CN103205655A - Sn-containing austenitic stainless steel and manufacturing method thereof - Google Patents
Sn-containing austenitic stainless steel and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses Sn-containing austenitic stainless steel and a manufacturing method thereof. The Sn-containing austenitic stainless steel is chemically composed of, by weight, </=0.030% of C, </=1.00% of Si, </=2.00% of Mn, </=0.045% of P, </=0.030% of S, 10.00-15.00% of Ni, 16.00-18.50% of Cr, 2.00-3.00% of Mo, </=0.10% of N, 0.01-1.00% of Sn, </=1.2% of Cu, and the balance Fe and unavoidable impurities. On the basis of existing 316L stainless steel, resistance to reducing sulfuric acid corrosion is improved through Sn micro-alloying, and better effect is obtained by compositely adding a small amount of Cu. On the basis of maintaining original low cost and mechanical performance, resistance to sulfuric acid corrosion is remarkably improved, and the Sn-containing austenitic stainless steel is suitable for SOx-containing corrosive environments more demanding in corrosion resistance.
Description
Technical field
The present invention relates to a kind of Cr-Ni-Mo type austenitic stainless steel, relate in particular to a kind of solidity to corrosion good contain the Sn austenitic stainless steel, can be applicable to solidity to corrosion and require harsh engine EGR system and power station flue gas desulfurization etc. to contain SO
xCorrosive environment.
Background technology
300 series austenitic stainless steel are extensive use of by people because of its excellent solidity to corrosion, plasticity and mechanical property etc., and 304 and two steel grades of 316L to occupy 300 be more than 80% of stainless steel total amount.304 belong to Cr-Ni type austenitic stainless steel, are widely used in household supplies, foodstuffs industry, medical apparatus, water-heater, boiler, auto parts machinery, building materials of general anti-corrosion environment etc.; 316L belongs to Cr-Ni-Mo type austenitic stainless steel, because its higher Ni content and the certain Mo content of interpolation, have better anti-pitting attack, uniform corrosion and intergranular corrosion ability, can be used for solidity to corrosions such as coastal equipment, printing and dyeing papermaking, flue gas desulfurization, nitric acid chemical industry, heat exchanger and require harsher corrosive environment.
According to national requirements for environmental protection, motor vehicle exhaust and power station fume emission limit value will be more and more stricter, and this just requires gas necessary through purifying treatment before discharging.The egr system of motor car engine can reduce NO effectively
xCan reduce power station SO with flue gas desulfurization (FGD) unit
xDischarging since in the fuel inevitably S burning back generate SO
2And SO
3, to meet water and then generate sulfuric acid, this just requires corresponding device materials that good corrosion resistance to sulfuric acid must be arranged.At present, relative unit adopts conventional 316L stainless steel (chemical ingredients of existing 316L steel grade in the country variant standard as shown in table 1) mostly both at home and abroad, but corrode still inevitable, lost efficacy during often with the EGR sport car and situations generations such as flue gas desulfurization (FGD) unit corrosion failure, because of its corrosion resistance against sulfuric acid poor.If adopt more excellent 317L or the 904L of solidity to corrosion, then cost is too high, and is uneconomical.
The chemical ingredients of existing 316L steel grade in the table 1 country variant standard
In the existing relevant patent, ferrite or Martensite Stainless Steel are carried out the Sn microalloying improve correlated performance: Sn can improve stainless machining property on the one hand, in 16～25wt%Cr ferritic stainless steel, add Sn less than 0.15wt% as Chinese patent CN1977062A, the machinability improved additives when can be used as low cutting; Japanese Patent JP62278252A, the Sn that adds 0.005～0.7wt% in the Cr that contains 7.5～30wt% and the special steel less than the Ni of 40wt% improves machinability.
Sn can improve Corrosion Resistance of Stainless Steels on the other hand, this corrosion resisting property comprises anti-muriate etc., but do not comprise corrosion resistance against sulfuric acid: as Chinese patent CN101981217A in the Cr of 10～14wt% Martensite Stainless Steel, by adding the Sn of 0.005～1.0wt%, can improve the resistance to rust under chloride environment, particularly more remarkable under the situation that Mn content is high not containing Cu, Ti.
Chinese patent CN101838772A is in the Martensite Stainless Steel of 11～15.5wt%Cr, and the Sn that adds 0.03～0.15wt% has improved the solidity to corrosion of martensitic stainless steel greatly, and is particularly more remarkable in the scope of quenching Vickers' hardness 300～600.
Chinese patent CN101903553A adds the Sn of 0.001～1wt% in 13～22wt%Cr high-purity ferrite stainless steel, passive film is carried out modification, and solidity to corrosion is improved.
Chinese patent CN1256716A adds the Sn of 0.0002～0.02wt% in the stainless steel of the above Cr of 10wt%, make Ag particle, Ag oxide compound and Ag sulfide disperse to separate out, and has the effect of the germ resistance of playing consistently.
Chinese patent CN102127715A adds 0.05～1.0wt% in 14～30wt% ferritic stainless steel Sn improves solidity to corrosion and germ resistance; Chinese patent CN102162062A adds 0.05～1.0wt%Sn and improves solidity to corrosion and germ resistance in the Martensite Stainless Steel of 12～18wt%Cr.
But the martensite of the above-mentioned Sn of containing, the common defective of ferritic stainless steel are to put into sulfuric acid corrosion severity, and corrosion resistance against sulfuric acid is very poor, can't be applied in the environment of sulfuric acid corrosion resistant.
Summary of the invention
The object of the present invention is to provide a kind of anti-dilute sulphuric acid corrosive nature good contain Sn austenitic stainless steel and manufacture method thereof, on the stainless basis of existing 316L, improve the reducing resistance sulfuric acid corrosion by the Sn microalloying, a spot of Cu effect of compound interpolation reaches better.The present invention contains the Sn austenitic stainless steel on the basis that keeps original low cost and mechanical property, has significantly improved corrosion resistance to sulfuric acid.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Sn austenitic stainless steel that contains, its following chemical components in percentage by weight is: C≤0.030%, Si≤1.00%, Mn≤2.00%, P≤0.045%, S≤0.030%, Ni:10.00～15.00%, Cr:16.00～18.50%, Mo:2.00～3.00%, N≤0.10%, Sn:0.01～1.00%, all the other are Fe and unavoidable impurities; The described Sn of containing austenitic stainless steel be thickness more than 2mm hot-rolled steel sheet or thickness less than the cold-rolled steel sheet of 2mm.
Further, described containing in the Sn austenitic stainless steel, described Mn content is 0.50～1.50wt%.
Further, the described Sn austenitic stainless steel that contains also comprises Cu, 0＜Cu≤1.2wt%.
Preferably, the described Sn austenitic stainless steel that contains is in smelting, and the high temperature ferrite δ content in its as cast condition austenite is less than 5wt%, and wherein the δ value adopts following formula to calculate:
δ＝3*(Cr%+Mo%)+4.5*Si%-2.8*Ni%-1.4*Mn%-84*(C%+N%)-19.8。
Above-mentioned high temperature ferrite refers to the ferrite that the above high temperature of 1260 ° of C is separated out.
The effect that contains each chemical element in the Sn austenitic stainless steel of the present invention is as follows:
C:C is a kind of interstitial element, can significantly improve the intensity of steel by solution strengthening, form and the stable austenite district, but C too can make particularly intergranular corrosion resistance degradation of stainless steel solidity to corrosion.Therefore, C should control at 0.030wt% or still less.
Si:Si is a kind of deoxidant element, but is a kind of ferrite former, also can significantly improve steel in the intergranular corrosion susceptibility of solid solution attitude.Therefore, Si should control at 1.00wt% or still less.
Mn:Mn is strong stable austenite element, can improve the intensity of steel and improve thermoplasticity.The easy formation MnS of being combined with S of Mn is mingled with the solidity to corrosion that influences steel.Therefore, Mn should control below 2.00wt%, more preferably 0.50～1.50wt%.
P and S:P and S are regarded as harmful element in stainless steel, influence stainless thermoplasticity and solidity to corrosion, and these two elements are controlled more low more well.
Ni:Ni is austenite former, improve stainless toughness and ductility, make steel be easy to processing, make and welding, Ni can also improve stainless antiacid corrosive power, but too high Ni influences manufacturing cost, so the present invention contains, and Ni controls at 10.0～15.0wt% in the Sn austenitic stainless steel.
Cr:Cr improves corrosion proof important element, solidity to corrosion is relatively poor when being lower than 16.0wt% can not reach service requirements, but can increase ferrite when surpassing 18.5wt% and form tendency, need more austenite element to cause material cost to increase, so steel grade of the present invention is preferably controlled at 16.0～18.5wt%.
Mo:Mo can significantly improve stainless corrosion-resistant ability and reducing resistance acid corrosion ability, be again ferrite former simultaneously but Mo is precious metal, so Mo should control at 2.00～3.00wt% in the steel of the present invention.
N:N is strong austenite former, in stainless steel except alternative noble metal Ni, under the prerequisite of not obvious reduction material plasticity and toughness, can obviously improve the intensity of material, can also improve stainless solidity to corrosion and delay carbide and separate out etc.But the solid solubility of N in steel is limited, subsurface bubble occurs for fear of process of setting, avoids too high intensity to cause processing difficulties simultaneously, and therefore, N should control below 0.10wt% in the steel of the present invention.
Sn:Sn is the solution strengthening element, and the intensity of material is improved, and Sn can improve the characteristic of stainless steel surface passive film, SnO simultaneously
2Thereby in passive film enrichment improved its stability and again repair ability improved stainless solidity to corrosion, but Sn is low melting point metal, the fusion fragility when too high meeting causes hot-work.Therefore, Sn controls at 0.01～1.00wt% in the steel of the present invention.
Cu:Cu is austenite former, can save Ni, improves the cold-formed property of steel, and Cu more effectively improves the effect of Sn in solidity to corrosion, both collaborative onsets as the additional compound interpolation element of Sn simultaneously.But Cu is not obvious to the corrosion proof synergy of Sn above after a certain amount of, and too much Cu also can reduce the hot workability of steel simultaneously.Therefore, Cu controls at 1.2wt% or following in the steel of the present invention.
The manufacture method that contains the Sn austenitic stainless steel of the present invention comprises the steps:
(1) smelt, cast: the proportioning according to the chemical ingredients that contains the Sn austenitic stainless steel adopts conventional vacuum induction furnace, electric furnace-AOD duplex is smelted or electric furnace-AOD-VOD three-step approach is smelted, and smelting back die casting or continuous casting become strand;
(2) hot rolling: the strand that obtains is heated in process furnace, and rolling then, 1200～1300 ℃ of Heating temperatures, finishing temperature be greater than 950 ℃, rolls the coiling temperature of back water-cooled to 600～750 ℃, batches the back air cooling, obtains hot-rolled sheet;
(3) hot-roll annealing pickling: the hot-rolled sheet that step (2) is obtained carries out solution annealing at 1000～1150 ℃, and soaking time is carried out according to steel plate thickness 1～3min/mm, and water-cooled obtains to contain the Sn austenitic stainless steel to room temperature then; This contains the Sn austenitic stainless steel is the hot-rolled steel sheet of thickness more than 2mm.
The manufacture method that contains the Sn austenitic stainless steel of the present invention also comprises:
(4) cold rolling: the sheet material after the hot-roll annealing pickling of step (3) is carried out cold rolling, cold rolling draft is not less than 50%;
(5) cold rolled annealed pickling: the sheet material after cold rolling is carried out solution annealing at 1000～1150 ℃, and soaking time is carried out according to steel plate thickness 1～3min/mm, and water-cooled obtains to contain the Sn austenitic stainless steel to room temperature then; This contains the Sn austenitic stainless steel is that thickness is less than the cold-rolled steel sheet of 2mm.
Preferably, in the step (1), Sn adds the modes such as adding ferro-tin alloy or hello Sn silk that adopts.
Preferably, during step (1) was smelted, the high temperature ferrite δ content in its as cast condition austenite was less than 5wt%, and its δ value is:
δ＝3*(Cr%+Mo%)+4.5*Si%-2.8*Ni%-1.4*Mn%-84*(C%+N%)-19.8。
Preferably, in the step (2), Heating temperature is 1220～1260 ℃, and coiling temperature is 650～700 ℃.
Preferably, in step (3) and the step (5), the solution annealing temperature is 1050～1100 ℃, and soaking time is 1～1.5min/mm.
The present invention compared with prior art has following beneficial effect:
The Sn austenitic stainless steel that contains of the present invention, both had good mechanical performance, good plasticity and toughness, compare with conventional 316L, keeping on original low-cost basis, significantly improved the solidity to corrosion of material, especially significantly improved the corrosion resistance to sulfuric acid of material, suitable solidity to corrosion is harsher contains SO
xAnti-corrosion bad border, can be applicable to solidity to corrosion and require harsh engine EGR system and contain power station flue gas desulfurization etc. to contain SO
2Corrosive environment.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail.
Embodiment 1
Adopt vacuum oven to smelt the steel of Chemical Composition shown in the embodiment 1 in the table 2, be molded into steel ingot, Sn is with Fe
60Sn
40The mode of alloy adds; Steel ingot cogging becomes the thick side's ingot of 50mm, and process furnace is incubated 1h after being warming up to 1250 ℃ with stove, and square ingot is come out of the stove, and to be hot-rolled down to 3mm thick, 1020 ℃ of finishing temperatures, then laminar flow water-cooled to 650 ℃ batch, air cooling; Hot-rolled sheet is at 1050 ℃ of solution annealing 3min, and water-cooled is to room temperature, then successively through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1080 ℃ of solution annealing 1min, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is tested according to GB/T4334.6-2000 " stainless steel 5% sulfuric acid corrosion test method ", 3 parallel samples are prepared in every group of test, before the test specimen surface is ground successively with granularity 150# waterproof abrasive paper to 600# waterproof abrasive paper, preparation 5wt% aqueous sulfuric acid, treat that putting into sample behind the etchant solution ebuillition of heated picks up counting, keep solution to seethe with excitement continuously and take out sample behind the 6h, clean up, calculate corrosion weight loss speed according to changes in weight before and after the corrosion.What embodiment 1 obtained contains the Sn austenitic stainless steel after testing, and its erosion rate is 6.01g/m
2H(and each Comparative Examples more as shown in table 3), be far superior to not contain the conventional 316L stainless steel of Sn, the erosion rate of conventional 316L is 25g/m
2H.
Embodiment 2
Adopt electric furnace, AOD duplex to smelt the steel of Chemical Composition shown in the embodiment 2 in the table 2, continuous casting becomes the thick strand of 200mm, and Sn is with Fe
60Sn
40The mode of alloy adds in AOD; Continuously cast bloom adds and to be incubated 2.5h after being heated to 1260 ℃ in the stove, and it is thick to be hot-rolled down to 4mm, 950 ℃ of finishing temperatures, then laminar flow be water-cooled to 700 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 5min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1.5mm, and cold-reduced sheet is at 1100 ℃ of solution annealing 1.5min, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 3.4g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 3
Adopt electric furnace, AOD, VOD three-step approach to smelt the steel of Chemical Composition shown in the embodiment 3 in the table 2, feed Fe-Sn alloy silk during VOD, continuous casting becomes the thick strand of 180mm; Continuously cast bloom adds and to be incubated 2h after being heated to 1220 ℃ in the stove, and it is thick to be hot-rolled down to 2mm, 950 ℃ of finishing temperatures, then laminar flow be water-cooled to 670 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 3min, and water-cooled then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling, obtains to contain Sn austenitic stainless steel hot-roll annealing plate to room temperature.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 2.2g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 4
Adopt electric furnace, AOD duplex to smelt the steel of Chemical Composition shown in the embodiment 4 in the table 2, continuous casting becomes the thick strand of 200mm, feeds Fe-Sn alloy silk during AOD; Continuously cast bloom adds and to be incubated 3h after being heated to 1240 ℃ in the stove, and it is thick to be hot-rolled down to 3mm, 990 ℃ of finishing temperatures, then laminar flow be water-cooled to 700 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 5min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1100 ℃ of solution annealing 1.5min, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 1.77g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 5
Adopt electric furnace, AOD, VOD three-step approach to smelt the steel of Chemical Composition shown in the embodiment 5 in the table 2, add the microalloying that the Fe-Sn alloy carries out Sn during VOD, continuous casting becomes the thick strand of 220mm; Continuously cast bloom adds and to be incubated 3h after being heated to 1200 ℃ in the stove, and it is thick to be hot-rolled down to 4mm, 1050 ℃ of finishing temperatures, then laminar flow be water-cooled to 630 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 5min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1.5mm, and cold-reduced sheet is at 1030 ℃ of solution annealing 3min, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 3.35g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 6
Adopt vacuum oven to smelt the steel of Chemical Composition shown in the embodiment 6 in the table 2, Sn adds in the mode of Fe-Sn alloy, is molded into the thick square ingot of 80mm, and shrinkage cavity strips off the skin; Process furnace is incubated 1.5h after being warming up to 1200 ℃ with stove, and square ingot is come out of the stove, and to be hot-rolled down to 3mm thick, 1000 ℃ of finishing temperatures, then laminar flow water-cooled to 600 ℃ batch, air cooling; Hot-rolled sheet is at 1140 ℃ of solution annealing 3min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1080 ℃ of solution annealing 1.5mm, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 0.53g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 7
Adopt electric furnace, AOD, VOD three-step approach to smelt the steel of Chemical Composition shown in the embodiment 7 in the table 2, feed the microalloying that Fe-Sn alloy silk carries out Sn during VOD, continuous casting becomes the thick strand of 200mm; Continuously cast bloom adds and to be incubated 2h after being heated to 1240 ℃ in the stove, and it is thick to be hot-rolled down to 3mm, 1010 ℃ of finishing temperatures, then laminar flow be water-cooled to 660 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 6min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1040 ℃ of solution annealing 1min, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 1.02g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 8
Adopt electric furnace, AOD duplex to smelt the steel of Chemical Composition shown in the embodiment 8 in the table 2, continuous casting becomes the thick strand of 180mm, adds the Fe-Sn alloy during AOD and carries out the Sn microalloying; Continuously cast bloom adds and to be incubated 2h after being heated to 1270 ℃ in the stove, and it is thick to be hot-rolled down to 3mm, 970 ℃ of finishing temperatures, then laminar flow be water-cooled to 740 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 4min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1.5mm, and cold-reduced sheet is at 1100 ℃ of solution annealing 1.5min, and water-cooled is to room temperature; Cold rolled annealed plate obtains to contain the Sn austenitic stainless steel through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 1.23g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Embodiment 9
Adopt electric furnace, AOD duplex to smelt the steel of Chemical Composition shown in the embodiment 9 in the table 2, continuous casting becomes the thick strand of 180mm, adds the Fe-Sn alloy during AOD and carries out the Sn microalloying; Continuously cast bloom adds and to be incubated 2.5h after being heated to 1250 ℃ in the stove, and it is thick to be hot-rolled down to 2mm, 960 ℃ of finishing temperatures, then laminar flow be water-cooled to 690 ℃ batch, air cooling; Hot-rolled sheet is at 1080 ℃ of solution annealing 2.5min, and water-cooled then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling, obtains to contain Sn austenitic stainless steel hot-roll annealing plate to room temperature.
Present embodiment obtains contains the Sn austenitic stainless steel, and its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property satisfies product standard (as shown in table 3) fully, with conventional 316L rigidity can be consistent; Its erosion rate is 4.39g/m according to the GB/T4334.6-2000 test
2H(and each Comparative Examples more as shown in table 3).
Comparative Examples 1
Adopt vacuum oven to smelt the steel of Chemical Composition shown in the Comparative Examples 1 in the table 2, be molded into steel ingot; Steel ingot cogging becomes the thick side's ingot of 50mm, and process furnace is incubated 1h after being warming up to 1240 ℃ with stove, and square ingot is come out of the stove, and to be hot-rolled down to 3mm thick, 1010 ℃ of finishing temperatures, and laminar flow water-cooled to 660 ℃ is batched then; Hot-rolled sheet is at 1060 ℃ of solution annealing 3min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1060 ℃ of solution annealing 1min, and water-cooled is to room temperature; Cold rolled annealed plate obtains the stainless steel of Comparative Examples 1 through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
The stainless steel of this Comparative Examples, its normal temperature tensile property is tested according to GB/T228-2002, mechanical property and conventional 316L rigidity energy identical (as shown in table 3); Its erosion rate is 25.34g/m2h according to the GB/T4334.6-2000 test.
Comparative Examples 2
Adopt electric furnace, AOD duplex to smelt the steel of Chemical Composition shown in the Comparative Examples 2 in the table 2, continuous casting becomes the thick strand of 200mm; Be incubated 2.5h after being heated to 1250 ℃ in the continuously cast bloom adding stove, it is thick to be hot-rolled down to 3mm, 1010 ℃ of finishing temperatures, and laminar flow is cooled to 680 ℃ and batches; Hot-rolled sheet is at 1080 ℃ of solution annealing 5min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1090 ℃ of solution annealing 1.5mm, and water-cooled is to room temperature; Cold rolled annealed plate obtains the stainless steel of Comparative Examples 2 through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
The stainless steel of this Comparative Examples, its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property is conventional 316L performance (as shown in table 3); Its erosion rate is 22.56g/m2h according to the GB/T4334.6-2000 test.
Comparative Examples 3
Adopt electric furnace, AOD, VOD three-step approach to smelt the steel of Chemical Composition shown in the Comparative Examples 3 in the table 2, feed the microalloying that Fe-Sn alloy silk carries out Sn during VOD, continuous casting becomes the thick strand of 200mm; Be incubated 2h after being heated to 1250 ℃ in the continuously cast bloom adding stove, it is thick to be hot-rolled down to 3mm, 990 ℃ of finishing temperatures, and laminar flow is cooled to 650 ℃ and batches; Hot-rolled sheet is at 1140 ℃ of solution annealing 5min, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1050 ℃ of solution annealing 1min, and water-cooled is to room temperature; Cold rolled annealed plate obtains the stainless steel of Comparative Examples 3 through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
The stainless steel of this Comparative Examples, its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property and conventional 316L performance are near (as shown in table 3); Its erosion rate is 12.15g/m2h according to the GB/T4334.6-2000 test.
Comparative Examples 4(standard 316L steel grade)
Adopt vacuum oven to smelt the steel of Chemical Composition shown in the Comparative Examples 4 in the table 2, be molded into the thick square ingot of 80mm, shrinkage cavity strips off the skin; Steel ingot is incubated 1.5h after process furnace is warming up to 1240 ℃ with stove, square ingot is come out of the stove, and to be hot-rolled down to 3mm thick, 1000 ℃ of finishing temperatures, and laminar flow water-cooled to 640 ℃ is batched then; Hot-rolled sheet is at 1040 ℃ of solution annealing 6mm, and water-cooled is to room temperature, then through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling; It is thick that acid-cleaning plate is cold-rolled to 1mm, and cold-reduced sheet is at 1080 ℃ of solution annealing 1.5mm, and water-cooled is to room temperature; Cold rolled annealed plate obtains the stainless steel of Comparative Examples 4 through technology scale removals such as scale breading, ball blast, electrolytic pickling, nitration mixture pickling.
The stainless steel of this Comparative Examples, its normal temperature tensile property is tested according to GB/T228-2002, and mechanical property and conventional 316L performance are near (as shown in table 3); Its erosion rate is 5.93g/m2h according to the GB/T4334.6-2000 test.
The Chemical Composition unit of table 2 embodiment and Comparative Examples: weight percent
To annotate: the δ value is+represent the high temperature ferrite content in its as cast condition austenite, it is 100% as cast condition austenite that the δ value be-represents it.
The erosion rate of table 3 mechanical property and 5wt% boiling sulphuric acid soln
By the embodiment 1-9 stainless mechanical property that Sn austenitic stainless steel and Comparative Examples 1-4 obtain containing of obtaining and erosion resistance (table 3) as seen:
Comparative Examples 1 and Comparative Examples 2 be not owing to contain Sn, and its sulfuric acid corrosion resistant speed is respectively 25.34g/m
2H, 22.56g/m
2H is far above the solidity to corrosion (6.01g/m that contains the Sn austenitic stainless steel of the present invention
2H is following); And do not contain Cu and contain the Comparative Examples 3 of Sn, its sulfuric acid corrosion resistant speed is 12.15g/m
2H slightly is better than Comparative Examples 1 and 2, but all far above the solidity to corrosion (6.01g/m that contains the Sn austenitic stainless steel of the present invention
2H is following), the synergy of this explanation Cu and Sn can improve the corrosion resistance to sulfuric acid of austenitic stainless steel of the present invention.The stainless steel of Comparative Examples 4 is owing to the Ni that contains up to 16.95wt%, and its anti-corrosion speed is 5.93g/m
2H approaches with the highest erosion rate of the present invention.
And Cr-Ni-Mo type austenitic stainless steel of the present invention is by behind the Sn microalloying, corrosion resistance against sulfuric acid is significantly higher than the 316L stainless steel of ad eundem composition system, and corrosion resistance against sulfuric acid approaches even more be better than containing the high-grade 316L austenitic stainless steel (Comparative Examples 4) of high Ni and high Mo content.The hot-rolled sheet that obtains according to the present invention or cold-reduced sheet can be applicable to contain SO
xThe corrosive environment that solidity to corrosion is harsher is as flue gas desulfurization device material, motor car engine egr system material etc.
The the present invention of above embodiment compares detailed introduction; but not only be confined to these embodiment; under the situation that does not break away from the present invention's design, more changeableization or improved other embodiment can also be arranged, and these changes and improvements all should fall within protection scope of the present invention.
Claims (10)
1. one kind contains the Sn austenitic stainless steel, its following chemical components in percentage by weight is: C≤0.030%, Si≤1.00%, Mn≤2.00%, P≤0.045%, S≤0.030%, Ni:10.00～15.00%, Cr:16.00～18.50%, Mo:2.00～3.00%, N≤0.10%, Sn:0.01～1.00%, all the other are Fe and unavoidable impurities.
2. the Sn austenitic stainless steel that contains as claimed in claim 1 is characterized in that, also comprises Cu, 0＜Cu≤1.2wt%.
3. the Sn austenitic stainless steel that contains as claimed in claim 1 or 2 is characterized in that, described Mn content is 0.50～1.50wt%.
4. as the arbitrary described manufacture method that contains the Sn austenitic stainless steel of claim 1-3, comprise the steps:
(1) smelt, cast: adopt vacuum induction furnace, electric furnace-AOD duplex smelting or electric furnace-AOD-VOD three-step approach to smelt according to the mentioned component proportioning, die casting or continuous casting become strand after smelting;
(2) hot rolling: the strand that obtains is heated in process furnace, and rolling then, 1200～1300 ℃ of Heating temperatures, finishing temperature be greater than 950 ℃, rolls the coiling temperature of back water-cooled to 600～750 ℃, batches the back air cooling, obtains hot-rolled sheet;
(3) hot-roll annealing pickling: the hot-rolled sheet that step (2) is obtained carries out solution annealing at 1000～1150 ℃, and soaking time is carried out according to steel plate thickness 1～3min/mm, and water-cooled obtains to contain the Sn austenitic stainless steel to room temperature then; This contains the Sn austenitic stainless steel is the hot-rolled steel sheet of thickness more than 2mm.
5. the manufacture method that contains the Sn austenitic stainless steel as claimed in claim 4 is characterized in that, also comprises the steps:
(4) cold rolling: the sheet material after step (3) the hot-roll annealing pickling is carried out cold rolling, cold rolling draft is not less than 50%;
(5) cold rolled annealed pickling: the sheet material after cold rolling is carried out solution annealing at 1000～1150 ℃, and soaking time is carried out according to steel plate thickness 1～3min/mm, and water-cooled obtains to contain the Sn austenitic stainless steel to room temperature then; This contains the Sn austenitic stainless steel is that thickness is less than the cold-rolled steel sheet of 2mm.
6. as claim 4 or the 5 described manufacture method that contain the Sn austenitic stainless steel, it is characterized in that, during step (1) was smelted, the high temperature ferrite δ content in the as cast condition austenite was less than 5wt%, δ=3 * (Cr%+Mo%)+4.5 * Si%-2.8 * Ni%-1.4 * Mn%-84 * (C%+N%)-19.8.
7. as claim 4 or the 5 described manufacture method that contain the Sn austenitic stainless steel, it is characterized in that in the step (1), Sn adds ferro-tin alloy or hello the Sn silk mode of adding that adopt.
8. the manufacture method that contains the Sn austenitic stainless steel as claimed in claim 4 is characterized in that, in the step (2), Heating temperature is 1220～1260 ℃, and coiling temperature is 650～700 ℃.
9. the manufacture method that contains the Sn austenitic stainless steel as claimed in claim 4 is characterized in that, in the step (3), the solution annealing temperature is 1050～1100 ℃, and soaking time is 1～1.5min/mm.
10. as claim 5 or the 9 described manufacture method that contain the Sn austenitic stainless steel, it is characterized in that in step (3) and the step (5), the solution annealing temperature is 1050～1100 ℃, soaking time is 1～1.5min/mm.
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