CN102102163A - Martensitic stainless steel and manufacturing method thereof - Google Patents
Martensitic stainless steel and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses martensitic stainless steel, which comprises the following components in percentage by mass: 0.10-0.15 percent of carbon, 0.20-0.50 percent of silicon, 0.50-1.50 percent of manganese, 2.00-4.00 percent of nickel, 15.00-17.00 percent of chromium, 0.03-0.30 percent of molybdenum, 0.020-0.200 percent of nitrogen, 0.01-0.10 percent of rare earth, less than or equal to 0.25 percent of copper, less than or equal to 0.025 percent of sulfur, less than or equal to 0.040 percent of phosphorous and the balance of Fe and inevitable impurities. The martensitic stainless steel has strength and plasticity, high low-temperature impact ductility and corrosion resistance, and can be applied to a hydraulic cylinder shaft for manufacturing a ship. The invention also discloses a manufacturing method of the martensitic stainless steel.
Description
Technical field
The present invention relates to Martensite Stainless Steel, relate in particular to have high-strength plasticity, the Martensite Stainless Steel of hydro-cylinder axle that can be used for making ship of high/low-temperature impact toughness and erosion resistance.
Background technology
Hydraulic system of ship is the hinge of hull power transmission, as working medium, utilizes the pressure of liquid can realize moving and a kind of type of drive of transmission of power with liquid.In recent years, along with boats and ships develop to maximization, high speed direction, comprehensive use properties to warship ship steel (ship steel) is had higher requirement, authentication requesting (high standard requirement) by European surveying society, the comprehensive use properties of such material should reach: tensile strength (Rm) 800MPa, yield strength (Rp0.2) 600MPa, unit elongation (A) 15%, relative reduction in area (Z) 50%, (20 ℃ are impacted A to low-temperature impact toughness
KVReach more than the 27J).
Press the steel class and distribute, ship steel generally can be divided into stainless steel peculiar to vessel and structure iron peculiar to vessel.Press the metallographic structure classification of steel, stainless material peculiar to vessel mainly contains: austenitic stainless steel, duplex stainless steel, Martensite Stainless Steel.The Martensite Stainless Steel peculiar to vessel of seawater corrosion resistance is a present purposes stainless steel peculiar to vessel comparatively widely.
At present, Martensite Stainless Steel peculiar to vessel mainly is divided into and does not contain Ni stainless steel (Ni content is less than 5%) and contain the Ni stainless steel.
Lower (the low Ni of the material manufacturing cost that does not contain Ni stainless steel (for example 17Cr16Ni2,14Cr16Ni2 and X17CrNi16-2), or do not contain Ni), it can satisfy common sea transport needs, still, its low-temperature impact toughness is relatively poor, only is that (for example-20 of 17Cr16Ni2 ℃ are impacted A to 10-20J
KVOnly be 10-15J ,-20 ℃ of 14Cr16Ni2 and X17CrNi16-2 are impacted A
KVOnly be 15-20J), this can not satisfy sea transport needs (the high standard authentication requesting-20 of the European surveying society ℃ impact A of low temperature ocean environment
KVGreater than 27J).
Better (the 20 ℃ of impact A of low-temperature impact that contain Ni stainless steel (for example X4CrNiMo16-5-1)
KVCan reach more than the 100J), can satisfy the sea transport needs of low temperature ocean environment, yet wherein Ni content is up to 5.0%-6.0%, because Ni is the noble metal element, so the cost of steel has limited the popularization and application of such material.
More existing patent applications relate to the Martensite Stainless Steel of high tenacity, the disclosed high tenacity Martensite Stainless Steel of CN200710099335.3 and CN200310104844.2 for example, but wherein the content of Mo, Ti element is higher, so smelting cost is obviously too high.
This shows, design a kind of Eco-power high performance Martensite Stainless Steel,, especially satisfy the high standard authentication requesting of European surveying society, become the technology pursue of steelmaker to satisfy the sea transport requirement of low temperature ocean environment.
Summary of the invention
The object of the present invention is to provide a kind of Martensite Stainless Steel, the standard that its comprehensive use properties reaches ship steel (is tensile strength (Rm) 800MPa, yield strength (Rp0.2) 600MPa, unit elongation (A) 15%, relative reduction in area (Z) 50%), the low-temperature impact toughness high standard authentication requesting that meets European surveying society (promptly-20 ℃ impacts A
KVReach more than the 27J), and low cost of manufacture.
Martensite Stainless Steel provided by the present invention, its composition quality per-cent is: carbon: 0.10-0.15%, silicon: 0.20-0.50%, manganese: 0.50-1.50%, nickel: 2.00-4.00%, chromium: 15.00-17.00%, molybdenum: 0.03-0.30%, nitrogen: 0.020-0.200%, rare earth: 0.01-0.10%, copper≤0.25%, sulphur≤0.025%, phosphorus≤0.040%, surplus is Fe and inevitable impurity.
Preferably, above-mentioned Martensite Stainless Steel, its composition quality per-cent is: carbon: 0.10-0.15%, silicon: 0.30-0.50%, manganese: 0.60-1.00%, nickel: 2.40-4.00%, chromium: 15.30-17.00%, molybdenum: 0.04-0.20%, nitrogen: 0.024-0.160%, rare earth: 0.01-0.10%, copper≤0.25%, sulphur≤0.025%, phosphorus≤0.040%, surplus is Fe and inevitable impurity.
Preferably, above-mentioned Martensite Stainless Steel, Cr eq=16.00-17.73% wherein, Ni eq=6.35-11.92%, and Cr eq/Ni eq is: 1.30-2.20;
Described Cr eq=Cr+2Si+1.5Mo+5V+5.5Al+1.5Ti+1.75Nb+0.75W;
Described Ni eq=Ni+0.5Mn+30C+25N+Co+0.3Cu.
Preferably, wherein said rare earth is the lanthanide series rare-earth elements lanthanum.
Preferably, above-mentioned Martensite Stainless Steel, its yield strength Rp0.2 is 600-750MPa, and tensile strength Rm is 800-950MPa, and unit elongation A is 15-25%, and relative reduction in area Z is 55-60% ,-20 ℃ are impacted A
KVBe 35-65J.
Another object of the present invention is to provide a kind of manufacture method of described Martensite Stainless Steel, and this method comprises:
(1) melting, refining, employing die casting process are produced steel ingot and annealing,
Described annealing comprises 720 ± 10 ℃ of insulations, be cooled to 150 ℃-250 ℃ with the speed that is no more than 50 ℃/hour then after air cooling;
(2) forge hot, annealing for the first time and annealing for the second time,
The holding temperature of described forge hot is 1150 ± 10 ℃, opens the forging temperature and is not less than 1050 ℃, and final forging temperature is not less than 900 ℃,
Described first time, annealing comprised 690 ± 10 ℃ of insulations, be cooled to 150 ℃ ± 50 ℃ with the speed that is no more than 50 ℃/hour then after air cooling,
Described second time, annealing comprised 690 ± 10 ℃ of insulations, be cooled to 150 ± 50 ℃ with the speed that is no more than 20 ℃/hour then after air cooling;
(3) modified thermal treatment comprises quenching, tempering for the first time, tempering for the second time,
Wherein quenching comprises 950～1050 ℃ of insulations, air cooling to 200 ℃ ± 50 ℃,
Wherein tempering for the first time comprises 700 ± 10 ℃ of insulations, then being no more than 30 ℃/hour speed slow cooling to 200 ℃ ± 50 ℃,
Wherein tempering for the second time comprises 690 ± 10 ℃ of insulations, and air cooling is to room temperature.
Preferably, annealing is carried out in 30 minutes after the steel ingot demoulding in the step (1).
Preferably, annealed soaking time in the step (1) 〉=16 hours.
Preferably, the steel ingot in the step (1) is 2.3 tons of ingot shapes, and its annealing soaking time is preferably 16-18 hour.
Preferably, the steel ingot in the step (1) is 3.7 tons of ingot shapes, and its annealing soaking time is preferably 18-20 hour.
Preferably, annealing is for the first time carried out in 30 minutes behind finish-forging in the step (2).
Preferably, the soaking time of forge hot was not less than 4 hours in the step (2).
Preferably, first and second annealed soaking times are more than 24 hours in the step (2).
Preferably, the annealed air cooling time is 2-4 hour for the first time in the step (2).
Preferably, obtain in the step (2) to forge rod, its specification is φ 100mm-400mm,
For the forging rod of φ 100mm-150mm, the Quenching Soaking Time in the step (3) is preferably 2-2.5h, and first and second times the tempered soaking time is preferably 3-4h;
For the forging rod of φ 151mm-250mm, the Quenching Soaking Time in the step (3) is preferably 3.5-4h, and first and second times the tempered soaking time is preferably 5-6h;
For the forging rod of φ 250mm-400mm, the Quenching Soaking Time in the step (3) is preferably 4-6h, and first and second times the tempered soaking time is preferably 6-8h.
Being described as follows of design of alloy of the present invention:
Carbon is the element of stable austenite, carbon forms carbide solid solution reinforcement matrix with alloying elements such as Cr, Mn, Mo in ferrite in stainless steel simultaneously, the intensity and the hardness of steel are increased substantially, but C is too high then unfavorable to toughness and intergranular corrosion, so carbon is controlled to be 0.10-0.15 and can obtaining high-intensity guarantee simultaneously good toughness and erosion resistance.
Manganese is austenite stabilizer element, but the effect of manganese does not lie in the formation austenite, but is that it reduces the critical quenching rate of steel, increases austenitic stability when cooling, suppresses austenitic decomposition.Therefore manganese can increase the hardening capacity of steel strongly, helps adopting aborning Direct Air-Cooled to be quenched and just can obtain martensitic stucture.Simultaneously, Mn also plays the effect of reductor and sweetening agent, but cleaning molten steel, but too high meeting impels crystal grain thick, and in addition, aspect the corrosion resistance nature that improves steel, the effect of manganese is little, therefore is controlled to be 0.50-1.50.
Silicon is ferrite former, to forming austenite bad influence is arranged, and the silicon solid solution has tangible strengthening effect in ferrite and austenite.Silicon reduces the solubleness of carbon in austenite, impels carbide to separate out, and improves intensity and hardness.Simultaneously, the avidity of silicon and oxygen is only second to aluminium and titanium, and is better than manganese, chromium, vanadium, be better reductant and reductor, can improve the density of steel, but the too high plasticity and the toughness that will significantly reduce steel of silicon, therefore being controlled to be 0.20-0.50 can guarantee good obdurability and intergranular corrosion resistance performance.
Chromium is carbide forming element, has promoted the passivation of steel and has made steel keep stablizing passive result.Simultaneously, chromium is again to form strongly and stablize ferritic element, is dissolved in strengthening matrix in the austenite and not reducing toughness, dwindles the austenitic area, postpones supercooled austenite and changes, and increases the hardening capacity of steel.The intensity and the hardness of steel are obviously improved, and are useful to anti intercrystalline corrosion and resistance of oxidation.Chromium can crystal grain thinning in addition, improves the temper resistance of quenched and tempered steel, and therefore, steel design chromium content of the present invention is 15.00-17.00%.
Nickel is to form and the element of stable austenite, improves the tissue of high chromium steel, and stainless corrosion resistance nature and processing performance are improved, and makes steel have good intensity and plasticity, flexible cooperate.But nickel is the main alloy element that influences the stainless steel cost, and therefore, control nickel content is 2.00-4.00%.
Nitrogen is the important alloying element in the stainless steel, it is a kind of effective element that improves stainless steel intensity, erosion resistance and stabilization of austenite, but except that instead of part nickel to save the valuable nickel element, mainly be intensity and the corrosion resistance nature that improves steel as the solution strengthening element, therefore consider that from strong plasticity and cold and hot working performance, fatigue property and high-temperature corrosion resistance performance the nitrogen that the present invention adds 0.020-0.200% is only content.
Molybdenum is formation and stable ferrite and the element that enlarges the ferrite phase region, can strengthen the anti-corrosion effect of chromium in the steel.But molybdenum can promote the precipitation of intermetallic phase in the stainless steel (as the σ phase), can have a negative impact to the plasticity and the toughness of steel.Therefore, take all factors into consideration, add 0.03-0.30%.
Rare earth improves hot workability in stainless steel be effectively, and rare earth has and purifies and metamorphism, can improve inclusion morphology, reduces separating out of σ phase, again can crystal grain thinning, therefore can improve the plasticity and the toughness of steel.Rare earth also can improve the oxidation-resistance of high temperature steel in addition.The rare earth that adds 0.01-0.10% can function as described above, and the present invention preferably adds lanthanide series rare-earth elements lanthanum (La).
Sulphur, phosphorus should reduce its content as far as possible under technical qualification permission situation, to reduce the poly-partially of original austenite crystal prevention place, improve toughness.Residual element (for example copper) and gas content are controlled at suitable low levels level, make steel have quite high purity, be dissolved in and reach the best proportioning content of ideal between carbon in the austenite and each element, thereby make material have over-all propertieies such as good intensity, toughness, erosion resistance.
The present invention also suitably adds rare earth element by optimizing with the chemical ingredients (increase Mn, N content, reduce Cr, Si content) of strict control steel, has improved the strong plasticity and the impelling strength of steel; The present invention is also by suitable annealing process and hardening and tempering process, and final acquisition is stablized, uniform quenched and tempered organization.Specifically, the present invention has the following advantages:
(1) the present invention has reduced nickel content, has reduced cost of alloy, has effectively saved nickel resources, compares with the X4CrNiMo16-5-1 Martensite Stainless Steel, and nickel has descended 2 percentage points;
(2) compare with conventional Cr-17 type Martensite Stainless Steel, the tensile strength of Martensite Stainless Steel of the present invention (Rm) (800-950Mpa) and yield strength (Rp0.2) (600-750Mpa) raising arranged slightly, elongation (A) (15-25%) and relative reduction in area (Z) (55-60%) raising of big (about 20%) ,-20 ℃ of impact value (A arranged
KV) (35-65J) improved more than 2 times.
Generally, the present invention has solved the on the low side and easy problem that stress crack and low-temperature brittle fracture take place of low-temperature impact toughness of existing Martensite Stainless Steel on the basis that does not increase smelting cost, Martensite Stainless Steel of the present invention can be used as ship steel, it can improve the resistance to overturning of ship's machinery, further satisfies the requirement of sea transport industrial development.Martensite Stainless Steel of the present invention especially is suitable for making ship hydraulic cylinder axle.
Description of drawings
Fig. 1 is the metallograph of organizing of X17CrNi16-2 steel;
Fig. 2 be embodiment 3 Martensite Stainless Steel organize metallograph.
The present invention will describe by preferred embodiment below, should be noted in the discussion above that these embodiments only are exemplary, do not limit scope of the present invention.
Embodiment
The embodiment chemical ingredients sees Table 1, and preparation technology parameter sees Table 2, and mechanical property sees Table 3, and its preparation process is as follows.The chemical ingredients of embodiment and X17CrNi16-2 and the contrast of mechanical property see Table 4.
The first step: smelt
40 tons of EAF electric arc furnace just refine, and end stir mode adopts nitrogen, and silicon carbide, silicon ball are used in the electric furnace reduction agent; Refining just finishes the back and changes the refining of 40 tons of AOD/LF stoves, draws reducing slag clearly before the tapping, adds alloy in the time of 1680 ℃, during oxygen decarburization to 0.30%, adds lime 800kg, during oxygen decarburization to 0.10%, adds lime 800kg again.End point carbon control＜0.03%, 1540-1550 ℃ of bull ladle temperature; 2.3 tons of steel ingots of die casting water finishes lifting after 120 minutes; Carried out 720 ℃ of insulation annealings of hot charging, annealing time 16 hours after the steel ingot demoulding in 30 minutes.
Second step: forge
Steel ingot is cold to be delivered to 4000 tons fast to forge coggings is 280 anistreely to forge personal bases, melt down and be heated to 1050 ℃ of insulations and deliver to 1300 tons of footpath forged piece φ 110mm after 1.5 hours and forge rod, the annealing of 900 ℃ of hot chargings of finish-forging, 690 ℃ of second stage annealings are incubated after 48 hours furnace cooling to 200 and ℃ come out of the stove.
The 3rd step: finished product is modified
Finished product is forged excellent whole modifier treatment, and quenching technology is 550 ℃ and advances stove, is heated to 950 ℃ of insulations dry quenching of coming out of the stove after 2.5 hours with the heat-up rate that per hour is not more than 50 ℃; Advance the stove tempering during air cooling to 200 ℃, tempering process is 700 ℃ of insulations slow cooling to 200 ℃ and then advance stove and be heated to 650 ℃ of insulations and cool to 250 ℃ with the furnace after 4 hours and come out of the stove after 4 hours.
The measuring mechanical property method
Brinell hardness (HBW) testing method is: GB/T 231.1 metal static hardness test part 1s: test method; Room temperature tensile (Rm, Rp0.2, A, Z) testing method is GB/T 228 metallic substance tensile test at room temperature methods; Impelling strength (A
Kv) testing method is that the 229 metal summers of GB/T are than test with notched test piece method.
Comparison diagram 1 and Fig. 2 as can be known, the matrix of Martensite Stainless Steel of the present invention is more careful and even than X17CrNi16-2 stainless steel.Contrast by table 4 as can be known, Martensite Stainless Steel of the present invention when not reducing intensity index bigger raising plasticity index, its low temperature impact properties is apparently higher than X17CrNi16-2, can satisfy requirement peculiar to vessel, especially for solving the low problem of axle impelling strength peculiar to vessel under the low temperature, and improve the crucial realistic meaning of seagoing transport efficient tool.
The chemical ingredients of table 4 embodiment and X17CrNi16-2 and performance comparison
Claims (14)
1. Martensite Stainless Steel, its composition quality per-cent is:
Carbon: 0.10-0.15%, silicon: 0.20-0.50%, manganese: 0.50-1.50%, nickel: 2.00-4.00%, chromium: 15.00-17.00%, molybdenum: 0.03-0.30%, nitrogen: 0.020-0.200%, rare earth: 0.01-0.10%, copper≤0.25%, sulphur≤0.025%, phosphorus≤0.040%, surplus is Fe and inevitable impurity.
2. Martensite Stainless Steel as claimed in claim 1, its composition quality per-cent is:
Carbon: 0.10-0.15%, silicon: 0.30-0.50%, manganese: 0.60-1.00%, nickel: 2.40-4.00%, chromium: 15.30-17.00%, molybdenum: 0.04-0.20%, nitrogen: 0.024-0.160%, rare earth: 0.01-0.10%, copper≤0.25%, sulphur≤0.025%, phosphorus≤0.040%, surplus is Fe and inevitable impurity.
3. Martensite Stainless Steel as claimed in claim 1 or 2, Cr eq=16.00-17.73% wherein, Nieq=6.35-11.92%, and Cr eq/Ni eq is: 1.30-2.20;
Described Cr eq=Cr+2Si+1.5Mo+5V+5.5Al+1.5Ti+1.75Nb+0.75W;
Described Ni eq=Ni+0.5Mn+30C+25N+Co+0.3Cu.
4. as any one described Martensite Stainless Steel of claim 1-3, wherein said rare earth is the lanthanide series rare-earth elements lanthanum.
5. as any one described Martensite Stainless Steel of claim 1-4, its yield strength Rp0.2 is 600-750MPa, and tensile strength Rm is 800-950MPa, and unit elongation A is 15-25%, and relative reduction in area Z is 55-60%, and-20 ℃ are impacted A
KVBe 35-65J.
6. as the preparation method of any one described Martensite Stainless Steel of claim 1-5, comprising:
(1) melting, refining, employing die casting process are produced steel ingot and annealing,
Described annealing comprises 720 ± 10 ℃ of insulations, be cooled to 150 ℃-250 ℃ with the speed that is no more than 50 ℃/hour then after air cooling;
(2) forge hot, annealing for the first time and annealing for the second time,
The holding temperature of described forge hot is 1150 ± 10 ℃, opens the forging temperature and is not less than 1050 ℃, and final forging temperature is not less than 900 ℃,
Described first time, annealing comprised 690 ± 10 ℃ of insulations, be cooled to 150 ℃ ± 50 ℃ with the speed that is no more than 50 ℃/hour then after air cooling,
Described second time, annealing comprised 690 ± 10 ℃ of insulations, be cooled to 150 ± 50 ℃ with the speed that is no more than 20 ℃/hour then after air cooling;
(3) modified thermal treatment comprises quenching, tempering for the first time, tempering for the second time,
Wherein quenching comprises 950～1050 ℃ of insulations, air cooling to 200 ℃ ± 50 ℃,
Wherein tempering for the first time comprises 700 ± 10 ℃ of insulations, then being no more than 30 ℃/hour speed slow cooling to 200 ℃ ± 50 ℃,
Wherein tempering for the second time comprises 690 ± 10 ℃ of insulations, and air cooling is to room temperature.
7. method as claimed in claim 6, wherein annealing is carried out in 30 minutes after the steel ingot demoulding in the step (1).
8. as claim 6 or 7 described methods, annealed soaking time in the step (1) 〉=16 hours wherein.
9. as any one described method of claim 6-8, wherein the steel ingot in the step (1) is 2.3 tons of ingot shapes or 3.7 tons of ingot shapes, and the annealing soaking time of described 2.3 tons of ingot shapes is 16-18 hour, and the annealing soaking time of described 3.7 tons of ingot shapes is 18-20 hour.
10. as any one described method of claim 6-9, wherein annealing is for the first time carried out in 30 minutes behind finish-forging in the step (2).
11. as any one described method of claim 6-10, wherein the soaking time of forge hot was not less than 4 hours in the step (2).
12. as any one described method of claim 6-11, wherein first and second annealed soaking times are more than 24 hours in the step (2).
13. as any one described method of claim 6-12, wherein the annealed air cooling time is 2-4 hour for the first time in the step (2).
14. as any one described method of claim 6-13, wherein obtain in the step (2) to forge rod, its specification is φ 100mm-400mm; For the forging rod of φ 100mm-150mm, the Quenching Soaking Time in the step (3) is 2-2.5h, and first and second tempered soaking times are 3-4h; For the forging rod of φ 151mm-250mm, the Quenching Soaking Time in the step (3) is 3.5-4h, and first and second tempered soaking times are 5-6h; For the forging rod of φ 251mm-400mm, the Quenching Soaking Time in the step (3) is 4-6h, and first and second tempered soaking times are 6-8h.
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