CN105525226A - Martensitic stainless steel wire rod and production method thereof - Google Patents
Martensitic stainless steel wire rod and production method thereof Download PDFInfo
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Abstract
The invention relates to a martensitic stainless steel wire rod and a production method thereof. The martensitic stainless steel wire rod is prepared from the following chemical components in weight percent: 0.30-0.65% of carbon, 0.20-0.50% of silicon, less than or equal to 0.60% of manganese, less than or equal to 0.30% of nickel, 11.50-17.00% of chromium, 0.20-0.50% of molybdenum, less than or equal to 0.25% of copper, less than or equal to 0.030% of sulfur, less than or equal to 0.040% of phosphorus, 0.02-0.20% of nitrogen, and the balance being ferrum and unavoidable impurities. The martensitic stainless steel wire rod which is excellent in surface, steady in performance and uniform in texture can be obtained by adopting the steps of smelting, casting, rolling, online hot charging annealing, salt bath, pickling, finishing to finished product inspecting and packaging, and the martensitic stainless steel wire rod has tensile strength of more than 600MPa, yield strength of more than 300MPa, elongation of more than 25%, percentage reduction of area of more than 50% and qualified product ratio of more than 85%. According to the invention, the comprehensive utilization performance of steel is improved, and the problem that surface stress cracking is easy to cause in annealing of high-carbon martensitic stainless steel in the prior art is solved on the basis of not increasing the smelting and rolling cost.
Description
Technical field
The present invention relates to a kind of Martensite Stainless Steel wire rod and manufacture method thereof.
Background technology
Martensite Stainless Steel is the stainless steel that a class can be adjusted its performance by thermal treatment (quenching, tempering).This kind of steel must possess two primary conditions: one is to have austenite phase field to exist in equilibrium phase diagram, long-time heating is carried out within the scope of this regional temperature, make after carbide is solidly soluted in steel, carry out quenching and form martensite, namely chemical composition must control in γ or γ+alpha phase zone, two is to make alloy form passive film that is corrosion-resistant and oxidation, and chromium content must more than 10.5%.By the difference of alloying element, martensitic chromium stainless steel and martensitic chromium nickel and stainless steel can be divided into.
Wire rod is also wire rod, is often referred to into the minor diameter round steel of dish.The diameter (GB/T4356-2002) within the scope of 5.5 ~ 30 millimeters of wire rod.Stainless steel wire rod is for the manufacture of Stainless Steel Wire, stainless steel spring steel wire, stainless upset steel wire and stainless steel wire rope steel wire.By the tissue typing of steel, the material of stainless steel wire rod mainly contains: austenitic stainless steel, ferritic stainless steel, Martensite Stainless Steel, duplex stainless steel and PH Stainless Steel.The Martensite Stainless Steel wire rod of Low-cost corrosion-resistant is current purposes stainless steel wire rod comparatively widely.
At present, Martensite Stainless Steel wire rod is mainly divided into two classes: 1) Chromium Stainless Steel wire rod (not nickeliferous): typical steel grade is 12Cr12,06Cr13,12Cr13, Y12Cr13,20Cr13,30Cr13,40Cr13,68Cr17,85Cr17,95Cr18, such material manufacturing cost lower (not containing Ni), intensity after tempering of quenching is 490 ~ 735MPa, and relative reduction in area is 8 ~ 25% (GB/T1220); But, along with the increase of intensity, the plasticity of this kind of stainless steel wire rod obviously reduces, and (intensity as 30Cr13 in GB/T1220 is >=735MPa, but relative reduction in area only has >=and 12%), this just causes the martensite wire rod of high strength (medium high carbon) very easily to ftracture because plasticity is low in process of production, reduces the lumber recovery of this kind of stainless steel wire rod, therefore needs to carry out softening annealing or Spheroidizing Annealing to it, add energy consumption, too increase the manufacturing cost of such wire rod; 2) chromium nickel stainless steel wire rod (nickeliferous): typical steel grade is 2Cr17Ni3, X3CrNiMo13-4, X4CrNiMo16-5-1, the intensity after tempering of quenching is higher, be 760 ~ 1100MPa, can meet the requirement of strength of stainless steel component product, also better (relative reduction in area of 2Cr17Ni3 is 17 ~ 25% to plasticity simultaneously; The relative reduction in area of X3CrNiMo13-4 is 15 ~ 20%; The relative reduction in area of X4CrNiMo16-5-1 is 20 ~ 25%), also not easily there is cracking in production process.But Ni content is up to 3.0 ~ 6.0% in steel, because Ni is precious metal element, this just significantly increases the cost of steel, inhibits the popularization and application of such material.
For Martensite Stainless Steel wire rod, current annealing process is mainly: 1) Full Annealing: be slowly heated to more than Ac3 (hypoeutectoid steel) or Ac1 (eutectoid steel or hypereutectoid steel) 30 ~ 50 DEG C (being generally 750 ~ 860 DEG C), keep appropriate time (being generally 4 ~ 8 hours), then Slow cooling gets off.The recrystallization of second-order phase transition in contrast to this occurred in austenite (once phase-change recrystallization) and process of cooling is changed into by the perlite (or also having the ferrite of pro-eutectoid or cementite) occurred in heat-processed, formation crystal grain is comparatively thin, lamella is thicker, the perlite of homogeneous microstructure (or also having proeutectoid ferrite or cementite), be mainly used in the foundry goods of hypoeutectoid steel, forging rolling part, weldment, to eliminate tissue defects (as Widmannstatten structure, banded structure etc.), tissue is attenuated and becomes evenly, to improve plasticity and the toughness of steel part; 2) underannealing: to be slowly heated between Ac1 and Ac3 between (hypoeutectoid steel) or Ac1 and Acm (hypereutectoid steel), be generally Ac1+ (40 ~ 60) DEG C (680 ~ 780 DEG C), insulation for some time (unusual according to specification is 6 ~ 12 hours) Slow cooling afterwards, make the recrystallization person of steel generating portion, be called underannealing, mainly be applicable to middle, high-carbon and low alloy steel, its objective is thinning microstructure and reduce hardness.
Therefore, the Martensite Stainless Steel wire rod of the medium high carbon ([C] >=0.30%) of design a kind of economical (low cost), meet the requirement of strength of standardized component and shaft forgings and not easy to crack, can reduce energy consumption, be the technology pursue of steelmaker simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of Martensite Stainless Steel wire rod and manufacture method thereof, by optimizing and the strict chemical composition controlling steel, adopt distinctive online annealing heat treatment process simultaneously, the final Martensite Stainless Steel wire rod manufacturing excellent, the stable performance in surface, homogeneous microstructure, to improve the comprehensive use properties of steel; The problem of surface stress cracking is easily there is when the basis not increasing smelting and rolling cost solves the annealing of existing medium high carbon Martensite Stainless Steel.
The present invention, by the proportion optimizing of alloying constituent, particularly reduces the interpolation of precious metal element and rational thermal treatment process, to reach the optimization of cost and material property.The Martensite Stainless Steel wire rod that the present invention produces, low cost of manufacture, excellent surface quality, comprehensive use properties is up to state standards, and meets user's service requirements; Meanwhile, the annealing energy consumption of existing Martensite Stainless Steel wire rod can be reduced, reduce Carbon emission, while protection of the environment, reduce manufacturing cost.The present invention, for particularly effective on medium high carbon martensite wire rod (especially 3Cr13,4Cr13,60Cr13Mo etc.), substantially increase lumber recovery, reduces surface imperfection incidence and manufacturing cost.
For achieving the above object, the present invention mainly adopts following technical scheme:
A kind of Martensite Stainless Steel wire rod, its chemical component weight per-cent is: carbon 0.30 ~ 0.65%, silicon 0.20 ~ 0.50%, manganese≤0.60%, nickel≤0.30%, chromium 11.50 ~ 17.00%, molybdenum 0.20 ~ 0.50%, copper≤0.25%, sulphur≤0.030%, phosphorus≤0.040%, nitrogen 0.02 ~ 0.20%, all the other are iron and inevitable impurity.
Further, the tensile strength > 600MPa of Martensite Stainless Steel wire rod of the present invention, yield strength > 300Mpa, elongation > 25%, relative reduction in area > 50%, lumber recovery > 85%.
In present component design:
Carbon: carbon is the element of stable austenite, simultaneously carbon forms carbide and is solid-solution in ferrite and strengthens matrix in stainless steel with the alloying element such as Cr, Mn, Mo, and the intensity of steel and hardness are increased substantially, but, carbon too high then to toughness and intergranular corrosion unfavorable.Therefore, it is 0.30 ~ 0.65% that carbon controls, and can guarantee good toughness and erosion resistance while acquisition high strength.
Manganese: manganese is austenite stabilizer element, but the effect of manganese does not lie in formation austenite, but be that it reduces the critical quenching rate of steel, increasing austenitic stability when cooling, suppressing austenitic decomposition.Therefore, manganese can increase the hardening capacity of steel, is conducive to adopting Direct Air-Cooled to quench aborning and just can obtains martensitic stucture.Meanwhile, manganese also plays the effect of reductor and sweetening agent, can cleaning molten steel, but too high meeting impels coarse grains, and in addition, in the corrosion resistance nature improving steel, the effect of manganese is little.Therefore, manganese≤0.60% is controlled.
Silicon: silicon is ferrite former, have bad impact, but silicon is solid-solution in ferrite and austenite, has obvious strengthening effect on formation austenite.Silicon reduces the solubleness of carbon in austenite, impels Carbide Precipitation, improves intensity and hardness.Meanwhile, the avidity of silicon and oxygen is only second to aluminium and titanium, and is better than manganese, chromium, vanadium, is good reductive agent and reductor, can improves the density of steel, but silicon is too high will significantly reduce plasticity and the toughness of steel.Therefore, it is 0.20 ~ 0.50% that silicon controls, and can ensure good obdurability and intergranular corrosion resistance performance.
Chromium: chromium is carbide forming element, facilitates the passivation of steel and makes steel keep stablizing the result of passive state.Stainless erosion resistance is mainly due to the formation of the rich surface chromium oxide film of steel.Meanwhile, chromium is again formed and stablize ferritic element, is dissolved in austenite and strengthens matrix and do not reduce toughness, reduce austenitic area, and postponing Cooling Austenite Transformation, is useful to anti intercrystalline corrosion and resistance of oxidation.In addition, chromium energy crystal grain thinning, improves the temper resistance of quenched and tempered steel.Therefore, in steel of the present invention, chromium content is 11.50 ~ 17.00%.
Nickel: be formed and the element of stable austenite, improve the tissue of high chromium steel, stainless corrosion resistance nature and processing performance are improved, makes steel have the cooperation of good intensity and plasticity, toughness.But nickel is the main alloy element affecting stainless steel cost.Therefore, controlling nickel content is≤0.30%.
Nitrogen: be the important element in Chromium Stainless Steel is a kind of effective element improving stainless steel intensity, erosion resistance and stabilization of austenite.Because nitrogen reduces solid matter partial dislocation in austenite, restriction containing the dislocation motion of interstitial impurity atomic group, therefore can be used as the intensity that solution strengthening element improves austenitic stainless steel, in addition, nitrogen is austenitizing forming element, can slow down centroid structure to body-centered and the martensitic transformation of close-packed hexagonal structure.Therefore, nitrogen, except part of nickel can be replaced to save except valuable nickel element, also can improve intensity and the corrosion resistance nature of steel.Therefore, consider from strong plasticity and cold and hot working performance, fatigue property and high-temperature corrosion resistance performance, the nitrogen that steel of the present invention adds 0.02 ~ 0.20% is most suitable content.
Meanwhile, sulphur, phosphorus should reduce its content as far as possible in technical qualification permission situation, to reduce the segregation at original austenite crystal prevention place, improve toughness.Residual element and Control of gas content are in suitable low levels level, steel is made to have quite high purity, be dissolved between carbon in austenite and each element and reach desirable optimum proportioning content, thus make material have the over-all propertieies such as good intensity, toughness, erosion resistance.
The manufacture method of a kind of Martensite Stainless Steel wire rod of the present invention, comprises the steps:
1) smelt, cast
Martensite Stainless Steel, its chemical component weight per-cent is: carbon 0.30 ~ 0.65%, silicon 0.20 ~ 0.50%, manganese≤0.60%, nickel≤0.30%, chromium 11.50 ~ 17.00%, molybdenum 0.20 ~ 0.50%, copper≤0.25%, sulphur≤0.030%, phosphorus≤0.040%, nitrogen 0.02 ~ 0.20%, all the other are iron and inevitable impurity; By above-mentioned chemical composition through smelting, being cast as continuously cast bloom or die casting base; Die casting base hot charging is annealed;
2) continuously cast bloom hot charging heating, or die casting base breaking down cogging+heating;
3) rod rolling
Start rolling temperature 1070 ~ 1140 DEG C, finishing temperature 850 ~ 980 DEG C, induction heating actuator temperature 1050 ± 50 DEG C, roll speed controls at 70 ~ 75m/s, wire spinning temperature 830 ~ 900 DEG C;
4) online hot charging annealing
Through the wire rod of rolling, through online heat collection drum collection, hot charging enters stove and anneals online, and online annealing process is: heating zone, is heated to 780 ~ 860 DEG C from 500 DEG C in 30 ~ 45min; Soaking zone, at 780 ~ 860 DEG C of soaking 45 ~ 60min;
5) annealing after air cooling, carry out salt bath+cleanup acid treatment, packaging and warehousing after surface examination and inspection after construction; Gained Martensite Stainless Steel wire rod tensile strength > 600MPa, yield strength > 300Mpa, elongation > 25%, relative reduction in area > 50%, lumber recovery > 85%.
Further, step 1) in die casting base hot charging annealing process be: >=300 DEG C are entered stove, are heated to 860 ± 10 DEG C with the speed of≤100 DEG C/h, and heating 12 ± 0.2h, is cooled to 400 ± 20 DEG C with the speed of≤50 DEG C/h and comes out of the stove.
Again, step 2) in continuously cast bloom hot charging heating process be: stove tail temperature≤800 DEG C, heat-up time >=2h, heating I section 950 ~ 1050 DEG C, heating II section 1120 ~ 1170 DEG C, soaking zone 1120 ~ 1170 DEG C, the temperature difference≤30 DEG C.
Step 2) middle die casting base breaking down cogging+heating; Cogged ingot heating process is: 1000 ± 10 DEG C of heating 0.5 ~ 0.75h, then in 2.5 ± 0.2h, is heated to 1280 ± 10 DEG C, at 1280 ± 10 DEG C of soaking 2 ~ 2.5h.
After testing, the tensile strength > 600MPa of the Martensite Stainless Steel that the present invention manufactures, yield strength > 300Mpa, elongation > 25%, relative reduction in area > 50%, lumber recovery > 85%.
Beneficial effect of the present invention:
1) present invention reduces nickel content, cost of alloy is reduced, effectively save nickel resources.Compared with 2Cr17Ni3 Martensite Stainless Steel, nickel reduces 3%, and as compared to X3CrNiMo13-4 with X4CrNiMo16-5-1 steel, nickel reduces 4 ~ 5%.
2) the present invention's rational chemical composition proportioning and manufacturing process combine and make the over-all properties of steel good, so that heat directly can be carried out without annealing send heating and rolling and not easy to crack by continuously cast bloom, economize on resources and reduce scaling loss fire consumption while reducing energy consumption.
3) chemical composition of the present invention is reasonable in design, and the Martensite Stainless Steel wire rod of hot-rolled state can be annealed without off-line.The hot charging annealing that the present invention adopts can make the annealing time of finished product shorten to 75 ~ 105 minutes from original 6 ~ 12 hours, and the Microstructure and properties of finished product evenly and surface quality is qualified, greatly reduce energy consumption, and effectively alleviate the annealing production capacity of steel mill, shortcoming easy to crack when solving the rolling of original medium high carbon Martensite Stainless Steel simultaneously and anneal.
4) chemical composition of the present invention is reasonable in design, has both ensured that its cost was lower, ensures that again its cold and hot working performance is not less than existing Cr-13 type and Cr-17 type Martensite Stainless Steel.In turn ensure that performance at joint nickel simultaneously, make it have good structure stability and hot and cold processing characteristics.
Accompanying drawing explanation
Fig. 1 is the die casting base hot charging annealing process schematic diagram of Martensite Stainless Steel of the present invention;
Fig. 2 is the breaking down cogging Heating Steel Ingots process schematic representation of Martensite Stainless Steel of the present invention;
Fig. 3 is the wire rod annealing process schematic diagram of Martensite Stainless Steel of the present invention;
Fig. 4 is the metallographic structure photo of conventional Cr-13 type Martensite Stainless Steel;
Fig. 5 is the metallographic structure photo after Martensite Stainless Steel wire rod of the present invention annealing.
Embodiment
Below by embodiment, the specific embodiment of the present invention is further described, but therefore protection scope of the present invention is not limited in the middle of embodiment.
Embodiment 1 ~ 6 adopts following technical process:
The first step: smelt, cast
In the electric arc furnace of 60 tons (or 40 tons), carry out molten steel just refine; The ladle refining of corresponding tonnage; Continuous casting produces 160 side's continuous casting square billets (or 2.3 tons of steel ingots are poured into a mould in die casting).
Wherein, stir mode at the bottom of EAF adopts nitrogen, probe temperature >=1600 DEG C, adopts ferrosilicon or silicon ball etc. to reduce, and reduction Bi Jinhang flows slag operation, and tapping temperature >=1630 DEG C, Cr content controls to lower limit.
AOD converts oxygen decarburization after steel; Add lime 800 ~ 1000Kg, calcined magnesite ball 400 ~ 1000Kg.Add alloy during T >=1680 DEG C, then add lime in batches, first adds 1000-1500kg, and second batch adds 1000-1500kg; End point carbon controls≤0.010%; Reduction process adds reductive agent by Al:Si=3:7, and reductive agent is 200kg aluminium ingot, and its surplus is SiFe.The superfine lime of 400 ~ 700kg is added and 100 ~ 300kg fluorite carries out secondary reduction after skimming.
LF ladle is in place, and energising heats up.Thermometric samples, trimming.Depending on slag situation, add appropriate lime, silicon stone, fluorite and reductor adjustment slag fluidity.Large bag to tundish adopts long sleeve pipe to add argon for protecting pouring, adopts immerseable long nozzle molding casting simultaneously, prevents molten steel secondary oxidation.
Continuous casting: starting pulling rate 1.2m/min, maximum pulling rate 1.8m/min; Induction stirring MEMS300/4 strength of current [A]/frequency [Hz]; FEMS70/15 strength of current [A]/frequency [Hz].Cross Section of CC Billet size: 160 × 160mm, length dimension: 8000 ~ 10000mm.
Die casting base hot charging annealing process schematic diagram as shown in Figure 1.
Second step: continuously cast bloom hot charging heats, or die casting base breaking down cogging+heating.
Breaking down cogging Heating Steel Ingots technique as shown in Figure 2.Continuously cast bloom heating process is as shown in table 1.
Table 1
3rd step: rod rolling
Start rolling temperature 1070 ~ 1140 DEG C, high pressure descaling is closed, and water rolling is closed in roughing, induction heating actuator temperature 1050 DEG C, finishing temperature 850 ~ 980 DEG C, wire spinning temperature 830 ~ 900 DEG C, rolls rear collection volume air cooling.
4th step: anneal online
Wire rod annealing process as shown in Figure 3.
Ring furnace I ~ III section temperature controls by 780 DEG C of execution, and IV ~ VI section burner is closed, and controls total time at 75 ~ 105 minutes in stove.Wire rod is direct upper C type hook air cooling packing after going out ring furnace.Inspection, finishing and packaging and warehousing after salt bath.
The component proportions of embodiment 1 ~ 6 is see table 2, and concrete technology parameter is see table 3, and the mechanical property of rod iron is see table 4.Table 5 is the present embodiment 1 ~ 6 and the cost of conventional 3Cr13 wire rod, international 3Cr13 and performance comparison.
From Fig. 4, Fig. 5, the matrix after Martensite Stainless Steel wire rod annealing of the present invention is more careful and even.From table 2 ~ table 4, the Martensite Stainless Steel wire rod that the present invention produces, room-temperature mechanical property improves the plasticity of steel while not reducing intensity index, and surface cracking probability is reduced greatly.Improve the surface quality qualification rate of medium high carbon Martensite Stainless Steel, reduce annealing energy consumption, particularly for the problem solving temperature production medium high carbon Martensite Stainless Steel wire rod and easily produce cracking, improve lumber recovery, reduce energy consumption.
Claims (6)
1. a Martensite Stainless Steel wire rod, its chemical component weight per-cent is: carbon 0.30 ~ 0.65%, silicon 0.20 ~ 0.50%, manganese≤0.60%, nickel≤0.30%, chromium 11.50 ~ 17.00%, molybdenum 0.20 ~ 0.50%, copper≤0.25%, sulphur≤0.030%, phosphorus≤0.040%, nitrogen 0.02 ~ 0.20%, all the other are iron and inevitable impurity.
2. Martensite Stainless Steel wire rod according to claim 1, it is characterized in that, the tensile strength > 600MPa of described Martensite Stainless Steel wire rod, yield strength > 300Mpa, elongation > 25%, relative reduction in area > 50%, lumber recovery > 85%.
3. a manufacture method for Martensite Stainless Steel wire rod, comprises the steps:
1) smelt, cast
Martensite Stainless Steel, its chemical component weight per-cent is: carbon 0.30 ~ 0.65%, silicon 0.20 ~ 0.50%, manganese≤0.60%, nickel≤0.30%, chromium 11.50 ~ 17.00%, molybdenum 0.20 ~ 0.50%, copper≤0.25%, sulphur≤0.030%, phosphorus≤0.040%, nitrogen 0.02 ~ 0.20%, all the other are iron and inevitable impurity; By above-mentioned chemical composition through smelting, being cast as continuously cast bloom or die casting base; Die casting base hot charging is annealed;
2) continuously cast bloom hot charging heating, or die casting base breaking down cogging+heating;
3) rod rolling
Start rolling temperature 1070 ~ 1140 DEG C, finishing temperature 850 ~ 980 DEG C, induction heating actuator temperature 1050 ± 50 DEG C, roll speed controls at 70 ~ 75m/s, wire spinning temperature 830 ~ 900 DEG C;
4) online hot charging annealing
Through the wire rod of rolling, through online heat collection drum collection, hot charging enters stove and anneals online, and online annealing process is: heating zone, is heated to 780 ~ 860 DEG C from 500 DEG C in 30 ~ 45min; Soaking zone, at 780 ~ 860 DEG C of soaking 45 ~ 60min;
5) annealing after air cooling, carry out salt bath+cleanup acid treatment, packaging and warehousing after surface examination and inspection after construction; Gained Martensite Stainless Steel wire rod tensile strength > 600MPa, yield strength > 300Mpa, elongation > 25%, relative reduction in area > 50%, lumber recovery > 85%.
4. the manufacture method of Martensite Stainless Steel wire rod according to claim 3, it is characterized in that, step 1) in die casting base hot charging annealing process be: >=300 DEG C are entered stove, 860 ± 10 DEG C are heated to the speed of≤100 DEG C/h, heating 12 ± 0.2h, is cooled to 400 ± 20 DEG C with the speed of≤50 DEG C/h and comes out of the stove.
5. the manufacture method of Martensite Stainless Steel wire rod according to claim 3, it is characterized in that, step 2) in continuously cast bloom hot charging heating process be: stove tail temperature≤800 DEG C, heat-up time >=2h, heating I section 950 ~ 1050 DEG C, heating II section 1120 ~ 1170 DEG C, soaking zone 1120 ~ 1170 DEG C, the temperature difference≤30 DEG C.
6. the manufacture method of Martensite Stainless Steel wire rod according to claim 3, is characterized in that, step 2) middle die casting base breaking down cogging+heating; Cogged ingot heating process is: 1000 ± 10 DEG C of heating 0.5 ~ 0.75h, then in 2.5 ± 0.2h, is heated to 1280 ± 10 DEG C, at 1280 ± 10 DEG C of soaking 2 ~ 2.5h.
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