CN104726785A - Medium-chromium ferritic stainless steel without corrosion channel at crystal boundary and production method of stainless steel - Google Patents
Medium-chromium ferritic stainless steel without corrosion channel at crystal boundary and production method of stainless steel Download PDFInfo
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Abstract
The invention claims a medium-chromium ferritic stainless steel without corrosion channel at crystal boundary and a production method of the stainless steel. The steel comprises the following chemical components in percentage by weight: 0.01-0.03% of C, 16.0-20.0% of Cr, 0.2-0.5% of Si, 0.2-0.5% of Mn, 0.02-0.1% of V, less than or equal to 0.2% of Ni, less than or equal to 0.1% of Mo, less than or equal to 0.1% of Cu, less than or equal to 0.2% of Sn, less than or equal to 0.05% of N, less than or equal to 0.05% of P, less than or equal to 0.01% of S, less than or equal to 0.2% of Nb, less than or equal to 0.2% of Ti, and the balance of Fe and unavoidable impurities, and the following conditions can be satisfied: Mo+Cu+Sn is equal to or greater than 0.2% and equal to or less than 0.5%, and Nb+Ti is equal to or greater than 0.2% and equal to or less than 0.5%. The surface crystal boundary of the medium-chromium ferritic stainless steel produced according to the invention excludes corrosion channel, the Vickers hardness is 120-150HV, the roughness Ra is less than or equal to 3.5mu m, and the medium-chromium ferritic stainless steel is widely applicable for industries of products like household appliances, decorations and computer hardware shells with strict request on stainless steel surface.
Description
Technical field
The present invention relates to middle chrome ferritic stainless steel and the production method thereof of the corrosion-free ditch of a kind of crystal boundary.
Background technology
SUS430 is typical middle chrome ferritic stainless steel, has the over-all propertieies such as good solidity to corrosion, plasticity and oxidation-resistance, is widely used in the arts such as heat-resisting utensil, burner, electrical home appliances, tableware, kitchen sink.Due to carbon and nitrogen element content higher, there is high temperature crystallization phenomenon in existing SUS430 stainless steel, the carbide (Cr of rich chromium after cooling in hot rolling and annealing process
23c
6) and nitride (Cr
2n) separate out at grain boundaries, cause poor chromium near crystal boundary and solidity to corrosion significantly declines.And due to different positions oxide skin textural difference and acid cleaning process fluctuation, there is intergranular corrosion and exist and significantly corrode ditch in SUS430 stainless steel coil of strip surface in pickling rear section in the acid solutions such as sulfuric acid, nitric acid and hydrofluoric acid, has a strong impact on surface quality and the use properties of follow-up goods.
In order to reduce stainless steel intercrystalline corrosion, can be realized by production technique approach such as optimizing components and the hot rolling of adjustment material, annealing, pickling.Chinese patent CN102367551A discloses a kind of ferritic stainless steel that can reduce intergranular corrosion risk, and this stainless steel is mainly through reducing C content thus reducing Cr
23c
6separate out, reduce the intergranular corrosion degree under applied at elevated temperature condition, thus improve the material military service life-span, mainly for heat exchanger industry.Chinese patent CN1625447A is by adjustment hot rolling finishing temperature and utilize the hot heat-treating methods that completes of rolling to avoid chromium carbide and separate out the relevant perishable phenomenon of the stainless steel intercrystalline corrosion that causes, and the method manufactures for austenitic stainless steel hot rolled band.
Summary of the invention
The object of the present invention is to provide middle chrome ferritic stainless steel and the production method thereof of the corrosion-free ditch of a kind of crystal boundary, the corrosion-free ditch of this steel surface grain boundaries, Vickers' hardness is 120 ~ 150HV, roughness Ra≤3.5 μm.
For achieving the above object, technical scheme of the present invention is:
The middle chrome ferritic stainless steel of the corrosion-free ditch of a kind of crystal boundary, its chemical component weight per-cent is: C:0.01 ~ 0.03%, Cr:16.0 ~ 20.0%, Si:0.2 ~ 0.5%, Mn:0.2 ~ 0.5%, V:0.02 ~ 0.1%, Ni≤0.2%, Mo≤0.1%, Cu≤0.1%, Sn≤0.2%, N≤0.05%, P≤0.05%, S≤0.01%, Nb≤0.2%, Ti≤0.2%, all the other are Fe and inevitable impurity, and above-mentioned element needs satisfied following relation simultaneously: 0.2%≤Mo+Cu+Sn≤0.5%, 0.2%≤Nb+Ti≤0.5%.
Further, the surperficial Vickers' hardness of described middle chrome ferritic stainless steel is 120 ~ 150HV, surface roughness Ra≤3.5 μm.
The microtexture of described middle chrome ferritic stainless steel is ferrite+carbide tissue.
In Composition Design of the present invention:
Cr:Cr is most important element in stainless steel, is to determine the corrosion proof topmost element of stainless steel.Cr is the main component of passivation film on stainless steel surface and oxide film, and generally, Cr content is higher, and solidity to corrosion is better, but excessive Cr causes cost to raise.Therefore, Cr content of the present invention controls 16 ~ 20%.
C, N:C and N have disadvantageous effect to material intergranular corrosion, easy at grain boundaries formation carbide (Cr after high temperature process cooling
23c
6) and nitride (Cr
2n).Therefore, C content of the present invention controls 0.01 ~ 0.03%, and N content controls≤0.05%.
Si:Si at high temperature reacts the SiO generating difficult pickling
2, be easy to form continuous inner oxide, cause pickling difficulty.Therefore, Si content of the present invention controls 0.2 ~ 0.5%.
S, P:S, P have disadvantageous effect to the solidity to corrosion of material and plasticity, and S content of the present invention controls to control≤0.05% at≤0.01%, P content.
Mo, Cu, Sn:Mo, Cu, Sn are the important elements improving stainless steel corrosion resisting property.Cu can suppress Corrosion of Stainless Steel, although Sn is less than Cu to suppressing the effect of Corrosion of Stainless Steel, stainless steel corrosion resisting property can be improved in Sn enrichment material surface, and Sn and Cu interaction is to raising stainless steel solidity to corrosion better effects if.Mo can improve the stability of stainless steel oxidation film and passive film, thus favourable to raising stainless steel intercrystalline corrosion performance.Therefore, content of the present invention controls at 0.2%≤Mo+Cu+Sn≤0.5%.
Nb, Ti, V:Nb, Ti and V can form stable carbide, and reduce Cr
23c
6and Cr
2n separates out at grain boundaries, and therefore, add Nb, Ti and V favourable to the corrosion among crystalline grains of chrome ferritic stainless steel in raising, the present invention controls 0.2%≤Nb+Ti≤0.5%, 0.02≤V≤0.1%.
The manufacture method of the middle chrome ferritic stainless steel of the corrosion-free ditch of crystal boundary of the present invention, it comprises the steps:
1) smelt, cast
Strand is become through smelting, continuous casting by above-mentioned chemical composition.
2) hot rolling, to batch
Strand is heated to 1050 ~ 1150 DEG C, through roughing, finish rolling, then batches, wherein, roughing temperature is 950 ~ 1050 DEG C, and final rolling temperature is 850 ~ 950 DEG C, and coiling temperature is 600 ~ 700 DEG C.
3) anneal
Annealing temperature is 800 ~ 870 DEG C, and soaking time is 12 ~ 24h;
4) pickling
Adopt the continuous pickling technique of scale breading-ball blast-pre-pickling-nitration mixture pickling.
Preferably, step 4) shot blasting velocity of described ball blast is 55 ~ 70m/s, ball blast flow is 400 ~ 1000kg/min.
Preferably, step 4) described pre-pickling is sulfuric acid washing, acid strength is 150 ~ 250g/L, and pickling temperature is 65 ~ 80 DEG C;
Preferably, step 4) described nitration mixture pickling is nitric acid and hydrofluoric acid mixed acid liquid, concentration of nitric acid is 80 ~ 160g/L, and hydrofluoric acid concentration is 5 ~ 15g/L, and pickling temperature is 45 ~ 55 DEG C.
Hot-rolled temperature of the present invention and coiling temperature have material impact to coil of strip surface corrosion among crystalline grains.If hot-rolled temperature is higher, coil of strip surface crystallization degree is high, or completely crystallization or coarse grains, the carbide (Cr of rich chromium after cooling
23c
6) and nitride (Cr
2n) separate out at grain boundaries, cause poor chromium near the crystal boundary of coil of strip surface and corrosion among crystalline grains significantly declines.Therefore, in order to reduce coil of strip surface corrosion ditch after pickling, must control coil of strip surface crystallization, i.e. roughing temperature controls below 1050 DEG C, and final rolling temperature controls below 950 DEG C, and oiler temperature control is below 700 DEG C.
Annealing temperature of the present invention has material impact to coil of strip surface corrosion among crystalline grains.If annealing temperature is higher, coil of strip perfect recrystallization even crystal grain becomes thicker, and material corrosion among crystalline grains obviously declines.The coil of strip that corrosion among crystalline grains is on the low side easily produces corrosion ditch in pickling rear surface in sulfuric acid, nitric acid and hydrofluoric acid acid solution.Therefore, in order to reduce coil of strip surface corrosion ditch after pickling, must control coil of strip surface crystallization, namely annealing temperature controls below 870 DEG C, and soaking time controls at 12 ~ 24h.
Acid cleaning process of the present invention has a significant impact coil of strip surface intergranular corrosion.If the uneven coil of strip overpickling easily causing ball blast degree heavy of ball blast, the sulfuric acid concentration of pre-pickling section and pickling temperature is higher also easily causes overpickling, nitration mixture section hydrofluoric acid concentration is higher and concentration of nitric acid is on the low side also easily causes overpickling.Overpickling will cause coil of strip generation intergranular corrosion and produce significantly corroding ditch.In order to avoid crossing coil of strip pickling, sulfuric acid concentration controls at below 250g/L, and concentration of nitric acid controls at more than 80g/L, and hydrofluoric acid concentration controls at below 15g/L.
Beneficial effect of the present invention:
1. chemical composition aspect: lower C and N content and appropriate Nb, Ti and V, can alleviate carbide (Cr in coilcooling process
23c
6) and nitride (Cr
2n) separate out, improve coil of strip corrosion among crystalline grains.
2. production technique aspect: by controlled rolling and annealing process condition, controls coil of strip surface crystallization degree, thus improves coil of strip corrosion among crystalline grains; By suitable acid cleaning process, reduce acid solution to coil of strip surface corrosion, thus avoid the appearance of corroding ditch.
3. microstructure aspect: microstructure of the present invention is ferrite+carbide tissue, ferritic structure imperfect crystal and the crystal grain of crystallization is tiny, carbide tissue is Dispersed precipitate, decreases poor chromium effect near crystal boundary, favourable to raising coil of strip corrosion among crystalline grains.
4. the corrosion-free ditch of middle chrome ferritic stainless steel surface grain boundaries of the present invention's production, roughness Ra≤3.5 μm; Coil of strip of the present invention is good through the accurate band steel surface quality of cold rolling production, through overlay film or adhesive tape are sticky take off after coil of strip surface without bright spot defect (i.e. golden dust or gold dust defect), household electrical appliances, decoration and computer hard disc housing etc. have strict demand goods industry to stainless steel surface can be widely used in.
Accompanying drawing explanation
Fig. 1 is the one-level intergranular corrosion surface topography map of existing ferritic stainless steel.
Fig. 2 is the secondary intergranular corrosion surface topography map of existing ferritic stainless steel.
Fig. 3 is three grades of intergranular corrosion surface topography maps of existing ferritic stainless steel.
Fig. 4 is the surface topography map of the embodiment of the present invention 1 steel.
Fig. 5 is the surface topography map of the embodiment of the present invention 2 steel.
Fig. 6 is the surface topography map of the embodiment of the present invention 3 steel.
Fig. 7 is the surface topography map of the embodiment of the present invention 4 steel.
Fig. 8 is the surface topography map of the embodiment of the present invention 5 steel.
Fig. 9 is the surface topography map of the embodiment of the present invention 6 steel.
Figure 10 is the surface topography map of the embodiment of the present invention 7 steel.
Figure 11 is the surface topography map of the embodiment of the present invention 8 steel.
Figure 12 is the surface topography map of the embodiment of the present invention 9 steel.
Figure 13 is the surface topography map of the embodiment of the present invention 10 steel.
Figure 14 is the surface topography map of the embodiment of the present invention 11 steel.
Figure 15 is the surface topography map of the embodiment of the present invention 12 steel.
Figure 16 is the surface topography map of the embodiment of the present invention 13 steel.
Figure 17 is the surface topography map of the embodiment of the present invention 14 steel.
Figure 18 is the surface topography map of the embodiment of the present invention 15 steel.
Figure 19 is the surface topography map of the embodiment of the present invention 16 steel.
Figure 20 is the surface topography map of the embodiment of the present invention 17 steel.
Figure 21 is the surface topography map of comparative example 1 steel.
Figure 22 is the surface topography map of comparative example 2 steel.
Figure 23 is the surface topography map of comparative example 3 steel.
Figure 24 is the surface topography map of comparative example 4 steel.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1
Adopt AOD and LF stove to smelt the steel of composition shown in table 1, continuous casting becomes base, and continuous blank heating temperature is 1050 DEG C, roughing temperature 950 DEG C, final rolling temperature 850 DEG C, and the thick hot-rolled sheet of 2 ~ 6mm is made in hot rolling, coiling temperature 650 DEG C.Above-mentioned hot rolled coil adopts cover annealing, annealing temperature 800 DEG C, soaking time 24h.Acid cleaning process shot blasting velocity 55m/s, ball blast flow 500Kg/min; Pre-pickling adopts 160g/L sulphuric acid soln, pickling temperature 65 DEG C, and nitration mixture is washed and adopted 150g/L nitric acid and 6g/L hydrofluoric acid mixed acid solution, pickling temperature 45 DEG C.
Embodiment 2
Adopt AOD and LF stove to smelt the steel of composition shown in table 1, continuous casting becomes strand, strand is heated to 1100 DEG C, roughing temperature 1000 DEG C, final rolling temperature 900 DEG C, and the thick hot-rolled sheet of 2 ~ 6mm is made in hot rolling, coiling temperature 675 DEG C.Hot rolling cover annealing temperature 835 DEG C, soaking time 19h.Acid cleaning process shot blasting velocity 65m/s, ball blast flow 700Kg/min; Pre-pickling adopts 200g/L sulphuric acid soln, pickling temperature 70 DEG C; Nitration mixture is washed and is adopted 120g/L nitric acid and 10g/L hydrofluoric acid mixed acid solution, pickling temperature 50 DEG C.
The chemical composition of embodiment of the present invention 1-17 and comparative example 1-4 is as shown in table 1.The technique of embodiment 3-17 and comparative example 1-4 is with embodiment 1, and concrete technology condition is see table 2.
The intergranular corrosion evaluation procedure of embodiment of the present invention 1-17 and comparative example 1-4 is as follows: steel coil head 1/4th position sampling after pickling, under scanning electron microscope, observe surface topography.With reference to USS A763-93 about ferritic stainless steel intergranular corrosion evaluation method, coil of strip surface intergranular corrosion degree is divided into three grades, and namely surperficial corrosion-free ditch is one-level, as shown in Figure 1; Surface have some corrosion ditches, but not completely surround crystal grain be secondary, as shown in Figure 2; There is more corrosion ditch on surface, and 1 and above crystal grain are corroded, ditch surrounds completely is three grades, as shown in Figure 3.
The surface topography of embodiment of the present invention 1-17 and comparative example 1-4 is as Fig. 4-24, and its intergranular corrosion evaluation result is see table 2.From Fig. 4-20, all corrosion-free ditch in embodiment 1-17 steel surface, intergranular corrosion degree is one-level.From Figure 21-24: there is corrosion ditch on comparative example 1,2,3 steel surface, but neither one crystal grain links up completely, and intergranular corrosion degree is secondary; There is more corrosion ditch on comparative example 4 steel surface, and has multiple crystal grain to link up completely, and intergranular corrosion degree is three grades.
Claims (9)
1. the middle chrome ferritic stainless steel of the corrosion-free ditch of crystal boundary, its chemical component weight per-cent is: C:0.01 ~ 0.03%, Cr:16.0 ~ 20.0%, Si:0.2 ~ 0.5%, Mn:0.2 ~ 0.5%, V:0.02 ~ 0.1%, Ni≤0.2%, Mo≤0.1%, Cu≤0.1%, Sn≤0.2%, N≤0.05%, P≤0.05%, S≤0.01%, Nb≤0.2%, Ti≤0.2%, all the other are Fe and inevitable impurity, and above-mentioned element needs satisfied following relation simultaneously: 0.2%≤Mo+Cu+Sn≤0.5%, 0.2%≤Nb+Ti≤0.5%.
2. the middle chrome ferritic stainless steel of the corrosion-free ditch of crystal boundary according to claim 1, is characterized in that, the surperficial Vickers' hardness of described middle chrome ferritic stainless steel is 120 ~ 150HV, surface roughness Ra≤3.5 μm.
3. the middle chrome ferritic stainless steel of the corrosion-free ditch of crystal boundary according to claim 1 and 2, is characterized in that, the microtexture of described middle chrome ferritic stainless steel is ferrite+carbide tissue.
4. the production method of middle chrome ferritic stainless steel as claimed in claim 1, is characterized in that, comprise the steps:
1) smelt, cast
Strand is become through smelting, continuous casting by chemical composition according to claim 1;
2) hot rolling, to batch
Strand is heated to 1050 ~ 1150 DEG C, through roughing, finish rolling, batches, wherein, roughing temperature is 950 ~ 1050 DEG C, and final rolling temperature is 850 ~ 950 DEG C, and coiling temperature is 600 ~ 700 DEG C;
3) anneal
Annealing temperature is 800 ~ 870 DEG C, and soaking time is 12 ~ 24h;
4) pickling
Adopt the continuous pickling technique of scale breading-ball blast-pre-pickling-nitration mixture pickling.
5. the production method of middle chrome ferritic stainless steel according to claim 4, is characterized in that, step 4) shot blasting velocity of described ball blast is 55 ~ 70m/s, ball blast flow is 400 ~ 1000kg/min.
6. the production method of middle chrome ferritic stainless steel according to claim 4, is characterized in that, step 4) described pre-pickling is sulfuric acid washing, acid strength is 150 ~ 250g/L, and pickling temperature is 65 ~ 80 DEG C.
7. the production method of middle chrome ferritic stainless steel according to claim 4, it is characterized in that, step 4) described nitration mixture pickling is nitric acid and hydrofluoric acid mixed acid liquid, concentration of nitric acid is 80 ~ 160g/L, hydrofluoric acid concentration is 5 ~ 15g/L, and pickling temperature is 45 ~ 55 DEG C.
8. according to any one of claim 4-7, the production method of chrome ferritic stainless steel, is characterized in that, the surperficial Vickers' hardness of described middle chrome ferritic stainless steel is 120 ~ 150HV, surface roughness Ra≤3.5 μm.
9. according to any one of claim 4-7, the production method of chrome ferritic stainless steel, is characterized in that, the microtexture of described middle chrome ferritic stainless steel is ferrite+carbide tissue.
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| CN111575452A (en) * | 2020-05-21 | 2020-08-25 | 山东泰山钢铁集团有限公司 | Method for reducing hot-rolled pickling surface roughness of 10Cr17 stainless steel |
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| CN111575452A (en) * | 2020-05-21 | 2020-08-25 | 山东泰山钢铁集团有限公司 | Method for reducing hot-rolled pickling surface roughness of 10Cr17 stainless steel |
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