CN103276307A - High-corrosion resistance high-toughness high-chromium ferrite stainless steel plate and manufacturing method thereof - Google Patents
High-corrosion resistance high-toughness high-chromium ferrite stainless steel plate and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a high-corrosion resistance high-toughness high-chromium ferrite stainless steel plate and a manufacturing method thereof. The high-corrosion resistance high-toughness high-chromium ferrite stainless steel plate comprises, by weight, 0.005 to 0.015% of C, 0.005 to 0.020% of N, 0.2 to 0.5% of Si, 0.2 to 0.5% of Mn, less than or equal to 0.035% of P, less than or equal to 0.010% of S, 25 to 28% of Cr, less than or equal to 4.0% of Ni, 2.0 to 4.0% of Mo, 0.1 to 0.3% of V, 0.10 to 0.30% of Ti, 0.2 to 0.4% of Nb, less than or equal to 0.005% of Al, less than or equal to 0.005% of O, and the balance Fe and unavoidable impurities, wherein based on Cr content, Mo content, Ti content, Nb content, C content and N content respectively represented by Cr, Mo, Ti, Nb, C and N, Cr+3.3*Mo is greater than or equal to 35% and Ti+Nb is greater than or equal to 16(C+N). The high-corrosion resistance high-toughness high-chromium ferrite stainless steel plate has a ductile-brittle transition temperature below -40 DEG C, pitting potential above 1000mv, a critical pitting temperature above 70 DEG C, a corrosion rate below 0.2g/m<2>h in boiling hydrochloric acid having a concentration of 1wt%, yield strength above 380MPa, tensile strength above 520MPa, an elongation rate A50mm above 25% and Vickers hardness of 180 to 220, and can be used in various harsh environments.
Description
Technical field
The present invention relates to a kind of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate and manufacture method thereof, the ductile-brittle transition temperature of this steel is below-40 ℃, pitting potential is more than 1000mv, critical pitting temperature is more than 70 ℃, and erosion rate is at 0.2g/m in the hydrochloric acid of 1% mass percent concentration that seethes with excitement
2Below the h, yield strength is more than 380MPa, and tensile strength is more than 520MPa, and unit elongation A50mm is more than 25%, and Vickers' hardness is 180-220.
Background technology
Ferritic stainless steel be chromium content 11～30%, have body-centered cubic crystal structure, under the use state based on the stainless steel of ferritic structure.Ferritic stainless steel also has good local corrosion performances such as anti-muriate spot corrosion, stress corrosion and crevice corrosion except having general corrosion resistance nature.In addition, the intensity height of ferritic stainless steel, the cold hardening tendency is lower, and thermal conductivity is 130～150% of austenitic stainless steel, linear expansivity only is 60～70% of austenitic stainless steel, is suitable for very much heat exchange purposes and the use occasion of expanding with heat and contract with cold, have thermal cycling.The ferritic stainless steel price is starkly lower than austenitic stainless steel simultaneously, therefore is widely used in fields such as household electrical appliances industry, automotive industry, building construction, petrochemical industry and environmental protection.
High chromium content ferrite stainless steel has high Cr content (21～30%) and excellent corrosion resistance nature thereof.Its corrosion resistance nature is much better than conventional ferritic stainless steel, and the ferritic stainless steel solidity to corrosion of the high trade mark is equivalent to super austenitic stainless steel and nickel-base alloy.Mainly use rigorous environment under arms, as require high building external plate, roof Material, the factory that produces organic acid (as acetic acid and lactic acid), caustic soda factory and power plant, chemical plant heat exchanger and diaphragm method solid caustic soda falling-film evaporator etc.Because Cr in the high chromium content ferrite stainless steel, Mo content are higher, therefore its low temperature brittleness problem is more outstanding, after temperature is lower than brittle transition temperature, its impelling strength significantly descends, brittle rupture easily takes place, the characteristic limitations that low-temperature flexibility is low high chromium content ferrite stainless steel in industrial promotion and application.
At present, with regard to ferritic stainless steel and manufacture method thereof multinomial patent application has been proposed both at home and abroad, the comparison of existing domestic and international high chromium content ferrite stainless steel chemical ingredients as shown in table 1.Chinese patent CN102392189A has added Mo, Ni improves corrosion resistance nature, and has adopted Nb, Ti bistableization, but its Ni content is lower, and does not add V, the low-temperature flexibility deficiency; Cr content is lower among the Chinese patent CN101381842, has added a spot of Cu, but does not contain Mo, Ni, V, and its corrosion resistance nature is on the low side; Chinese patent CN101525724 only contains the Mo of minute quantity, does not contain Ni and stabilizing element Nb and Ti; Chinese patent CN201006392 adopts Ti monostable fixed, has added Cu and rare earth element, does not add Ni, Nb and V, impurity elements such as O is not limited; Japanese Patent JP05320764A and JP08253813A have adopted higher Cr content improving erosion resistance, but do not add Ni and V improves low-temperature flexibility; European patent EP 0097254 (A2) has also been added a large amount of Cu and Zr simultaneously though added Ni, does not add V to improve toughness.
By above patent comparative analysis as can be known, high chromium content ferrite stainless steel of the prior art can't satisfy the requirement of using at present and making fully, exist solidity to corrosion difference or low-temperature flexibility poor, therefore need the high chromium content ferrite stainless steel of a kind of high anti-corrosion of exploitation, high low-temperature flexibility.
Summary of the invention
The object of the present invention is to provide a kind of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate and manufacture method thereof, this ferritic stainless steel steel plate not only has excellent corrosion resistance nature and excellent machinability, and the low-temperature impact toughness with excellence, its ductile-brittle transition temperature is below-40 ℃, pitting potential is more than 1000mv, critical pitting temperature is more than 70 ℃, and erosion rate is at 0.2g/m in the hydrochloric acid of 1% mass percent concentration that seethes with excitement
2Below the h, yield strength is more than 380MPa, tensile strength is more than 520MPa, unit elongation A50mm is more than 25%, Vickers' hardness is 180-220, can be applicable to various military service rigorous environment, to substitute high super austenitic stainless steel and the nickel-base alloy of part price, require high building external plate, roof Material as being used for, produce factory, caustic soda factory and power plant, chemical plant heat exchanger and the diaphragm method solid caustic soda falling-film evaporator etc. of organic acid (as acetic acid and lactic acid).
To achieve these goals, the present invention adopts following technical scheme:
The present invention passes through to improve Cr, Mo content on common ferritic stainless steel basis, control C, N content, adopt fixedly C, the N in the steel of Ti, Nb bistableization, and highly corrosion resistant performance and the excellent machinability of measures such as impurity element such as Al, the O realization steel grade in the control steel; By adding an amount of Ni and micro alloying element V, and avoid the generation of fragility precipitated phase by temperature, cooling control, thereby guarantee that steel grade of the present invention has good low-temperature impelling strength, the high chromium content ferrite stainless steel cold-reduced sheet that final acquisition has high corrosion resistance and high tenacity.
A kind of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate, its chemical component weight per-cent is: C:0.005～0.015%, N:0.005～0.020%, Si:0.2～0.5%, Mn:0.2～0.5%, P≤0.035%, S≤0.010%, Cr:25～28%, Ni≤4.0%, Mo:2.0～4.0%, V:0.1～0.3%, Ti:0.10～0.30%, Nb:0.2～0.4%, Al≤0.005%, O≤0.005%, and satisfy Cr+3.3 * Mo 〉=35%, Ti+Nb 〉=16 (C+N), all the other are Fe and unavoidable impurities; Its ductile-brittle transition temperature is below-40 ℃, and pitting potential is more than 1000mv, and critical pitting temperature is more than 70 ℃, and erosion rate is at 0.2g/m in the hydrochloric acid of 1% mass percent concentration that seethes with excitement
2Below the h, yield strength is more than 380MPa, and tensile strength is more than 520MPa, and unit elongation A50mm is more than 25%, and Vickers' hardness is 180-220, and this steel plate thickness is 0.5-5.0mm.
High corrosion resistance high ductility high chromium ferritic stainless steel steel plate of the present invention, high Cr adds Mo, controls ultralow C, N content, adopts Ti, Nb bistableization, and adds alloying elements such as Ni, V, has excellent corrosion resistance nature and excellent low-temperature flexibility.
The design of steel plate alloying constituent of the present invention is as follows:
The effect of Cr and Mo: Cr is most important alloying element in the stainless steel, along with the increase of chromium content, stainless steel in the oxidizing acid medium solidity to corrosion, at Cl
-Anticorrosion stress-resistant, spot corrosion, crevice corrosion ability are significantly increased in the solution.Mo is the element that is only second to Cr in the ferritic stainless steel, can improve intensity and the corrosion resistance nature of steel equally.Therefore for guaranteeing that ferritic stainless steel has excellent corrosion resistance nature, the Cr content in the ferritic stainless steel of the present invention is limited between 25～28%, and Mo content is limited between 2.0～4.0%, the equivalent of spot corrosion simultaneously PRE=Cr+3.3 * Mo 〉=35.After adopting high Cr to add Mo, easily form intermetallic compounds such as α ', σ, χ in the steel, not only reduce the erosion resistance of steel, and reduce toughness, plasticity, cold formability and the weldability of steel, so need to adopt suitable production technique to avoid the generation of these precipitated phases.
The effect of V: V is a kind of important micro alloying element, has obtained more application in steel alloy, uses less in the stainless steel.Add an amount of alloying element V and can significantly improve toughness of material, improve the intensity of material, its mechanism mainly is V (C, N) separating out of precipitate reduced macrobead carbonitride on the crystal boundary, σ phase, χ and equated separating out of intermetallic phase, reduce the dislocation motion resistance, avoid dislocation pileup group top stress concentration, thereby improve the toughness of material.Therefore added 0.1～0.3% V in the ferritic stainless steel of the present invention.
The effect of Ni: adding Ni in the ferritic stainless steel, mainly is in order to improve the low-temperature flexibility of steel, and the adding of Ni not only significantly improves the toughness of steel, and brittle transition temperature is moved down.Ni can improve the anti-general corrosion of steel, anti-spot corrosion and slit and corrosion resistant performance simultaneously, but harmful to anticorrosion stress-resistant.The price of Ni is expensive simultaneously, therefore takes all factors into consideration control Ni content≤4.0% in the ferritic stainless steel of the present invention.
The effect of C, N: C, N are harmful and unavoidable elements in the ferritic stainless steel, mainly are because C, the N solubleness in ferrite is very low, and easy and Cr reaction is separated out M at crystal boundary
23C
6, Cr
2N etc. significantly reduce the corrosion resistance nature of ferritic stainless steel, worsen toughness of material, and the material fragility transition temperature is risen.Therefore, must reduce C, N content by smelting as far as possible, and adopt strong carboritride forming element to be fixed.Take all factors into consideration the each side factors such as performance, technological feasibility and cost of steel in the ferritic stainless steel of the present invention, the content of control C is 0.005～0.015%, and the content of control N is 0.005～0.020%.
The effect of Nb, Ti: Nb, Ti and C, N have very strong chemosynthesis, by forming stable (Ti, Nb) (CN) compound, prevent from forming C, the N compound of Cr, thereby improve corrosion resistance nature.TiN has increased the ratio of equiax crystal in the continuously cast bloom as the forming core particle, can improve processability, the grain growth when TiN stops welding, thus improve weld properties.In addition, the crystal grain of all right refinement ferritic stainless steel of Nb, the toughness of raising steel reduces brittle transition temperature.For this reason, add 0.2～0.4% Nb in the ferritic stainless steel of the present invention and be no more than 0.1～0.3% Ti, controlled stabilization simultaneously than Ti+Nb 〉=16 (C+N).
The effect of Si, Mn: all adopt Si and Mn as reductor in the general ferritic stainless steel smelting process, generally control in lower level.Therefore control Si content is 0.2～0.5% in the ferritic stainless steel of the present invention, and control Mn content is 0.2～0.5%.
The effect of Al, O: Al has the effect of resistance to high temperature oxidation, sulfuration in the ferritic stainless steel.Aluminium also is the deoxidant element of using always, and aluminium is mainly residual element in the ferritic stainless steel that does not adopt aluminium deoxidation, generally controls in lower level.Oxygen is harmful element in steel, should reduce its content as far as possible.Oxygen has far-reaching influence to stainless steel final finished quality, especially can reduce the impelling strength of ferritic stainless steel.Therefore in the ferritic stainless steel of the present invention Al and O are limited to very low level, control Al≤0.005%, O≤0.005%.
The effect of P, S: phosphorus, sulphur are impurity element in steel, and S reduces the high-temp plastic of steel, in the ferritic stainless steel hot procedure, easily and other factors act on simultaneously and defective such as cause that the limit is split.In addition, S, P also can reduce the corrosion resistance nature of ferritic stainless steel.Therefore should reduce the content of P, S, control P≤0.035%, S≤0.010% as far as possible.
The manufacture method of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate of the present invention comprises the steps:
(1) smelt:
Proportioning according to above-mentioned chemical ingredients adopts electric furnace EF, argon oxygen decarburizing furnace AOD and vacuum oxygen refining furnace VOD three-step approach to smelt, and obtains molten steel.
(2) continuous casting and slab reconditioning:
Molten steel continuous casting under induction stirring that step (1) is obtained becomes continuously cast bloom, and continuously cast bloom carries out the hot repair mill again with the speed slow cooling less than 20 ℃/h between 300～600 ℃.
(3) heating, hot rolling:
To carry out hot rolling after the continuously cast bloom heating behind the hot repair mill and the insulation, being cooled to coiling temperature with the speed of cooling of 8～15 ℃/s water spray then batches, obtain coil of strip, the coil of strip that batches the back acquisition is dropped into quick water-cooled in the pond immediately, the speed control of water-cooled 30 ℃/more than the min, prevent the generation of fragility precipitated phase; Wherein, Heating temperature is 1100～1200 ℃, and soaking time is 160～240min, and the finishing temperature of hot rolling is 800～900 ℃, and rolling total deformation control is between 95～98%, and coiling temperature is 500～700 ℃.
(4) hot-roll annealing:
Coil of strip after step (3) water-cooled is carried out continuous annealing under 1000～1100 ℃, insulation 1～12min, soaking time is according to the thickness difference and proper extension, and annealing adopts water-cooled to cool off fast, and the speed of water-cooled is greater than 10 ℃/s.
(5) pickling:
Cleanup acid treatment after the coil of strip sandblast of step (4) acquisition is removed surface scale, adopt H during pickling
2SO
4Aqueous electrolysis and employing nitration mixture carry out pickling.
(6) cold rolling:
Coil of strip after the pickling is carried out cold rolling acquisition cold rolled strip, and cold rolling total draft is between 70%～85%.
(7) cold rolling after annealing:
The cold rolled strip that step (6) is obtained carries out recrystallize continuous annealing under 1000～1100 ℃, and is incubated 1～5min, and the annealing back adopts that air cooling, mist are cold, three sections segmentations of water-cooled are cooled off fast, and rate of cooling is greater than 40 ℃/s.
(8) smooth:
The band steel that step (7) is obtained carries out smooth at levelling machine, it can not only eliminate the yield phenomenon of steel plate, can also improve the surface quality of steel plate, finally obtains described high corrosion resistance high ductility high chromium ferritic stainless steel steel plate; Its ductile-brittle transition temperature is below-40 ℃, and pitting potential is more than 1000mv, and critical pitting temperature is more than 70 ℃, and erosion rate is at 0.2g/m in the hydrochloric acid of 1% mass percent concentration that seethes with excitement
2Below the h, yield strength is more than 380MPa, and tensile strength is more than 520MPa, and unit elongation A50mm is more than 25%, and Vickers' hardness is 180-220, and this steel plate thickness is 0.5-5.0mm.
Preferably, the thickness 5mm of the high corrosion resistance high ductility high chromium ferritic stainless steel steel plate of the present invention's acquisition.
Preferable, in the step (2), pour into continuously cast bloom at the vertical bending type slab caster during continuous casting.The thickness of continuously cast bloom can be 200mm, 150mm etc.
Preferable, in the step (5), H
2SO
4H in the aqueous solution
2SO
4Concentration control is at 300～500g/L; Described nitration mixture is the aqueous solution of nitric acid and hydrofluoric acid, and wherein hydrofluoric acid concentration control is at 30～50g/L, and concentration of nitric acid is controlled at 100～300g/L.
Further, the band steel of the cold rolling after annealing of step (7) also comprises acid pickling step, adopts the nitration mixture aqueous solution of nitric acid and hydrofluoric acid to carry out pickling during pickling; In the nitration mixture aqueous solution, hydrofluoric acid concentration is controlled at 30～50g/L, and concentration of nitric acid is controlled at 100～300g/L.
The high corrosion resistance high ductility high chromium ferritic stainless steel steel plate that the present invention adopts mentioned component design and processes control method to make compared with prior art has following beneficial effect:
(1) ferritic stainless steel of the present invention has adopted high Cr, has added the Mo processing, guarantees Cr+3.3 * Mo 〉=35, has the highly corrosion resistant performance;
(2) ferritic stainless steel of the present invention has added an amount of Ni and V, controls the harmful element of impact performances such as Al, O simultaneously, has effectively improved the low-temperature flexibility of steel grade, thereby has satisfied the demand of industrial steel plate;
(3) ferritic stainless steel of the present invention has adopted Nb, Ti bistableization, and fixedly the C in the steel and N avoid the formation of the carbonitride of Cr, further improve its corrosion resistance nature and forming property;
(4) ferritic stainless steel of the present invention avoids generation and the slab of harmful precipitated phase laterally to ftracture by measures such as the cooling of control slab and reconditioning temperature;
(5) ferritic stainless steel of the present invention is effectively controlled the slab surface film oxide and is constituted by the control of hot rolling Heating temperature, improves the hot rolled coil surface quality;
(6) ferritic stainless steel of the present invention passes through to adopt lower finishing temperature and coiling temperature, and batches the back water-cooled, avoids the generation of harmful precipitated phase, has improved the forming property of material simultaneously;
(7) ferritic stainless steel of the present invention guarantees that by suitable annealing process setting hot-rolled product and cold-rolled products have good single-phase ferritic structure, low-temperature flexibility and other over-all propertieies.
In a word, high corrosion resistance high ductility high chromium ferritic stainless steel steel plate of the present invention has over-all propertieies such as highly corrosion resistant performance, high low-temperature impact toughness and excellent machinability, can be applicable to various military service rigorous environment.
Description of drawings
Fig. 1 is the typical gold phase constitution of the embodiment of the invention 1 steel.
Fig. 2 is the critical pitting temperature CPT test result figure of the embodiment of the invention 1 steel.
Fig. 3 is the compound precipitated phase pattern of TiCrVC under the transmission electron microscope of the embodiment of the invention 3 steel.
Fig. 4 is the compound precipitated phase composition of TiCrVC under the transmission electron microscope of the embodiment of the invention 3 steel.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail.
Embodiment
The chemical ingredients of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate embodiment of the present invention is as shown in table 2, concrete processing parameter is as shown in table 3, each embodiment makes the steel plate that thickness is 0.5mm, 1.0mm, 2.0mm and four kinds of thickness of 5.0mm respectively, the chemical ingredients of Comparative Examples 1-2 steel is as shown in table 2, and concrete processing parameter is as shown in table 3.
(1) smelt: the proportioning according to the chemical ingredients shown in the table 1 adopts the EF+AOD+VOD three-step approach to smelt the acquisition molten steel.During smelting, earlier with desiliconization, dephosphorization is blast-melted and 400 be that the stainless steel steel scrap is blended among the electric furnace EF by a certain percentage, add high-carbon Cr-Fe alloy and carry out the heater configuration mother liquor of stainless steel; Again mother liquor of stainless steel is blended into argon oxygen decarburizing furnace AOD and adopts Ar, O
2Ferro-molybdenum and nickelalloy are according to chemical composition added in decarburization, hang in further decarburization in the vacuum oxygen refining furnace VOD stove after skimming, and add ferrocolumbium, ferro-vanadium and feed the titanium wire processing behind peroxidation, reduction, vacuum decarburization.
(2) continuous casting and slab reconditioning: the molten steel that step (1) is obtained becomes continuously cast bloom at continuous casting on the vertical bending type slab caster and under induction stirring, the thickness 200mm of continuously cast bloom, continuously cast bloom carries out the hot repair mill again with the speed slow cooling less than 20 ℃/h between 300～600 ℃.
(3) heating, hot rolling: will carry out hot rolling after the continuously cast bloom heating behind the hot repair mill and the insulation, being cooled to coiling temperature with the speed of cooling of 8～15 ℃/s water spray then batches, obtain coil of strip, the coil of strip that batches the back acquisition is dropped into quick water-cooled in the pond immediately, the speed control of water-cooled 30 ℃/more than the min, prevent the generation of fragility precipitated phase; Wherein, Heating temperature is 1100～1200 ℃, and soaking time is 160～240min, and the finishing temperature of hot rolling is 800～900 ℃, and rolling total deformation control is between 95～98%, and coiling temperature is 500～700 ℃.
(4) hot-roll annealing: the coil of strip after step (3) water-cooled is carried out continuous annealing under 1000～1100 ℃, insulation 1～12min, soaking time is according to the thickness difference and proper extension, and the annealing back adopts water-cooled to cool off fast, and the speed of water-cooled is greater than 10 ℃/s.
(5) pickling: cleanup acid treatment after the coil of strip sandblast of step (4) acquisition is removed surface scale, adopt H during pickling earlier
2SO
4Aqueous electrolysis adopts nitration mixture to carry out pickling again.H
2SO
4H in the aqueous solution
2SO
4Concentration control is at 300～500g/L; Described nitration mixture is the aqueous solution of nitric acid and hydrofluoric acid, and wherein hydrofluoric acid concentration control is at 30～50g/L, and concentration of nitric acid is controlled at 100～300g/L.
(6) cold rolling: the coil of strip after the pickling is carried out cold rolling acquisition cold rolled strip, and cold rolling total draft is between 70%～85%.
(7) cold rolling after annealing: the cold rolled strip that step (6) is obtained carries out recrystallize continuous annealing under 1000～1100 ℃, and is incubated 1～5min, and the annealing back adopts that air cooling, mist are cold, three sections segmentations of water-cooled are cooled off fast, and rate of cooling is greater than 40 ℃/s.
(8) smooth: the band steel that step (7) is obtained carries out smooth at levelling machine, finally obtains the high corrosion resistance high ductility high chromium ferritic stainless steel steel plate of each embodiment.
Table 2 unit: weight percent
In the table 2, Cr content is lower than embodiment 2,4 steel in embodiment 1,3 steel, and embodiment 2 steel do not add the Ni element, and embodiment 1-4 has adopted the steel capital Nb, Ti bistableization, and has all added a certain amount of V element.Comparative Examples 1 steel is not for containing the common high chromium content ferrite stainless steel 445 of Ni, V, and Comparative Examples 2 steel are to contain noble metal Ni to reach 25% super austenitic stainless steel 904L.
Embodiment of the invention rigidity can be tested as follows:
1, tissue
The ferritic stainless steel steel plate that embodiment 1 is obtained obtains typical gold phase constitution as shown in Figure 1 after testing, and this is organized as single-phase ferritic structure, and the metallographic structure of embodiment 2～5 steel also all is single-phase ferritic structure.
2, mechanical property
The ferritic stainless steel steel plate that each embodiment obtains through 1050 ℃ cold rolled annealed after mechanical property as shown in table 4, tension specimen thickness all is 1.0mm.From table 4 as seen, high corrosion resistance high ductility high chromium ferritic stainless steel of the present invention is owing to contain higher Cr and Mo content, therefore all has higher yield strength and tensile strength, unit elongation is all more than 25%, can satisfy follow-up processing request fully, and Vickers' hardness (HV5 represents the hardness of 5Kg power) is between 180-220.And the high austenitic stainless steel 904L unit elongation of price is higher.
Table 4
3, after the hot rolling process for cooling to the influence of mechanical property
Table 5 is that different process for cooling are to the influence of the mechanical property of hot rolling attitude embodiment 1 steel.Adopt fast speed of cooling (rate of cooling control 30 ℃/more than the min) after the hot rolling, can effectively avoid the generation of fragility precipitated phase, strength of materials hardness reduces, and unit elongation improves.Tension specimen sampling direction is perpendicular to rolling direction in the table 5, and wherein HV5 represents the Vickers' hardness of 5Kg power.
Table 5
4, different annealing temperature is to the influence (5mm) of steel room temperature impelling strength of the present invention
Table 6 be annealing temperature to the influence of the room temperature impelling strength of product, sample thickness is 5mm impact of collision sample.As seen embodiment 1-5 steel has all significantly improved room temperature impelling strength by Ni and the V that adds appropriate amount, and its room temperature notched bar impact strength all is significantly higher than common high chromium content ferrite stainless steel Comparative Examples 1.There is an optimum temps interval in annealing temperature simultaneously, namely near 1050 ℃; When annealing temperature was lower than 1000 ℃, recrystallize can't take place in material, had a large amount of intermetallic phases that is rich in Cr, Mo simultaneously, increased material fragility; After temperature was higher than 1100 ℃, material fragility also increased, and the fragility precipitated phase has been eliminated in too high back although its reason mainly is temperature, causes ferrite crystal grain too to grow up.
Table 6
| The material impact merit | 900℃ | 950℃ | 1000℃ | 1050℃ | 1100℃ | 1150℃ |
| Embodiment 1 (J) | 32 | 35 | 78 | 120 | 118 | 105 |
| Embodiment 2 (J) | 18 | 20 | 53 | 82 | 80 | 72 |
| Embodiment 3 (J) | 38 | 45 | 88 | 132 | 130 | 121 |
| Embodiment 4 (J) | 31 | 33 | 69 | 110 | 108 | 100 |
| Embodiment 5 (J) | 15 | 17 | 49 | 80 | 79 | 70 |
| Comparative Examples 1 | 4 | 4 | 19 | 33 | 22 | 10 |
5, erosion resistance
The pitting potential of adopted GB/T17899-1999 " stainless steel pitting potential measuring method " standard test embodiment 1-5 steel and Comparative Examples 1-2 steel, as shown in table 7.As seen the pitting potential of embodiment 1-5 steel all more than 1000mv, apparently higher than common high chromium content ferrite stainless steel 445, also is higher than super austenitic stainless steel 904L.
Table 7
| ? | Pitting potential (mV) |
| |
1050 |
| |
1080 |
| |
1150 |
| |
1120 |
| |
1100 |
| Comparative Examples 1 | 510 |
| Comparative Examples 2 | 900 |
6, critical pitting temperature
The critical pitting temperature of adopted ASTM G150 " stainless steel critical pitting temperature-electrochemical process " standard test embodiment 1-5 steel and Comparative Examples 1-2 steel, as shown in table 8.As seen the critical pitting temperature of embodiment 1-5 steel is all more than 70 ℃, and the critical pitting temperature of common high chromium content ferrite stainless steel 445 is at 28 ℃, and the critical pitting temperature of super austenitic stainless steel 904L is at 60 ℃.The critical pitting temperature curve of embodiment 1 steel and Comparative Examples 1-2 steel as shown in Figure 2.
Table 8
| ? | Critical pitting temperature (℃) |
| |
70.8 |
| |
71.6 |
| |
73.2 |
| |
72.0 |
| |
71.8 |
| Comparative Examples 1 | 28.2 |
| Comparative Examples 2 | 60.5 |
7, the erosion rate of each steel in 1% concentration HCl solution of boiling
Table 9 is embodiment 1-2 steel and the anti-HCl uniform corrosion of Comparative Examples 1-2 steel performance.HCl is a kind of strong reducing property medium, and general stainless steel all is difficult to resist its corrosion, yet embodiment 1 steel, embodiment 2 steel but have good erosion resistance equally in the hydrochloric environment of boiling 1%HCl (mass percent concentration), and its erosion rate is at 0.2g/m
2Suitable with Comparative Examples 2 steel below the h, almost there is not weight loss.And the erosion rate of Comparative Examples 1 common high chromium content ferrite stainless steel 445 is 78g/m
2H, the two is not at the same order of magnitude.
Table 9
| ? | Erosion rate (g/m2h) |
| |
0.11 |
| |
0.17 |
| Comparative Examples 1 | 78 |
| Comparative Examples 2 | 0.23 |
8, low-temperature flexibility
The low-temperature flexibility difference is the natural characteristics of ferritic stainless steel, has seriously restricted the application of high chromium content ferrite stainless steel plate of moderate thickness at industrial circle.Embodiment 1-5 steel has significantly improved impelling strength by adding Ni and the V of appropriate amount.Ductile-brittle transition temperature is an index weighing toughness of material, and ductile-brittle transition temperature is more low, and material at low temperature toughness is more good.Table 10 is the ductile-brittle transition temperature of embodiment 1-5 steel and Comparative Examples 1-2 steel, sample thickness is the 5mm impact of collision, as seen the ductility transmition temperature of embodiment 1-5 steel all significantly is lower than common high chromium content ferrite stainless steel Comparative Examples 1, and compare very big gap in addition with the super austenitic stainless steel, so 5mm and above steel of the present invention are not suitable for being applied to the environment below-80 ℃.The thickness of ferrite steel plate of the present invention is preferably 0.5-5mm.
Table 10
| ? | Ductile-brittle transition temperature (℃) |
| Embodiment 1 | -70 |
| Embodiment 2 | -40 |
| Embodiment 3 | -75 |
| Embodiment 4 | -60 |
| Embodiment 5 | -40 |
| Comparative Examples 1 | 25 |
| Comparative Examples 2 | -196 |
9, the compound precipitated phase of TiCrVC
Fig. 3, Fig. 4 are respectively the compound precipitated phase pattern of embodiment 3 steel TiCrVC under transmission electron microscope and the compound precipitated phase composition of TiCrVC thereof, under the visible dual function just because of Ni and V, make high chromium content ferrite stainless steel of the present invention have outstanding low-temperature flexibility.The mechanism that V improves toughness of material mainly is V (C, N) separating out of precipitate reduced macrobead carbonitride on the crystal boundary, σ phase, χ and equated separating out of intermetallic phase, reduce the dislocation motion resistance, avoid dislocation pileup group top stress concentration, thereby improve the toughness of material.
To sum up, high corrosion resistance high ductility high chromium ferritic stainless steel steel plate of the present invention not only has excellent corrosion resistance nature, and the low-temperature impact toughness with excellence, can be applied to various military service rigorous environment, to substitute high super austenitic stainless steel and the nickel-base alloy of part price, as require high building external with plate, roof Material, the factory that produces organic acid (as acetic acid and lactic acid), caustic soda factory and power plant, chemical plant heat exchanger and diaphragm method solid caustic soda falling-film evaporator etc.Its market competitiveness is strong, has bright development prospect.
Claims (6)
1. high corrosion resistance high ductility high chromium ferritic stainless steel steel plate, its chemical component weight per-cent is: C:0.005～0.015%, N:0.005～0.020%, Si:0.2～0.5%, Mn:0.2～0.5%, P≤0.035%, S≤0.010%, Cr:25～28%, Ni≤4.0%, Mo:2.0～4.0%, V:0.1～0.3%, Ti:0.10～0.30%, Nb:0.2～0.4%, Al≤0.005%, O≤0.005%, and satisfy Cr+3.3 * Mo 〉=35%, Ti+Nb 〉=16 (C+N), all the other are Fe and unavoidable impurities; Its ductile-brittle transition temperature is below-40 ℃, and pitting potential is more than 1000mv, and critical pitting temperature is more than 70 ℃, and erosion rate is at 0.2g/m in the hydrochloric acid of 1% mass percent concentration that seethes with excitement
2Below the h, yield strength is more than 380MPa, and tensile strength is more than 520MPa, and unit elongation A50mm is more than 25%, and Vickers' hardness is 180-220, and this steel plate thickness is 0.5-5.0mm.
2. high corrosion resistance high ductility high chromium ferritic stainless steel steel plate as claimed in claim 1 is characterized in that steel plate thickness≤5mm.
3. the manufacture method of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate as claimed in claim 1 or 2 comprises the steps:
(1) smelt:
Proportioning according to above-mentioned chemical ingredients adopts electric furnace EF, argon oxygen decarburizing furnace AOD and vacuum oxygen refining furnace VOD three-step approach to smelt, and obtains molten steel;
(2) continuous casting and slab reconditioning:
Molten steel continuous casting under induction stirring that step (1) is obtained becomes continuously cast bloom, and continuously cast bloom carries out the hot repair mill again with the speed slow cooling less than 20 ℃/h between 300～600 ℃;
(3) heating, hot rolling:
Will hot repair carry out hot rolling after continuously cast bloom heating behind the mill and the insulation, be cooled to coiling temperature with the speed of cooling water spray of 8～15 ℃/s then and batch, obtain coil of strip, will batch the quick water-cooled of coil of strip that the back obtains, the speed control of water-cooled 30 ℃/more than the min; Wherein, Heating temperature is 1100～1200 ℃, and soaking time is 160～240min, and the finishing temperature of hot rolling is 800～900 ℃, and rolling total deformation control is between 95～98%, and coiling temperature is 500～700 ℃;
(4) hot-roll annealing:
Coil of strip after step (3) water-cooled is carried out continuous annealing under 1000～1100 ℃, insulation 1～12min, the annealing back adopts water-cooled to cool off fast, and the speed of water-cooled is greater than 10 ℃/s;
(5) pickling:
Cleanup acid treatment after the coil of strip sandblast of step (4) acquisition is removed surface scale, adopt H during pickling
2SO
4Aqueous electrolysis and employing nitration mixture carry out pickling;
(6) cold rolling:
Coil of strip after the pickling is carried out cold rolling acquisition cold rolled strip, and cold rolling total draft is between 70%～85%;
(7) cold rolling after annealing:
The cold rolled strip that step (6) is obtained carries out recrystallize continuous annealing under 1000～1100 ℃, and is incubated 1～5min, and the annealing back adopts that air cooling, mist are cold, three sections segmentations of water-cooled are cooled off fast, and rate of cooling is greater than 40 ℃/s;
(8) smooth:
The band steel that step (7) is obtained carries out smooth, finally obtains described high corrosion resistance high ductility high chromium ferritic stainless steel steel plate, and this steel plate thickness is 0.5-5.0mm; Its ductile-brittle transition temperature is below-40 ℃, and pitting potential is more than 1000mv, and critical pitting temperature is more than 70 ℃, and erosion rate is at 0.2g/m in the hydrochloric acid of 1% mass percent concentration that seethes with excitement
2Below the h, yield strength is more than 380MPa, and tensile strength is more than 520MPa, and unit elongation A50mm is more than 25%, and Vickers' hardness is 180-220.
4. the manufacture method of high corrosion resistance high ductility high chromium ferritic stainless steel steel plate as claimed in claim 3, it is characterized in that, the band steel of the cold rolling after annealing of step (7) also comprises acid pickling step, adopts the nitration mixture aqueous solution of nitric acid and hydrofluoric acid to carry out pickling during pickling; In the nitration mixture aqueous solution, hydrofluoric acid concentration is controlled at 30～50g/L, and concentration of nitric acid is controlled at 100～300g/L.
5. as the manufacture method of claim 3 or 4 described high corrosion resistance high ductility high chromium ferritic stainless steel steel plates, it is characterized in that, in the step (2), pour into continuously cast bloom at the vertical bending type slab caster during continuous casting.
6. as the manufacture method of claim 3 or 4 described high corrosion resistance high ductility high chromium ferritic stainless steel steel plates, it is characterized in that, in the step (5), H
2SO
4H in the aqueous solution
2SO
4Concentration control is at 300～500g/L; Described nitration mixture is the aqueous solution of nitric acid and hydrofluoric acid, and wherein hydrofluoric acid concentration control is at 30～50g/L, and concentration of nitric acid is controlled at 100～300g/L.
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