WO2007055400A1 - Tole en acier pour emaillage par coulage continu avec une tres grande improbabilite d’ecaillage et son procede de production - Google Patents

Tole en acier pour emaillage par coulage continu avec une tres grande improbabilite d’ecaillage et son procede de production Download PDF

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Publication number
WO2007055400A1
WO2007055400A1 PCT/JP2006/322786 JP2006322786W WO2007055400A1 WO 2007055400 A1 WO2007055400 A1 WO 2007055400A1 JP 2006322786 W JP2006322786 W JP 2006322786W WO 2007055400 A1 WO2007055400 A1 WO 2007055400A1
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steel sheet
oxides
steel
oxide
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PCT/JP2006/322786
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English (en)
Japanese (ja)
Inventor
Hidekuni Murakami
Satoshi Nishimura
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Nippon Steel Corporation
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Application filed by Nippon Steel Corporation filed Critical Nippon Steel Corporation
Priority to EP06823434.3A priority Critical patent/EP1950317B1/fr
Priority to US12/084,609 priority patent/US20090047168A1/en
Priority to JP2007544239A priority patent/JP4954889B2/ja
Priority to ES06823434.3T priority patent/ES2568678T3/es
Priority to CN2006800507081A priority patent/CN101356295B/zh
Publication of WO2007055400A1 publication Critical patent/WO2007055400A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D5/00—Coating with enamels or vitreous layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

Definitions

  • the present invention relates to an enameled steel sheet having excellent enamel characteristics (foam resistance / spot resistance, adhesion, resistance to picking) and processing characteristics, and a method for producing the same, and is characterized by being obtained by continuous forging.
  • Patent No. 3 2 0 60 4 4 6, Patent No. 3 3, for example, can produce a steel sheet for enamel with good heat resistance by B.
  • Patent Document 1 discloses that since the deoxidizing ability of B is small, the amount of oxygen in the steel can be kept high.
  • Patent No. 3 6 1 3 8 1 0 is unknown in detail, but B is effective in preventing claw jumping and foaming. Abnormal etching of grain boundaries on the steel sheet surface by sulfuric acid pickling before enamelling Further, the present inventors have tried to improve a steel sheet for brazing containing B and having excellent tensile properties and deep drawability. -8 0 9 3 4 and Japanese Patent Application Laid-Open No.
  • the present invention develops the technology of the above-mentioned steel sheet for brazing steel, and it is possible to further improve the toughness by controlling not only the nitride but also the oxide form.
  • the purpose is to provide a steel sheet for continuous forging enamel that has excellent resistance to tearing and that can be spun into a brazing wax, and its manufacturing method.
  • Akira is a conventional steel sheet, obtained through examination of the seeds to optimize the steel sheet manufacturing method to the utmost limit, and with regard to the loose characteristics of the enameled steel sheet, especially for B-containing steels. As a result of investigating the influence of manufacturing conditions, especially melting conditions, the following items 1) to 5) were newly discovered.
  • the magnitude of the variation of the element concentration in the oxide can be controlled by the addition of elements during melting, especially the timing of addition of oxide-forming elements.
  • the present invention has been completed based on the above findings.
  • oxides having different compositions or integrated oxides in a final product that has undergone a process in which rolling is performed either hot or cold. Even a product is characterized by having a large compositional variation in the interior and also presenting it in a specific preferred form.
  • the gist of the present invention is as follows.
  • a 1 0.0 3 0% or less
  • N b Less than 0.04% (including zero),
  • the steel sheet for continuous forging enamel having excellent toughness resistance according to any one of the above (1) to (3).
  • the steel sheet for continuous forging brazing excellent in toughness resistance according to any one of the above (1) to (4), characterized by comprising:
  • B There is a distribution of mass concentration, and the ratio of B mass concentration (B ma X%) in the high concentration part to B mass concentration (B min%) in the low concentration part is B ma X / B min ⁇ 1.2
  • B ma X the ratio of B mass concentration in the high concentration part to B mass concentration (B min%) in the low concentration part is B ma X / B min ⁇ 1.2
  • the composite oxide has a linear distance between the centers of both composite oxides of 0.1 m or more and within 20 Atm, and the straight line connecting the centers of both composite oxides is within ⁇ 10 ° from the rolling direction.
  • the steel sheet for continuous and forged enamel which is excellent in toughness resistance according to any one of the above (1) to (7), characterized in that it exists at an angle of
  • Mn mass concentration of complex oxides in which oxides such as Fe, Mn, Si, A1, Nb, B, V, Cr, etc. in the plate are combined and integrated (%) Of another composite oxide with an Mn mass concentration (%) of at least 1.2 times or less than 1 / 1.2 times the linear distance between the centers of both composite oxides of at least 0.1 m, Any one of the above (1) to (8), characterized in that a straight line connecting the centers of both composite oxides exists within an angle of ⁇ 10 ° from the rolling direction. Steel sheet for continuous forging enamel with excellent resistance to tears as described.
  • N b Less than 0.04% (including zero),
  • a method for producing a steel sheet for continuous forging enamel having excellent durability and resistance according to (10) or (11), characterized by comprising
  • the thickness of the strip is 1 to 4 layers, and the cooling rate during solidification is ⁇ 10 ° CZ seconds.
  • FIG. 1 is a diagram for explaining the state of oxides when rolling steel containing a coarse composite oxide having a large concentration difference between B and Mn.
  • Fig. 2 is a diagram for explaining the state of an oxide when rolling steel containing a conventional coarse oxide.
  • Fig. 3 is a diagram illustrating the state of oxides when rolling steel containing fine oxides.
  • FIG. 4 is a diagram for explaining that when a steel containing a coarse composite oxide having a large concentration difference between B and Mn is rolled, voids around the composite oxide become large.
  • Fig. 5 is a diagram for explaining that the voids around the composite oxide are small when rolling steel containing coarse composite oxide with no concentration difference.
  • the diameter of the oxide to be controlled in the present invention is set to 0.10 zm or more. Oxides smaller than this range are subject to special control because they greatly reduce the effect of improving the resistance to squeezing, that is, the hydrogen permeation-preventing ability, which is a major characteristic of the steel of the present invention. There is no need. Preferably, even for oxides of 0.50 ⁇ or more, more preferably 1.0; m or more, and even more preferably 2.0 m or more, Features are recognized.
  • the upper limit of the diameter is not particularly limited in consideration of the effect of the present invention. However, depending on the oxygen content, if the amount of coarse oxide increases, the number density of the oxide decreases and the effect of inhibiting hydrogen permeation decreases.
  • the average of oxide It is preferable that the diameter is 15 m or less, preferably 10 / zm or less, and more preferably 5 m or less.
  • One of the characteristics of the oxide defined in the present invention is the B concentration of the oxide.
  • it is necessary to specify a high density and a low density, and 1 0 0 111 1 0 0 111 which is a size of 0.0 or more in the field of view is measured. That is, there are non-integral oxides with different B concentrations in the concentrations measured for the oxide in the observation field of 100 ⁇ m X 100 m in the cross section of the plate, and a high concentration of B concentration (B max ) And low concentration B concentration (B min), B max / B min ⁇ l.
  • the B concentration ratio is 1.2 or more, as will be described later, the shape change of the oxide during rolling and the formation of voids associated therewith can be performed efficiently.
  • the property is remarkably improved.
  • it is 1.5 or more, more preferably 2.0 or more, still more preferably 4.0 or more, and still more preferably 6.0 or more.
  • the concentration of each element in the oxide for defining the present invention is not particularly limited, but the concentration of each oxide needs to be specified. is there.
  • an energy dispersive X-ray dispersive analyzer EDAX
  • the measurement method may be a normal method. However, since it is necessary to determine the concentration in a very small area, care must be taken such as making the beam diameter of the electron beam sufficiently small.
  • the ratio of the heights of the detection peaks may be used. It should be noted that the density ratio between the high density part and the low density part tends to increase as the size of the measurement area decreases. Ultimately, if the concentration of a region of one atom is measured, it can be assumed that the high concentration part is 100% and the low concentration part is 0%. In the present invention, an electron beam irradiation area of a general TEM or SEM that is usually used by the present inventor is considered, and an average value in an area of about 0.01 to 0.1 m is used. Shall.
  • the information obtained is from a wide area of the set electron beam diameter.
  • the reason for improving the resistance to slipping that is, the hydrogen permeation blocking ability is not clear, but it is considered as follows.
  • the oxide dispersed in the steel of the present invention was originally an integral oxide as described later.
  • the oxide was mainly stretched in the hot rolling process, and is mainly crushed in the cold rolling process.
  • the degree of stretching differs depending on the oxide part, and the shape of the oxide becomes complicated.
  • the thinned (thinned) part is preferentially crushed, and the part with a large variation in shape is subject to deformation stress. It is expected that crushing will be given priority due to concentration. As a result, the parts having different compositions are efficiently crushed and dispersed. During such efficient crushing, a large number of voids are formed, which become hydrogen trap sizes in the steel, remarkably exhibiting the hydrogen permeation-preventing ability required for steel plates, that is, the anti-slip property. It is thought that it is the power of improvement. The above will be explained in detail using figures. When there is a large concentration difference of BM n in the oxide, the coarse composite oxide 1 is crushed by hot rolling 2, stretching 3, and cold rolling 4 as shown in Fig.
  • the effect of the present invention can be sufficiently obtained when the gaps between the complex oxides formed in this way are crushed and lost by rolling in the same hot rolling process.
  • This is shown schematically in Figure 45.
  • the composite oxide itself has the same size and arrangement, in the invention steel as shown in Fig. 4 where there is a large concentration difference of BM n in the composite oxide and the composite oxide containing a large void forming ability,
  • the void around the complex oxide is larger than 1 1, which is preferable for improving the anti-slip property.
  • the oxide with the same concentration shown in Fig. 5 has a small void.
  • composite oxides with different compositions However, it also has a specific relative positional relationship in the steel sheet.
  • a complex oxide exhibiting a high B concentration and a complex oxide exhibiting a low B concentration have a concentration ratio of 1.2 times or more, and the straight line connecting the centers of the complex oxides is an angle of ⁇ 10 ° from the rolling direction.
  • the composite is characterized in that it exists within 0.1 O m or more and 2 O wm or less in the linear distance between the oxide centers.
  • the angle is preferably within an angle of 7 ° on the soil, more preferably within an angle of ⁇ 5 °, and more preferably within an angle of ⁇ 3 °, and is characterized by being arranged linearly in the rolling direction.
  • the reason for this is not clear, but it is important that the hydrogen permeation blocking capability required for this steel sheet efficiently prevent hydrogen permeation from the center of the steel sheet thickness to the surface.
  • the composite oxide featured in the present invention can be further improved in characteristics by being arranged in parallel to the steel plate surface. Needless to say, as long as it is parallel to the surface of the steel sheet, it is not limited to a specific angle from the rolling direction as described above. Since it is difficult to arrange the composite oxides, it is assumed that the composite oxide is dispersed by rolling, and in the present invention, the arrangement is defined by the angle from the rolling direction.
  • the distance between the target complex oxides is characterized by a linear distance of 0 to 10 nm or more and 20 m or less. Outside this range, the resistance to picking will deteriorate. Preferably it is 0.20 m or more, more preferably 0.30 mm or more, more preferably 0 to 40 m or more, and further preferably 0.5 0 / m or more. Is preferred. The reason why the effect of the invention is affected by the lower limit of the distance is not clear, but there are finer complex oxides and concentrations between the target complex oxides. There are also complex oxides with a small difference, and it is considered that the hydrogen permeation blocking ability is also influenced by these complex oxides.
  • the upper limit is preferably 20 m or less, more preferably 10 m or less, further preferably 5 ⁇ m or less, and further preferably 1 m or less. The reason for specifying the upper limit is that if the target complex oxide is too far away, it is in line with the idea of stretching and crushing the coarse complex oxide that was originally integrated, as assumed in the present invention. This is because it disappears. According to the normal manufacturing method, it is often placed within 0.5; m.
  • the effects of the present invention are exhibited even when complex oxides having different compositions are not completely separated. That is, there is a variation in B concentration within one complex oxide present in the steel sheet, and the ratio between the B concentration (B max) in the high concentration part and the B concentration (B min) in the low concentration part is B max. / B min ⁇ 1.2 is sufficient. Preferably, it is 1.5 or more, more preferably 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. Similarly, there is a variation in Mn concentration within one complex oxide present in the steel sheet, with the Mn concentration (Mnmax) in the high concentration part and the Mn concentration (Mnmin) in the low concentration part. The specific power of ⁇ M nmax / nmin ⁇ 1.2 is sufficient. Preferably, it is 1.5 or more, more preferably 2.0 or more, more preferably 4.0 or more, and still more preferably 6.0 or more.
  • the reason for this is that, as described above, the coarse composite oxide, which was originally integral, is stretched and crushed. This is because, in usual observations, it is possible to think that the bonds are partially connected. Even in such a case, the shape of the complex oxide becomes very complex, and voids are effectively formed around it, acting as a hydrogen wrapping layer, and the concentration of the complex oxide is mainly changed. Defects formed along with the change in deformability caused by the hydrogen wraps hydrogen so that the effect of the present invention can be detected.
  • a particularly desirable composite oxide exists as a B 1 M n 1 Fe composite oxide. It is a feature of the present invention that the composition and form (arrangement) of this composite oxide are optimally controlled.
  • different composite oxide compositions mean that the composite oxide has different properties, such as hardness and ductility, and has a significant effect on the state of stretching and crushing of the composite oxide during hot rolling and cold rolling.
  • the situation is Controlling the content of each element in the complex oxide is extremely important for improving the properties of the steel sheet.
  • ⁇ S is compositely precipitated in the composite oxide, and the effect of the present invention is made more remarkable due to a large difference in stretchability and friability between the sulfide and the oxide.
  • the interaction effect of MnS and oxides on the anti-slip property is more effective in steels containing ⁇ than in conventional steels, and therefore, composite oxidation containing ⁇ and ⁇ . This is thought to be a feature of MnS, in which precipitation is promoted with the material as the nucleus.
  • the lower the C the better the workability.
  • it is set to not more than 0.010%.
  • it is desirable to make it not more than 0.025%. Even better The preferred range is below 0. 0 0 1 5%.
  • the lower limit is not particularly limited, but lowering the C content increases the steelmaking cost, so 0.000% or more is desirable.
  • S i can also be included in a small amount to control the composition of the oxide.
  • the content should be 0.0 0 1% or more.
  • the excessive content not only tends to inhibit the enamel characteristics, but also forms a large amount of Si oxide that is poor in ductility in hot rolling, which may reduce the resistance to tensile strength.
  • it is 0.030% or less, and more preferably 0.015% or less. From the standpoint of improving foam resistance, sunspot resistance, etc. and obtaining better enamel surface properties, the preferred range is 0.08% or less.
  • M n is an important component that affects the oxide composition variation in relation to the amounts of oxygen and Nb added. At the same time, it is an element that prevents hot brittleness caused by S during hot rolling. In the present invention containing oxygen, the content is 0.03% or more. Desirably, it is 0.05% or more. In general, when the amount of M n is high, the enamel adhesion becomes poor and bubbles and black spots are likely to occur. However, in the steel of the present invention that makes maximum use of M n as an oxide, the addition of M n Therefore, the deterioration of these characteristics is small. Rather, it is added actively because the oxide composition can be easily controlled by increasing Mn. That is, the upper limit of the Mn amount is specified as 1.30%. The upper limit is desirably 0.80%, and more preferably, the upper limit of M n is 0.60%.
  • O is an essential element in the present invention because it directly affects the toughness and workability, and at the same time affects the toughness resistance in relation to the amounts of M n and N b.
  • 0.005% or more is necessary.
  • it is 0.0 10% or more, more preferably 0.015% or more, and still more preferably 0.020% or more.
  • the upper limit is preferably 0.085%.
  • it is 0.065% or less, more preferably 0.055% or less.
  • a 1 is an oxide-forming element, and it is desirable that an appropriate amount of oxygen in the steel be present in the steel as an oxide in order to improve the enamelability as an enamel characteristic. In order to acquire this effect, it is contained 0.02% or more.
  • a 1 is a strong deoxidizing element. If it is contained in a large amount, it becomes difficult not only to keep the oxygen amount required by the present invention in the steel, but also to the ductility in hot rolling. It may form a large amount of poor A 1 oxide and reduce the resistance to sticking. Therefore, A 1 is set to 0.0 3 0% or less. Preferably it is not more than 0.015%, more preferably not more than 0.010%, more preferably not more than 0.05%.
  • N is an interstitial solid solution element like C. If it is contained in a large amount, Nb, and even if nitride-forming elements such as V and B are added, workability tends to deteriorate. It is difficult to manufacture non-aging steel sheets. For this reason, the upper limit of N is set to 0.0 0 5 5%. Desirably, it is 0.00 4 5% or less.
  • the lower limit is not particularly limited, but it is costly to melt to less than 0.0 0 10% in the current steelmaking technology, so it is desirable that the lower limit is 0.0 0 10% or more.
  • the P content is not more than 0.035%.
  • the P content is not more than 0.025%, more preferably not more than 0.015%, more preferably not more than 0.010%.
  • S forms an Mn sulfide and, in particular, precipitates this sulfide in an oxide complex, thereby effectively forming voids during rolling and improving the resistance to squeezing. It may be 0% which is not contained at all, but in order to obtain this effect, 0.02% or more is necessary.
  • it is 0.05% or more, more preferably 0.010% or more, and even more preferably 0.015% or more.
  • the upper limit is made 0.080%.
  • it is 0.060% or less, more preferably 0.040% or less.
  • B is an essential element in the present invention.
  • B fixes N, improves deep drawability, is non-aging, and is necessary for imparting high workability, and also has an effect of improving adhesion.
  • the added B combines with the oxygen in the steel to form an oxide, which works effectively in preventing stiction.
  • 0.0 3 or more is required. More preferably 0.0 0 0 8% or more, still more preferably 0.0 0 1 2% or more, still more preferably 0.0 0 1 5% or more, and still more preferably 0. 0 0 2 0% or more.
  • the upper limit is 0.0. 5 0%.
  • it is not more than 0.0 1 5 0%, more preferably not more than 0.0 0 80%.
  • Elements that have the same effect as B include Nb and V.
  • Nb When Nb is added alone, the effect of improving the r-value is remarkable, but there is also the aspect that the deterioration of elongation is large and hinders the improvement of the additive property, but in the steel according to the present invention containing B essentially, the recrystallization temperature is Remarkably increased, and annealing at very high temperatures is required to obtain good workability after cold rolling and annealing, reducing the productivity of annealing Let For this reason, it is preferable to keep it low, and it should not exceed 0.0 400%. Further, it is preferably 0.025% or less, more preferably 0.0015% or less. If it is 0, it is not necessary to consider the adverse effect of Nb.
  • V is related to the effect on workability.
  • the upper limit is wide because of the balance with the amount of oxygen remaining in the steel, which is equivalent to Nb.
  • the effect of increasing the crystal temperature is smaller than that of N b, and also has the effect of remarkably improving the anti-tack property by forming a composite oxide by adding it together with B.
  • 0.0 3% or more is necessary.
  • it is 0.06% or more, more preferably 0.010% or more, and still more preferably 0.015% or more.
  • Addition cost and foam resistance From the viewpoint of sunspot resistance, the upper limit is 0.15%.
  • the content of B is 0.001 to 5% or more and the effect of the invention is obtained with B alone, 0.0 60% or less, and further 0.04 0% or less This is sufficient.
  • Cu is added to control the reaction between glass and steel during enamel firing.
  • Cu segregated on the surface during pretreatment has the effect of promoting microscopic fluctuations in the reaction and improving adhesion.
  • the effect due to surface prayer is small, but it affects the microscopic reaction between laxatives and steel.
  • 0.0 1% or more is added as necessary. Inadvertently excessive addition not only hinders the reaction between glass and steel, but may also degrade workability. To avoid such adverse effects, the content should be 0.5 0 0% or less. Is preferred.
  • a preferable range ffl is 0.01 5 to 0.200%.
  • the total of one or more species is 1.0% or less, preferably 0.5.
  • % Or less more preferably 0.1% or less. If it is contained in a large amount, the reaction with the oxide-forming element cannot be ignored, and the composition and form of the oxide become unfavorable. However, the effects of the present invention can be achieved even when more amounts are added. Is not lost, and expects merit in terms of manufacturing or quality other than the one assumed by the present invention.
  • the addition procedure of Mn and B to molten steel is 80% or more of the total amount of Mn. It is advantageous from the viewpoint of productivity to allow 1 minute or more to elapse after addition of 80%, and to add 80% or more of the total addition amount of B, and forging within 60 minutes.
  • V and N b which have the same effect as B, it is basically preferable to add from elements with weak deoxidizing ability, and in the order of M n, V, N b and B
  • the effect of the present invention can be obtained more remarkably.
  • 80% or more of the total added amount of each element is added, and then the next element is added.
  • the amount added at less than 10% of the total amount added to adjust the final components after the addition of each element shall be excluded from consideration of the amount added here. It is preferable to allow each element to be added for a period of 1 minute or longer. More preferably, 2 minutes or more, more preferably 3 minutes or more. Also, forging within 60 minutes after adding all elements It is preferably within 40 minutes, more preferably within 20 minutes.In the forging process, the cooling rate during solidification with a thickness of the strip thickness of 1 4 ® is less than 10 seconds. As a result, the effect of the invention becomes more prominent. Preferably less than 5 ° CZ seconds, more preferably less than 2 at / second
  • it is 1 ° C / second or less, more preferably 0.5 ° C / second or less, further preferably 0.1 to Z seconds or less.
  • M n VN b B can be combined at one time.
  • the effect of the present invention can be obtained even if any two or more elements are added at once or separately.Mn VN b B can be added all at once. If two or more elements are added at once or separately, it is necessary to adjust the oxygen concentration in the molten steel to the range of 0 0 1 0 0 .0 70 0%. May fall.
  • B nitride is one of the purposes. With It binds with high affinity N to form B nitride, and does not effectively form B oxide sufficient to function as a hydrogen trap size.
  • Mn oxide is formed by adding Mn first as in the above-described manufacturing method. After that, B is compounded with oxides such as Mn by adding B or adjusting and adding the oxide itself having an effective concentration distribution. An oxide having a large variation is formed.
  • the formation of the optimum complex oxide as described above does not occur only due to the change of the component due to the addition of elements or the elapsed time, but is also strongly related to temperature.
  • the solubility of various elements in the steel also changes greatly, and this has a considerable effect on composition fluctuations.
  • the cooling rate at the time of solidification is important in order to obtain the effect of the invention sufficiently.
  • the cooling rate of the slab during forging differs depending on the position in the thickness direction.
  • the thickness is defined by the cooling rate with a thickness of 14 layers. 1 Z 4 layer cooling rate is
  • the composite oxide targeted in the present invention can obtain the effect of the invention remarkably at the stage where the average diameter is 1.O ⁇ m or more at the time of the piece having been solidified.
  • the average diameter is 1.O ⁇ m or more at the time of the piece having been solidified.
  • it is 4 O / ⁇ m or more, more preferably ⁇ ⁇ ⁇ or more, more preferably ⁇ is 15 m or more, and more preferably 20 m or more.
  • the oxide is coarse at the end of forging because if it is fine, the extensibility of the oxide at the time of slab processing becomes poor, and crushing is less likely to occur. It is. What is specified here is the average diameter, which is usually measured for complex oxides of a size that can be observed with an optical microscope or a low-power scanning electron microscope.
  • the composite oxide of is stretched and crushed by rolling, and changed into a form more suitable for the intended characteristics.
  • a certain amount of processing is necessary, and it is preferable that the thickness of the steel slab after completion of forging is 5 Om m or more.
  • the steel sheet is rolled to about 18 mm by hot rolling, and further to about 20.2 mm by cold rolling, so that the total strain is 3 to 5 or more in logarithmic strain.
  • the composite oxide in the hot rolling process, the composite oxide is softened due to the high temperature, and the hardness difference from the base metal, which is the parent phase, is small. Fracture hardly occurs and the composite oxide is stretched. In addition, when the temperature is lower than 100 ° C. and about 90 ° C. or less, the composite oxide becomes difficult to stretch, but does not cause significant crushing as in the case of cold rolling, and generates minute cracks. Some cracks occur. In order to obtain a composite oxide that has been stretched moderately and has microcracks at the same time before cold rolling, temperature control during hot rolling, strain in each temperature range, and hot working are required. Therefore, control of strain rate is important because of the remarkable recovery of deformed steel and composite oxides.
  • Hot rolling heating temperature, coiling temperature, etc. can be set as usual within the normal operating range.
  • the hot rolling heating temperature may be 100000 or less, but in order to sufficiently obtain the effect of stretching the complex oxide in the hot rolling described above, 1 If the above rolling is performed at 0 00, the temperature is 1 0 5 0 1 3 0 0 ° C and the cutting temperature is about 4 0 0 8 0 0.
  • the cold rolling rate it is preferable to set the cold rolling rate to 60% or more in order to sufficiently crush the complex oxide and to obtain a steel sheet with good deep drawability. Especially when deep drawability is required, the cold rolling rate is preferably 75% or more.
  • the characteristics of the present invention are not changed.
  • the characteristics of the present invention are exhibited as long as the temperature is equal to or higher than the recrystallization temperature.
  • continuous annealing is preferable in order to manifest the characteristics of the present invention, such as excellent deep drawability and good enamel characteristics. It can be performed mainly at 6 5 0 7 5 0 X for box annealing and 7 0 0 8 9 0 V for continuous annealing.
  • the steel sheet in which the composition fluctuation of the composite oxide is controlled as in the present invention has a very good anti-slip property even if it is applied once or twice.
  • the steel plate for enamel has excellent enamel adhesion without generating bubbles and sunspot defects.
  • the method of glazing can be applied not only to wet glazes, but also to dry and powder enamelling without problems.
  • the application is not limited in any way, and it exhibits its characteristics in the field of steel plate enamel as a technical classification, such as bath tubs, tableware, kitchenware, building materials, home appliance panels.
  • A is the sum of true strains applied at 1 00 0 or more and strain rate of 1 nose or more
  • B is 1 00 0 t or less and strain rate of 10 seconds or more Means the sum of true strains given in.
  • the relative position of the oxide that showed high concentration and low concentration ratio is A: Angle ⁇ 5. Within a distance of 0.5 ⁇ m, B: A condition is not satisfied, angle soil is within 10 °, and distance is within 20 m, and C: B condition is not satisfied.
  • the oxide is a composite oxide in which oxides such as Fe, Si, Mn, Al, Nb, V, and B are combined and integrated. In contact with another oxide. Any two complex oxides that are not, and any one complex oxide that is not separated from the same oxide.
  • the enamel was dry-processed by powder electrostatic coating, applied with 100 m of lower glaze and 10 ⁇ ⁇ of upper glaze, and baked in air at 85 CTC for 3 minutes at a dew point of 60.
  • a squeezing acceleration test is performed by placing the fired plate in a thermostatic bath at 160 ° for 10 hours, and the state of occurrence of the pinching is visually observed.
  • the enamel adhesion is usually performed by the P.E.I. adhesion test method (ASTC 3 1 3-5 9), so there is no difference in adhesion, so a 2 kg ball head weight is dropped from the lm height. Let the deformed part peel off Was measured with 16 9 palpation needles and evaluated by the area ratio of the unpeeled portion. As is apparent from the results in Table 3, the steel sheet of the present invention has enamel characteristics.
  • it is a steel plate for enamel that has outstanding resistance to tearing.
  • the effect of improving the durability by controlling the concentration difference of the composite oxide by controlling the production method is clear.
  • the steel sheet satisfying the steel components specified in the present invention has a B ma x / min ratio of another oxide (as defined in claim 1), a M n ma x / of another oxide. min ratio (as defined in claim 2), separate oxide distribution (in claim 8 B insect)
  • M claim 9 defines M n), and 'm a X m i n ratio in the same oxide (B in permanent term 6 and M n in claim 7)
  • steel sheet has 75 to 85% adhesion, foam • excellent enamel characteristics for sunspot, adhesion and anti-slip properties (B ) Or slightly better (C), but the overall evaluation was excellent overall and the intended effect of the present invention was obtained.
  • the comparative example (11 to n2) does not satisfy the requirement for the ma XZ min ratio of B of another oxide (as defined in claim 1),
  • the enamel characteristics (bubbles / spots, adhesion, and resistance to tearing) were inferior, and the effects of the present invention could not be obtained.
  • A is the sum of true strains applied at 100 0 or more and strain rate of 1 / second or more
  • B is applied at 1 00 or less and strain rate of 10 Z seconds or more Means the sum of true distortions.
  • the relative position of oxides with high and low concentration ratios is: A: within an angle ⁇ 5 ° and within a distance of 0.5 m, B: satisfies the A condition This means that the angle is within ⁇ 10 ° and the distance is within 20 m, and C: B condition is not satisfied.
  • the oxide refers to a composite oxide in which oxides such as Fe, Si, Mn, A, Nb, V, B, etc. are combined and integrated. Contact with another oxide. It means any two complex oxides that are not, and any one complex oxide that is not separated from the same oxide.
  • the above oxide is added to the steel number ol only by continuous forging molding.
  • the enameled steel sheet of the present invention satisfies all of the required resistance to enameling, such as anti-foaming / spot resistance, enamel adhesion, and surface characteristics.
  • the anti-tack property is significantly improved, and the defective product rate in the enamel product manufacturing process is greatly reduced, which has great industrial significance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Metal Rolling (AREA)
  • Continuous Casting (AREA)

Abstract

La présente invention concerne une tôle en acier pour émaillage par coulage continu qui présente une très grande improbabilité d’écaillage et une meilleure capacité de piégeage d’hydrogène obtenues en améliorant la capacité à former des alvéoles dans la tôle en acier. La tôle en acier contient, en pourcentage en masse, jusqu'à 0,010 % de C, de 0,03 à 1,30 % de Mn, jusqu'à 0,100 % de Si, jusqu'à 0,030 % d’Al, jusqu'à 0,0055 % de N, jusqu'à 0,035 % de P, jusqu'à 0,08 % de S, de 0,005 à 0,085 % d’O et de 0,0003 à 0,0250 % de B en tant que composants de l’acier. Des oxydes qui diffèrent en termes de concentration en masse en bore ou en manganèse sont contenus dans la tôle en acier, les oxydes n’ayant pas été unis ou ayant été unis. Le rapport de la concentration maximale sur la concentration minimale de ceux-ci est régulée à une valeur supérieure ou égale à 1,2. Lorsque les oxydes n'ont pas été unis, ils sont de ce fait présents de sorte que la distance entre les centres des oxydes différant en termes de concentration soit de 0,10 µm à 20 µm et la ligne droite reliant les centres des deux oxydes ait un angle de ±10° par rapport à la direction de roulement.
PCT/JP2006/322786 2005-11-09 2006-11-09 Tole en acier pour emaillage par coulage continu avec une tres grande improbabilite d’ecaillage et son procede de production WO2007055400A1 (fr)

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EP06823434.3A EP1950317B1 (fr) 2005-11-09 2006-11-09 Tole en acier pour emaillage par coulage continu avec une grande resistance a l`ecaillage et son procede de production
US12/084,609 US20090047168A1 (en) 2005-11-09 2006-11-09 Continuously Cast Enameled Steel Sheet Remarkably Excellent in Fishscale Resistance and Method of Production of the Same
JP2007544239A JP4954889B2 (ja) 2005-11-09 2006-11-09 耐つまとび性に著しく優れた連続鋳造ほうろう用鋼板およびその製造方法
ES06823434.3T ES2568678T3 (es) 2005-11-09 2006-11-09 Hoja de acero para esmaltar mediante colada continua con una resistencia a la descamación excelente y método para producirla
CN2006800507081A CN101356295B (zh) 2005-11-09 2006-11-09 抗鳞爆性显著优异的连铸搪瓷用钢板及其制造方法

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WO2011074787A2 (fr) * 2009-12-18 2011-06-23 주식회사 포스코 Tôle d'acier pour un émaillage de surface sans défaut, et procédé de fabrication de cette dernière
WO2012091340A2 (fr) * 2010-12-27 2012-07-05 주식회사 포스코 Tôle d'acier sans défaut de surface pour émaillage et son procédé de fabrication
JPWO2021193953A1 (fr) * 2020-03-27 2021-09-30

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CA2829032C (fr) 2011-03-09 2016-05-03 Nippon Steel & Sumitomo Metal Corporation Feuilles d'acier destinees a l'estampage a chaud, procede pour leur fabrication et procede pour la fabrication de parties hautement resistantes
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US11236427B2 (en) 2017-12-06 2022-02-01 Polyvision Corporation Systems and methods for in-line thermal flattening and enameling of steel sheets
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JP2010043312A (ja) * 2008-08-11 2010-02-25 Nippon Steel Corp 耐爪飛び性に優れたほうろう用鋼板
WO2011074787A2 (fr) * 2009-12-18 2011-06-23 주식회사 포스코 Tôle d'acier pour un émaillage de surface sans défaut, et procédé de fabrication de cette dernière
WO2011074787A3 (fr) * 2009-12-18 2011-10-27 주식회사 포스코 Tôle d'acier pour un émaillage de surface sans défaut, et procédé de fabrication de cette dernière
JP2013514460A (ja) * 2009-12-18 2013-04-25 ポスコ 表面欠陥がないほうろう用鋼板およびその製造方法
WO2012091340A2 (fr) * 2010-12-27 2012-07-05 주식회사 포스코 Tôle d'acier sans défaut de surface pour émaillage et son procédé de fabrication
WO2012091340A3 (fr) * 2010-12-27 2012-09-07 주식회사 포스코 Tôle d'acier sans défaut de surface pour émaillage et son procédé de fabrication
JP2014500397A (ja) * 2010-12-27 2014-01-09 ポスコ 表面欠陥のないホウロウ用鋼板およびその製造方法
US9382597B2 (en) 2010-12-27 2016-07-05 Posco Steel sheet for enamel having no surface defects and method of manufacturing the same
JPWO2021193953A1 (fr) * 2020-03-27 2021-09-30
JP7115653B2 (ja) 2020-03-27 2022-08-09 日本製鉄株式会社 鋼板およびほうろう製品

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TW200718789A (en) 2007-05-16
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JP4954889B2 (ja) 2012-06-20
EP1950317A1 (fr) 2008-07-30
ES2568678T3 (es) 2016-05-03
JPWO2007055400A1 (ja) 2009-04-30
CN101356295B (zh) 2012-07-04
KR20080058477A (ko) 2008-06-25
CN101356295A (zh) 2009-01-28
US20090047168A1 (en) 2009-02-19
EP1950317A4 (fr) 2010-03-24
TWI346710B (en) 2011-08-11
KR101019225B1 (ko) 2011-03-04

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