CN102274937B - Method for preparing ferrite stainless steel thin tape containing inversion segregation stannum - Google Patents
Method for preparing ferrite stainless steel thin tape containing inversion segregation stannum Download PDFInfo
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- CN102274937B CN102274937B CN 201110237025 CN201110237025A CN102274937B CN 102274937 B CN102274937 B CN 102274937B CN 201110237025 CN201110237025 CN 201110237025 CN 201110237025 A CN201110237025 A CN 201110237025A CN 102274937 B CN102274937 B CN 102274937B
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Abstract
The invention relates to the technical field of ferrite stainless steel thin tapes, in particular to a method for preparing a ferrite stainless steel thin tape containing inversion segregation stannum. The method comprises the following steps of: smelting ferrite stainless steel which contains 0.1 to 0.8 weight percent of stannum and serves as a raw material in a medium frequency induction furnace in a high vacuum environment to obtain molten steel; casting and rolling by using double-roller thin tape casting and rolling equipment to obtain ferrite stainless steel tape blank which contains the inversion segregation stannum and has the thickness of between 1.0 and 3.2 millimeters, wherein the pouring temperature is between 1,550 and 1,640 DEG C, the speed of casting and rolling is between 2 and 80 meters per minute, and a preset gap between rollers is between 0.0 and 2.2 millimeters; performing follow-up rolling and annealing to finally obtain the ferrite stainless steel thin tape containing the inversion segregation stannum. By the ferrite stainless steel thin tape containing the inversion segregation stannum, the strength and the plastic performance of the thin tape are ensured, the corrosion resistant performance of the thin tape is greatly improved, the production cost is stabilized and reduced, and rare metal resources are saved.
Description
Technical field
The present invention relates to ferritic stainless steel strip preparing technical field, be specifically related to a kind of preparation method of stanniferous ferritic stainless steel strip of inverse segregation tin.
Background technology
The chromium content of ferritic stainless steel, at 11～30wt%, is to have body-centered cubic crystal structure, take ferritic structure as main stainless steel.The advantages such as the excellent corrosion-proof performance of ferritic stainless steel, have cold work hardening tendency low, and thermal conductivity factor is high, and linear expansion coefficient is little, the shortcoming such as the intergranular corrosion resistance tendency is large, brittle transition temperature is high but have simultaneously, and the low and cold forming performance of toughness is poor.Huge advance made along with the smelting iron and steel technology, the industrialization of ultrapureization (C+N≤150ppm) technology and the interpolation of stabilizing element Nb, Ti, reduced the content of solid solution carbon, nitrogen in the ferritic stainless steel, thereby reduced the brittle transition temperature of ferritic stainless steel, improved toughness, weaken its intergranular corrosion resistance tendency, improved corrosion resistance, improved the sheet moulding performance; Simultaneously, because ferritic stainless steel is not nickeliferous or only contain a small amount of nickel, it is a kind of nickel-saving type stainless steel, under the environment of the serious scarcity of nickel resources and international nickel valency fluctuation, this nickel-saving type ferritic stainless steel is with a wide range of applications, and can replace expensive chromiumnickel austenite stainless steel in some field.
In order further to improve the corrosion resistance of ferritic stainless steel, need add Mo, Cu or a small amount of Ni and a large amount of rare metals such as Cr to it, this easily causes because rare metal resources shortage and price fluctuation cause the production cost fluctuation, and the restriction ferritic stainless steel continues, stable development.Current research shows, in ferritic stainless steel, Sn is present in top layer as a kind of metal and oxide and contributes to increase the stability of passivating film and the regeneration of passivating film self containing in the passivating film of Cr oxide.In ferritic stainless steel, add micro-tin and can significantly improve its corrosion resistance, thereby reduce, Mo, Cu and Ni etc. are had to the demand of improving the corrosion resistance rare metal, increase the stable of production cost.The patent that the patent No. is 200910306563.2 disclose in the thin-belt casting rolling process, be enriched in interdendritic low melting point element under the effect of roll-force near the segregation strip top layer, Sn is as a kind of low melting point element, if can in strip casting process, produce the inverse segregation of tin, form the enrichment region of Sn near top layer, can further improve the corrosion resisting property of stainless steel strip, reduce production costs, strengthen product competitiveness.
Summary of the invention
The present invention is directed to the problem that existing ferritic stainless steel exists, a kind of preparation method of stanniferous ferritic stainless steel strip of inverse segregation tin is provided, obtain having the stanniferous ferritic stainless steel strip of inverse segregation tin by the inventive method, significantly improve the corrosion resistance of strip, contributed to reduction to there is to Mo, Cu, Ni and Cr etc. the demand of improving matrix corrosion resistance rare metal simultaneously.
The casting preparation method of the stanniferous ferritic stainless steel strip of inverse segregation tin of the present invention is mainly that to take the ferritic stainless steel that stanniferous percentage by weight is 0.1～0.8 be base stock, the stanniferous ferritic stainless steel strip that obtains inverse segregation tin by intermediate frequency vacuum induction furnace smelting, the casting of double roll strip casting rolling plant and follow-up rolling and annealing in process.
The preparation method of the stanniferous ferritic stainless steel strip of inverse segregation tin of the present invention carries out according to following steps:
(1) smelt: by ferritic stainless steel raw material preheating to 100～300 ℃, put into the intermediate frequency vaccum sensitive stove, under the high vacuum environment that is 0.1～20Pa in vacuum, smelt and obtain molten steel;
(2) roll casting sheet: the molten steel that smelting is obtained utilizes the casting of double roll strip casting rolling plant under the pouring temperature of 1550～1640 ℃, wherein roll casting speed is 2～80m/min, roller gap is preset as 0.0～2.2mm, the stanniferous ferritic stainless steel band base that acquisition thickness is 1.0～3.2mm inverse segregation tin;
(3) reprocessing: by the stanniferous ferritic stainless steel band base pickling of the inverse segregation tin that obtains, then under ℃ condition of room temperature～700, be rolled, the rolling drafts is 40%～75%, the thickness that rear stainless steel made-up belt is depressed in rolling is 0.4～1.5mm, be heated to again 820～1100 ℃, after insulation 2～300min, air cooling, to room temperature, obtains the stanniferous ferritic stainless steel strip of inverse segregation tin.
The present invention has following outstanding advantage and beneficial effect:
(1) the inventive method is in the thin-belt casting rolling technical process, and inferior rapid solidification occurs molten steel, and cooling velocity is up to 10
2～10
4℃/S, in process of setting, volume contraction causes causing roll casting sheet and separating of roll chilling layer that again heating up appears in made-up belt, the part dendrite remelting, impel interdendritic to form the remelting passage, meanwhile, be enriched in externally roll-force of interdendritic low melting point element tin, under the acting in conjunction of molten steel solidification volume contraction and the internal pressure that causes by the remelting passage, cause casting band central core tin content to reduce, produce the enrichment of tin near top layer, can't eliminate this segregation phenomena after follow-up rolling and annealing, the final stanniferous ferritic stainless steel strip that forms inverse segregation tin, tin is present in the stability that contributes to increase passivating film in the passivating film of top layer chromium-containing oxide as a kind of metal and oxide, contribute to the regeneration of passivating film self, therefore, near tin segregation top layer will contribute to improve stability and the power of regeneration of top layer passivating film, and then strengthen the anti-corrosion of strip,
(2) the inventive method is compared with the traditional processing technology of existing ferrite stainless steel band, in corrosion resistance under identical condition, can reduce Mo, Cu, Ni and Cr etc. and there is the content that improves matrix corrosion resistance rare metal, save rare metal, reduced the fluctuation of the production cost caused due to the rare metal price fluctuation, simultaneously, because thin-belt casting rolling technique belongs to abbreviated system, shortened the production procedure of ferrite stainless steel band, this also contributes to the stable of production cost and reduces the enhancing of product competitiveness.
The accompanying drawing explanation
Tin element distribution map in Fig. 1 embodiment of the present invention 1 on the cast-rolling thin strip through-thickness;
Tin element distribution map in Fig. 2 embodiment of the present invention 1 on traditional handicraft production board through-thickness;
Fig. 3 be in the embodiment of the present invention 1 cast-rolling thin strip and traditional handicraft production board from top layer to the quantitative scatter chart of central core tin element;
Fig. 4 be in the embodiment of the present invention 1 cast-rolling thin strip and traditional handicraft production board through laboratory FeCl
3solution soaks 24 hours post-etching patterns: wherein, and (a) pattern after the cast-rolling thin strip corrosion of the embodiment of the present invention 1 preparation; (b) the rear pattern of traditional handicraft production board corrosion in embodiment 1.
The specific embodiment
In the embodiment of the present invention, adopt the double roll strip casting mill parameter to be: Casting Roller diameter 500-800mm; Body of roll width 110-254mm; The type of cooling is internal water cooling.
In the embodiment of the present invention, pickling all adopts conventional acid washing process for stainless steel, and the aqueous solution of the hydrofluoric acid that the red fuming nitric acid (RFNA) that the employing mass concentration is 65% and mass concentration are 35%, wherein water: red fuming nitric acid (RFNA): the volume ratio of hydrofluoric acid is 32:4:1.
The smelting furnace adopted in the embodiment of the present invention is vacuum medium frequency induction furnace, and model is: ZG
1-0.05.
The composition of the ferritic stainless steel adopted in the embodiment of the present invention is Sn 0.1 ~ 0.8 by weight percentage, C≤0.01, N 0.01, and Nb 0 ~ 0.4, Ti 0 ~ 0.4, Cr 14.4 ~ 18.0, Si≤0.75, Mn≤1, surplus is Fe and inevitable impurity, P≤0.035% wherein, S≤0.03%, O≤0.005%.
Comparative sample in embodiment adopts traditional handicraft production, and main technologic parameters is as follows:
Comparative sample adopts vacuum induction furnace smelting with steel, is cast into the 35Kg strand.Strand is heated to 1200 ℃ of insulations and carries out hot rolling after 2 hours on the hot rolling experimental machine.Wherein, the roughing start rolling temperature is 1050 ℃, through 4 passages, is rolled to 22mm; The finish rolling start rolling temperature is 800 ℃, and finishing temperature is 750 ℃, through 4 passages, is rolled to 5mm.The hot rolled plate obtained completes hot-roll annealing in 2.5 minutes and cold rolling on cold rolling experiment machine after pickling 950 ℃ of insulations, obtains the thick cold-reduced sheet of 1.0mm after 80% cold roling reduction.Cold-reduced sheet is incubated to 2.5 minutes under 980～1050 ℃ and air cooling to room temperature completes cold rolled annealedly, obtains the stanniferous ferritic stainless steel production board that traditional handicraft is produced.
Embodiment 1
The stanniferous ferritic stainless steel method for preparing thin strip thereof step of the present embodiment inverse segregation tin is as follows:
1, smelt
The raw material constituent of apolegamy ferritic stainless steel, percentage by weight is: C 0.0065 N 0.0060 Nb 0.14 Ti 0.08 Sn 0.26 Cr 16.4 Si 0.17 Mn 0.06, all the other are Fe and inevitable impurity;
By raw material preheating to 100 ℃, put into the intermediate frequency vaccum sensitive stove, under the high vacuum environment of 0.1～10Pa, smelted, obtain molten steel;
2, roll casting sheet
The molten steel that smelting is obtained utilizes the double roll strip casting rolling plant to carry out casting under the pouring temperature of 1580 ℃, and roll casting speed is 2m/min, and roller gap is preset as 2.2mm, and obtaining thickness is the stanniferous ferritic stainless steel band base of 3.2mm;
3, rolling and annealing
By after the pickling of above-mentioned stainless steel made-up belt, at room temperature be rolled, be rolled to 0.8mm thick after 75% drafts, under 1100 ℃, insulation 2 minutes and air cooling to room temperature completes cold rolled annealedly, obtains stanniferous ferrite stainless steel cast-rolling thin strip.
The yield strength of stanniferous ferrite stainless steel cast-rolling thin strip prepared by the present embodiment is 255MPa, and tensile strength is 395MPa, and percentage elongation is 30.5%.Detect the distribution of tin element through electron probe, find tin element skewness on the strip thickness direction, near enrichment tin top layer, central core tin content is relatively low, has the inverse segregation of tin, as shown in Figure 1.
Simultaneously, smelted the conventional strand that there is identical component with the present embodiment, and obtained stanniferous ferritic stainless steel production board after the traditional handicraft rolling.Wherein, for the stanniferous ferrite stainless steel cast-rolling thin strip that guarantees comparative sample and above-mentioned inverse segregation tin has same chip size, the stanniferous ferritic stainless steel production board that traditional handicraft is produced is incubated 2.5 minutes and completes cold rolled annealed under 980 ℃.Its yield strength is 260MPa, and tensile strength is 395MPa, and percentage elongation is 30%.Detect the distribution of tin element through electron probe, find that tin is evenly distributed on the production board thickness direction, there do not is the segregation of tin, as shown in Figure 2, this shows the close of the intensity of cast-rolling thin strip and toughness and traditional handicraft, but has the enrichment of tin near the top layer of cast-rolling thin strip, there is the inverse segregation of tin, wherein, the content of maximum enrichment place of tin element is higher than 38.5% of the tin content of traditional handicraft, as shown in Figure 3 near top layer.
The corrosion resistance of the sample of comparative sample production board prepared by traditional handicraft and the stanniferous ferrite stainless steel cast-rolling thin strip of inverse segregation tin of the present invention is liquor ferri trichloridi (the 100g FeCl by room temperature being soaked in 6%
36H
2o+900ml 0.05mol/l hydrochloric acid) 24 hours post-etching speed is estimated; As shown in Figure 4, wherein, the corrosion rate of traditional handicraft and cast-rolling thin strip is respectively 9.4499g/m to sample topography after corrosion experiment completes
2h and 8.0841g/m
2h, the corrosion rate of cast-rolling thin strip reduces by 14.45%.
Embodiment 2
Preparation method's step of the stanniferous ferritic stainless steel strip of the present embodiment inverse segregation tin is as follows:
1, smelt
The raw material constituent of apolegamy ferritic stainless steel, percentage by weight is: C 0.0080 N 0.0090 Nb 0.1 Sn 0.1 Cr 14.4 Si 0.23 Mn 0.23, all the other are Fe and inevitable impurity;
By raw material preheating to 300 ℃, put into the intermediate frequency vaccum sensitive stove, smelt and obtain molten steel under the high vacuum environment of 5～20Pa;
2, roll casting sheet
The molten steel that smelting is obtained utilizes the double roll strip casting rolling plant to carry out casting under the pouring temperature of 1640 ℃, and roll casting speed is 80m/min, and roller gap is preset as 2.0mm, the stanniferous ferritic stainless steel band base that acquisition thickness is 2.5mm;
3, rolling and annealing
By after the stainless steel made-up belt pickling of above-mentioned preparation, under 700 ℃, be rolled, be rolled to 1.5mm thick after 40% drafts, then under 1100 ℃, insulation 2 minutes and air cooling to room temperature completes cold rolled annealedly, obtains stanniferous ferritic stainless steel strip.
Simultaneously, smelted the conventional strand that there is identical component with the present embodiment, and obtained stanniferous ferritic stainless steel production board after the traditional handicraft rolling.Wherein, for guaranteeing to have same chip size with the stanniferous ferrite stainless steel cast-rolling thin strip of above-mentioned inverse segregation tin, the stanniferous ferritic stainless steel production board that traditional handicraft is produced is incubated 2.5 minutes and completes cold rolled annealed under 1050 ℃.After the detection distributed through mechanical property and tin element, find the close of the intensity of this ferritic stainless steel strip and toughness and traditional handicraft.Equally, the enrichment of tin occurs near the top layer of strip, have the inverse segregation of tin element, wherein, the content of maximum enrichment place of tin element is higher than 30% of the tin content of traditional handicraft near top layer.
The sample of traditional handicraft production board and cast-rolling thin strip is soaked in 6% the liquor ferri trichloridi 24 hours that temperature is room temperature.Finally, the corrosion rate of traditional handicraft and cast-rolling thin strip is respectively 11.7580 g/m
2h and 10.7198g/m
2h, the corrosion rate of cast-rolling thin strip reduces by 8.84%.
Embodiment 3
Preparation method's step of the stanniferous ferritic stainless steel strip of the present embodiment inverse segregation tin is as follows:
1, smelt
The constituent of apolegamy ferritic stainless steel, percentage by weight is: C 0.0040 N 0.0045 Ti 0.14 Sn 0.8 Cr 18.0 Si 0.27 Mn 0.16, all the other are Fe and inevitable impurity;
By raw material preheating to 220 ℃, put into the intermediate frequency vaccum sensitive stove, smelt and obtain molten steel under the high vacuum environment of 0.1～5Pa;
2, roll casting sheet
The molten steel that smelting is obtained utilizes the double roll strip casting rolling plant to carry out casting under the pouring temperature of 1550 ℃, and roll casting speed is 6m/min, and roller gap is preset as 0.0mm, the stanniferous ferritic stainless steel band base that acquisition thickness is 1.0mm.
3, rolling and annealing
By after stanniferous ferritic stainless steel band base obtained above pickling, under 400 ℃, be rolled, be rolled to 0.4mm after 60% drafts.Under 820 ℃, insulation 300 minutes and air cooling to room temperature completes cold rolled annealedly, obtains stanniferous ferritic stainless steel strip.
Simultaneously, smelted the conventional strand that there is identical component with the present embodiment, and obtained stanniferous ferritic stainless steel production board after the traditional handicraft rolling.Wherein, for guaranteeing to have same chip size with the stanniferous ferrite stainless steel cast-rolling thin strip of above-mentioned inverse segregation tin, the stanniferous ferritic stainless steel production board that traditional handicraft is produced is incubated 2.5 minutes and completes cold rolled annealed under 1020 ℃.After the detection distributed through mechanical property and tin element, find the close of the intensity of this ferritic stainless steel strip and toughness and traditional handicraft.Equally, the enrichment of tin occurs near the top layer of strip, have the inverse segregation of tin.Wherein, near top layer the content of maximum enrichment place of tin element higher than 45.0% of the tin content of traditional handicraft.
The sample of traditional handicraft production board and cast-rolling thin strip is soaked in 6% the liquor ferri trichloridi 24 hours that temperature is room temperature.After immersion completes, the corrosion rate of traditional handicraft and cast-rolling thin strip is respectively 6.5295g/m
2h and 5.3150g/m
2h, the corrosion rate of cast-rolling thin strip reduces by 18.60%.
Claims (1)
1. the casting preparation method of the stanniferous ferritic stainless steel strip of an inverse segregation tin, it is characterized in that carrying out according to the following steps: selecting is Sn 0.1 ~ 0.8 by weight percentage, C≤0.01, N 0.01, Nb 0 ~ 0.4, Ti 0 ~ 0.4, Cr 14.4 ~ 18.0, Si≤0.75, Mn≤1, surplus is Fe and inevitable impurity, P≤0.035% wherein, S≤0.03%, the ferritic stainless steel of O≤0.005% is base stock, by heating raw materials to 100～300 ℃, put into the intermediate frequency vaccum sensitive stove, carry out melting under the high vacuum environment of 0.1～20Pa, obtain molten steel, melted molten steel is utilized under the pouring temperature of 1550～1640 ℃ the double roll strip casting rolling plant carry out casting, wherein roll casting speed is 2～80m/min, roller gap is made as 0.0～2.2mm, obtains the stanniferous ferritic stainless steel band base of the inverse segregation tin that 1.0～3.2mm is thick, the stanniferous ferritic stainless steel band base of inverse segregation tin is rolled after pickling under ℃ condition of room temperature～700, the rolling drafts is 40%～75%, thickness after rolling is pressed is 0.4～1.5mm, be heated to again 820～1100 ℃, after insulation 2～300min, air cooling, to room temperature, obtains the stanniferous ferritic stainless steel strip of inverse segregation tin.
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| JP6050701B2 (en) * | 2012-03-01 | 2016-12-21 | 新日鐵住金ステンレス株式会社 | Ferritic stainless steel sheet for exterior panels |
| CN104846176B (en) * | 2015-05-29 | 2016-09-28 | 东北大学 | A kind of eliminate the casting-rolling method of delta ferrite in martensite aged stainless steel strip |
| CN105014025A (en) * | 2015-07-23 | 2015-11-04 | 烟台万隆真空冶金股份有限公司 | Production method for copper-nickel-tin alloy strip |
| CN105543711B (en) * | 2015-12-22 | 2017-06-20 | 东北大学 | Suppress the chromium of super austenitic stainless steel and the casting-rolling method of molybdenum element center segregation |
| US10173260B2 (en) * | 2016-04-19 | 2019-01-08 | Nucor Corporation | Method of operation of twin roll strip caster to reduce chatter |
| WO2018066019A1 (en) * | 2016-10-06 | 2018-04-12 | Ｊｆｅスチール株式会社 | Steel for crude oil tanker and crude oil tanker |
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| DE102006001195A1 (en) * | 2006-01-10 | 2007-07-12 | Sms Demag Ag | Casting-rolling process for continuous steel casting involves coordinating roll speeds and temperatures to provide higher end temperature |
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