%.
3. according to claim 1 or claim 2 the hard attitude low-nickel austenitic stainless steel of no magnetic is characterized in that Nb:0.02-0.1%.
4. like the hard attitude low-nickel austenitic stainless steel of the arbitrary described no magnetic of claim 1-3, it is characterized in that the equivalence ratio Creq/Nieq of chromium and nickel is 1.44-1.90.
5. like the hard attitude low-nickel austenitic stainless steel of the arbitrary described no magnetic of claim 1-4, it is characterized in that its Md30/50 temperature is lower than-35 ℃.
6. like the hard attitude low-nickel austenitic stainless steel of the arbitrary described no magnetic of claim 1-5, it is characterized in that PREN >=18.
7. like the method for manufacture of the hard attitude low-nickel austenitic stainless steel of the arbitrary described no magnetic of claim 1-6, comprise the steps:
Press mentioned component and smelt, die casting or continuous casting form strand, forge then or hot rolling, and annealing and pickling is handled;
To required thickness, intensity that acquisition needs and hardness and steel plate do not produce magnetic, have the hard attitude low-nickel austenitic stainless steel of good corrosion proof no magnetic thereby prepare with cold-rolling of steel plate or Cold Forging.
8. method as claimed in claim 7 is characterized in that, in the smelting; Adding electric furnaces such as ferrochrome, ferronickel and steel scrap are melted, pour molten steel into the AOD stove after molten clear, in the AOD stove, take off C, take off S and increase the blowing of N, control N; When the smelting composition reaches requirement, pour molten steel into tundish, and continuous casting becomes slab; Wherein the superheating temperature of continuous casting is 30-80 ℃, and the slab pulling rate is 0.6-2m/min;
Then continuous casting steel billet is heated to 1100-1250 ℃, batches after being rolled down to desired thickness again;
Carry out cold rollingly after the continuous pickling annealing, draught is 0-80%.
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