WO2006027854A1 - 極薄容器用の鋼板およびその製造方法 - Google Patents
極薄容器用の鋼板およびその製造方法 Download PDFInfo
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- WO2006027854A1 WO2006027854A1 PCT/JP2004/013493 JP2004013493W WO2006027854A1 WO 2006027854 A1 WO2006027854 A1 WO 2006027854A1 JP 2004013493 W JP2004013493 W JP 2004013493W WO 2006027854 A1 WO2006027854 A1 WO 2006027854A1
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- 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%
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- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
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- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- 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
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- 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
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- 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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
Definitions
- the present invention relates to a steel plate used for a metal container such as a beverage can and a method for producing the same.
- Thinning has progressed, and materials of 0.2 mm or less have been applied.
- One of the problems that has emerged when containers are made of such ultra-thin materials is the deformation of the containers.
- the welded part may be further formed after the steel plate is welded. In such a case, the deformation tends to concentrate on a specific part, and from this point, good ductility is required. .
- the nitriding technology at the time of annealing is disclosed in Japanese Patent Laid-Open Nos. 0-8-17O12 2 No. 2, Japanese Laid-Open Patent Publication No. 2 0 0 1 — 1 0 7 1 4 8, Japanese Laid-Open Patent Publication No.
- the present invention solves the problems of the prior art as described above, and applies nitridation to the material of the surface layer and the inner layer of the material for the deformation that is a problem in a container manufactured using an extremely thin material. It is an object to provide a steel sheet having a good ductility even when it is hard, and a method for manufacturing the same.
- the present inventors have studied the composition of a steel sheet having a thickness of 0.4 mm or less manufactured through a nitriding process and the relationship between the nitriding condition and the material, and the components, particularly By limiting the amount of N to a specific range and further adjusting the nitriding conditions optimally, it is possible to preferably control the nitride form of the surface layer and inner layer of the material. It has been found that the deformation which is a problem in the used container can be greatly suppressed.
- the deformation resistance of the can is not improved so much by simply forming the surface hardness by performing nitriding after cold rolling and increasing the amount of nitrogen in the steel.
- nitriding conditions necessary to improve the deformation resistance of cans with thin materials, and the control method. Show.
- the first aspect of the steel sheet for an ultrathin container according to the present invention is, in mass%, C: 0.080% or less, N: 0.6600% or less, S i: 2.0% or less, Mn: 2 0% or less, P: 0. 10% or less, S: 0.05% or less, A 1: 2.0% or less, diameter 1 xm or less 0.02 z / m or more of nitride
- the surface layer of 1 Z 8 has a number density of 0.2 in the thickness of Z ⁇ m 3 or more, and satisfies the following formula (A).
- a second embodiment of the steel sheet for an ultrathin container according to the present invention is, in mass%, C: 0.080% or less, N: 0.6600% or less, Si: 2.0% or less, Mn: 2 0% or less, P: 0. 10% or less, S: 0.05% or less, A 1: 2.0% or less, and nitrides with a diameter of 1 m or less and 0.02 m or more are ) Is satisfied.
- both the deformation resistance and can moldability of the container can be significantly improved without sacrificing one.
- extremely good can characteristics can be realized at a thickness of 0.400 mm or less.
- the steel sheet for ultra-thin containers of the present invention in the plate thickness 1Z4 position of the steel sheet, nitridation the number density of more than 0. 02 m or less in diameter 1 m may be not more than 10 Z m 3.
- T i 0.08% or less
- Nb 0.08% or less
- B 0.015% or less
- Cr 2.0% or less
- 1 type or 2 types or more It may contain.
- the total of Sn, Sb, Mo, Ta, V, W is 0.
- the balance of the steel component may be Fe and inevitable impurities.
- a first aspect of the method for producing a steel sheet for an ultrathin container according to the present invention is as follows:
- N 0.0300% or less
- Si 2.0% or less
- Mn 2.
- the second aspect of the method for producing a steel sheet for an ultrathin container according to the present invention is, in mass%, C: 0.0800% or less, N: 0.0300% or less, Si: 2.0% or less, Mn : 2.0% or less, P: 0.10% or less, S: 0.05% or less, A1: 2.0% or less of steel containing steel Nitriding is performed after crystal annealing, and the following formula (B) is satisfied for nitrides with a diameter of 1 m or less within the thickness of 1/8 of the surface layer of the steel sheet, and N in the steel sheet is expressed by mass%. Therefore, it should be 0. 600% or less.
- a third aspect of the method for producing a steel sheet for an ultrathin container according to the present invention is, in mass%, C: 0.0800% or less, N: 0.0300% or less, Si: 2.0% or less, Mn : 2.0% or less, P: 0.10% or less, S: 0.05% or less, A1: 2.0% or less of steel containing steel Nitriding is performed after crystal annealing. For nitrides with a diameter of 12 m or less and 0.02 xm or more, the following formula (C) is satisfied, and N in the steel sheet is 0.6% or less by mass%.
- an ultra-thin container steel sheet that can be remarkably improved without sacrificing one of the deformation resistance and can moldability of the container with high productivity. Can be obtained.
- the plate thickness is 0.400 mm or less, it is possible to produce a steel plate for an extremely thin container having extremely good can characteristics with high productivity.
- the product of temperature and time should be 48000 (° C 'seconds) or less in the temperature range of 550 ° C or higher, or average cooling from 550 ° C to 300 ° C
- the speed may be 10 ° CZ seconds or more.
- Fig. 1 is a diagram showing the position in the thickness direction of the steel sheet.
- Fig. 2 shows the relationship between the indentation amount and the indentation load in the deformation test.
- Figure 3 shows the relationship between nitriding time and can strength.
- Figure 4 shows the relationship between the ratio of the number of nitrides before and after nitriding and the can strength.
- the steel material component in this invention is demonstrated. All components are in weight percent.
- the upper limit of the C amount is necessary to avoid deterioration of workability, and C: 0.0800% or less. Preferably it is 0.0600% or less, more preferably 0.040% or less.
- C Necessary strength can be ensured even if it is less than 0.0050%, and it may be less than 0.0010%, and if it is 0.005% or less, there is a balance with the amount of nitriding, but it is also possible to manufacture extremely soft materials In view of improving the r value and keeping the drawability high, C is preferably low.
- N The upper limit of the amount of N before nitriding is also necessary to avoid deterioration of workability, and N: 0.0300% or less.
- N 0.0200% or less, more preferably N: 0.0150% or less, more preferably N: 0.0100% or less,
- the N content before nitriding is low. It should be noted that N added by nitriding as described later exists in different amounts depending on the thickness position of the steel sheet in order to give the can deformation resistance effect, etc. N has a slightly different effect.
- the upper limit of the amount of N after nitriding is necessary not only for avoiding deterioration of workability but also for avoiding deterioration of surface treatment properties such as plating, and is N: 0.60% or less.
- a higher N content is preferable in terms of making the hardened portion by nitriding harder.
- Si is added for strength adjustment, but if it is too much, the workability deteriorates, so it is 2.0% or less.
- nitride and N that have entered the steel by nitriding form at the grain boundaries to form a nitride and cause brittle cracking, which may impair the effects of the present invention.
- the Si amount is preferably low, and the moldability is improved by setting it to 0.5% or less, and further to 0.1% or less.
- Mn is added to adjust the strength, but if it is too much, the workability deteriorates, so the content should be 2.0% or less.
- the Mn content is preferably low, and the moldability is improved by setting it to 0.6% or less, and further to 0.2% or less.
- the P is added to adjust the strength, but if it is too much, the workability deteriorates, so 0.1% or less.
- the P content is preferably low, and the moldability is improved by setting it to 0.05% or less, and further 0.01% or less.
- S deteriorates the hot ductility and becomes a hindering factor for hot rolling, so 0.05% or less.
- the S content is low.
- the moldability is improved by setting the content to 0.02% or less, and further to 0.01% or less.
- a 1 is an element added for deoxidation, but if it is high, forging becomes difficult. Due to harmful effects such as increased surface wrinkles, the content should be 2.0% or less.
- a 1 amount is 0.2% If it is higher than the above, it will combine with N that penetrates the steel sheet by nitriding, forming a large amount of A 1 N in the steel and making the nitriding part hard.
- the amount of A1 is low, and it is 0.2% or less, more preferably 0.1% or less, and a portion with a low degree of nitriding. The moldability is improved.
- Ti raises the recrystallization temperature of the steel sheet and significantly degrades the annealing passability of the ultrathin steel sheet targeted by the present invention. For this reason, it is set to 0.080% or less. In normal applications where a high r value is not required, it is not necessary to add Ti, and it should be 0.04% or less, more preferably 0.01% or less.
- Ti dissolved in the steel before nitriding is combined with N that has penetrated into the steel sheet by nitriding, forming fine Ti N in the steel, and has a strong effect of hardening the nitrided part.
- Nb has the same effect as Ti, raises the recrystallization temperature, and remarkably deteriorates the sheet-passability of the ultrathin steel sheet targeted by the present invention. For this reason, it is set to 0.08% or less. In normal applications that do not require particularly high r values, it is not necessary to add N b in normal applications that do not require particularly high r values, and it should be 0.04% or less, more preferably 0.01% or less.
- Nb solid-dissolved in the steel before nitriding combines with N that has entered the steel sheet by nitriding, forming fine NbN in the steel, and has a strong effect of hardening the nitrided part.
- the steel sheet thickness center layer with a low degree of nitriding may appear harder than necessary, if it is necessary to obtain a soft steel sheet, a lower Nb content is preferable. If the content is less than or equal to%, and further less than or equal to 0.003%, inadvertent hardening of the steel sheet can be suppressed.
- the soot that is dissolved in the steel before nitriding is combined with the soot that has entered the steel sheet by nitriding, forming a fine soot in the steel and making the nitrided part hard.
- the ratio of the soot content before nitriding and the soot content is BZN> 0.8.
- the ratio of the soot content before nitriding to the soot content should be BZN ⁇ 0.8, and more strictly, ⁇ 0.
- Cr dissolved in the steel before nitriding combines with the soot that has penetrated into the steel sheet by nitriding, and has the effect of forming fine Cr nitride in the steel and hardening the nitrided part. For this reason, the material may be hardened more than necessary, but conversely, the nitride can be utilized to effectively increase the hardness of the nitrided portion.
- Cr is preferably added in an amount of 0.01% or more. On the other hand, however, Cr increases the recrystallization temperature of the steel sheet, and if added excessively, the annealing passability of the ultrathin steel sheet that is the subject of the present invention may be significantly deteriorated.
- Sn, Sb, Mo, Ta, V, W in total in an amount of 0.1% or less in order to impart properties not specified in the present invention.
- the inclusion of Sn and Sb may lower the nitriding efficiency, so it is necessary to control the nitride by applying nitriding. Care must be taken in the event.
- “Surface 1/8 thickness” represents the corresponding area in FIG. Note that the region corresponding to “surface layer 1 Z8 thickness” exists on both surfaces of the steel sheet, but in the present invention, either one of the surfaces falls within the scope of the present invention. It is relatively easy to change the nitride distribution on the front and back surfaces by a surface treatment before nitriding, or some kind of treatment after nitriding. This is also the target. This is because the deformation resistance intended by the present invention can be obtained even on only one side.
- plate thickness 1 Z8 position represents the corresponding position in FIG.
- plate thickness 1 ⁇ 4 position represents the corresponding position in FIG. Note that positions corresponding to these exist on both surfaces of the steel sheet, but in the present invention, any one of them is within the scope of the present invention.
- plate thickness 1Z20 position refers to a position at a depth of 1 / 20th of the plate thickness from the surface of the steel plate in the same way as “plate thickness 1/8 position”.
- the size and number density of nitride existing in a specific position or a specific layer in the thickness direction of the steel sheet are defined.
- Existing precipitates can be identified with diffraction patterns such as electron microscopes and attached X-ray analysis equipment. Of course, it can be identified by other methods such as chemical analysis.
- the average diameter of the nitride targeted in the present invention is 1. O ⁇ m or less.
- the diameter is preferably 0.40 m or less, more preferably 0. or less, and further preferably 0.10 m or less. These diameters and the number density described later can be quantified, for example, by observation with an electron microscope.
- Control of the nitride size and number density is very important from the viewpoint of achieving both high strength and workability retention. This is because they not only affect the strength and workability, but also the behavior that changes the strength or workability when they are changed. In other words, it is necessary to control to a region where the strength increasing effect is high and the workability deterioration efficiency is low. For this purpose, it is effective to appropriately control the temperature and time in the above-mentioned temperature range of 450 to 700 ° C and the cooling rate immediately before entering this temperature range. This is the same as the formation of precipitates.
- the extracted replica obtained by the SPEED method is basically observed with an electron microscope with an EDX in the present invention.
- the thin film may be observed with a transmission electron microscope.
- the composition is determined by EDX analysis, and when the non-metallic element that is mainly observed is N, the nitride is determined.
- Fe, Ti, Nb, B, Cr, etc. are detected even if the characteristic spectrum of N is not clear, and clear spectra such as 0, S, etc. are not observed, and it can be identified as nitride.
- Precipitates that can be almost determined to be nitrides from a comparison with other precipitates are also taken into account in the present invention as nitrides.
- Nitride identification is not based on techniques such as EDX or electron diffraction patterns, and any analytical instrument that currently has significant performance improvements may be used.
- it is sufficient that the type, size, and number density of the precipitates can be determined by a method that is recognized as appropriate.
- it may be difficult to distinguish between carbide and nitride. Any conventional analytical instrument whose type cannot be determined properly is excluded from the present invention.
- the diameter and number of nitrides are measured in a visual field where there is no bias.
- the magnification is set so that the number of nitrides of the target diameter is about 500 in one field of view, and 10 fields of view are randomly selected.
- all the target nitrides in the field of view must be measured.
- the number of nitrides and the diameter can also be obtained using image analysis or the like.
- the shape is elongated, but for the shape that is not isotropic, the average of the major axis and the minor axis is the diameter of the precipitate.
- the number density of the precipitates is that all the electric charge applied to the sample surface during the electrolysis process in the replica making process is consumed while the steel plate is electrolyzed as Fe divalent ions (Fe 2+ ), and all the precipitates that remain as residues during electrolysis Calculated as supplemented on replica.
- Fe divalent ions Fe 2+
- the number density of the precipitates is that all the electric charge applied to the sample surface during the electrolysis process in the replica making process is consumed while the steel plate is electrolyzed as Fe divalent ions (Fe 2+ ), and all the precipitates that remain as residues during electrolysis Calculated as supplemented on replica.
- electrolysis is performed at an electric quantity of 50 C (coulomb) / cm 2 on the sample surface area, precipitates within the thickness from the sample surface will be observed on the replica.
- the steel plate to be measured is very thin, for example, if precipitates within a thickness of 18 m are observed together, it will be unclear which position of the plate thickness the observation position corresponds to.
- the electrolytic thickness in the SPEED method is 18 m. It is not limited to. Ideally on a zero-thickness surface Although existing precipitates should be observed, this raises the risk of increased measurement error. Although it depends on the plate thickness, the electrolytic thickness should be about 5-20 ⁇ , and polishing should be performed so that the target plate thickness position is at the center of the thickness of the electrolytic section.
- electrolysis is performed not from the plate surface to the plate thickness direction but from the plate thickness cross section to the plate surface direction to create a replica including information on the plate thickness direction, and the number density of nitride on this replica in the plate thickness direction It is also possible to determine the number density of nitride at a specific plate thickness position from this distribution.
- the technology targeted by the present invention is basically applied to the ultrathin steel plate for containers with excellent can characteristics, in which the components and materials of the surface layer and the central layer are appropriately controlled as filed in Japanese Patent Application No. 2002-337647.
- the present invention is not limited to this.
- the nitride state is mainly in the region of “surface layer 1Z8 thickness” and “plate thickness 1 Z20 position”, “plate thickness 1/8 position”, “plate thickness 1/4 position”.
- the main effect of the present invention is to control the nitride state at the plate thickness position depending on these, and the effect in Japanese Patent Application No. 2002-337647 is achieved by controlling the nitride state in this way. Can be obtained more preferably.
- the present invention mainly disperses the nitride in the surface layer portion in a larger amount and finer than the central portion, and is it a general nitriding method assumed as one of the production methods of the present invention? Therefore, the assumption is that the steel sheet surface should be preferentially nitrided and the amount of nitride produced by nitriding should increase compared to the central layer.
- the nitride formed at this time is not preferable for the purpose of the present invention, but is rather preferable, and it is preferable that the nitride is finely dispersed depending on the heat history after nitriding, especially cooling conditions. Therefore, in the present invention, the fine nitride is controlled.
- one of the features of the present invention is to make a difference in the state of nitride at the steel plate thickness position.
- This difference is due to the fact that the nitride targeted by the present invention is (surface layer 1 / 8 thickness) has a number density of 0.2 / ⁇ m 3 or more, and (number density at (plate thickness 1Z8 position) of steel plate)> (plate thickness (1Z4 position) ) Is limited by number density).
- the number density of the nitride is limited in the range that can be taken in relation to the N content and the size of the nitride, but is preferably 0.2 Z xm 3 or more, more preferably 2 Z m 3 or more. If it is 20 pieces m 3 or more, further 200 pieces m 3 or more, further 1000 pieces / m 3 or more, it is very effective in terms of hardening.
- This ratio is greater than 1.5, preferably 3 or more It is preferably 6 or more, more preferably 10 or more, further preferably 30 or more, and further preferably 100 or more. If this ratio is small, the effect of the present invention is reduced and the intended steel sheet cannot be obtained.
- the ratio is larger than 1.5, preferably 3 or more, preferably 6 or more, more preferably 6 or more, more preferably 10 or more. More preferably, it is 30 or more, more preferably 100 or more. Needless to say, the greater the ratio, the greater the effect of the present invention.
- the main control object of the present invention is to disperse a large amount of fine nitride in the steel sheet surface layer as compared with the central layer of the steel sheet, it is clear that a large amount of fine nitride is dispersed in the steel sheet central layer.
- nitriding is not more than a diameter lm of 0.02 ⁇ m or more at (plate thickness 1/4 position). it is preferable that the object number density of 10 pieces ⁇ ⁇ ⁇ 3 below.
- nitriding conditions will be described. It is convenient from the viewpoint of productivity that the nitriding treatment of the present invention is carried out simultaneously with the recrystallization annealing after the cold rolling or subsequently, followed by the recrystallization annealing, but it is not particularly limited.
- the annealing method can be applied regardless of batch type or continuous annealing.
- the continuous annealing method is much more advantageous from the standpoint of nitriding productivity and uniformity of the nitride material in the coil.
- the nitriding time and the subsequent thermal history become longer. From the standpoint of profitability, it is preferable that at least the nitriding treatment be performed in a continuous annealing facility. If there is no special reason, continuous annealing shall be applied.
- the process of partially controlling the atmosphere in the furnace in the continuous annealing process, recrystallization in the first half, and nitriding in the second half has many advantages such as productivity, material uniformity, and easy control of the nitriding state. .
- nitriding is performed before recrystallization is completed, recrystallization is remarkably suppressed, an unrecrystallized structure remains, and remarkable workability deterioration may occur.
- This limit is complicatedly determined by the nitriding conditions, recrystallization annealing conditions, etc. of the steel components, but it is easy for those skilled in the art to find conditions where no unrecrystallized structure remains after a reasonable trial. is there.
- the nitriding treatment takes into account not only the amount of N increase in the steel sheet due to nitriding, but also the steel composition and recrystallization annealing conditions, as well as the thermal history after nitriding, etc. It is necessary to decide in consideration of physical changes. If only the material determined by Rockwell hardness, tensile test or the like is used as an index, the preferred deformation resistance intended by the present invention cannot be obtained.
- nitriding needs to be performed at a plate temperature of 550 to 800 ° C. It is possible to perform nitriding at the same time by setting the plate temperature within this range by setting the nitriding atmosphere to this temperature and passing the steel plate through the atmosphere as in normal annealing, and the nitriding atmosphere has a lower temperature. The nitriding may be advanced by allowing a steel sheet heated to a temperature in this range to enter the steel sheet.
- the temperature of the nitriding atmosphere When the temperature of the nitriding atmosphere is raised to this temperature, the nitriding efficiency of the steel sheet may decrease due to the change and decomposition of the atmosphere unrelated to the nitriding of the steel sheet, so the temperature is set to 550 to 750 ° C. Preferably it is 600-700 degreeC, More preferably, it is 630-680 degreeC.
- the nitriding atmosphere contains nitrogen gas in a volume ratio of 10% or more, more preferably 20% or more, more preferably 40% or more, more preferably 60% or more, and hydrogen gas is contained in 90% or less, more preferably as required. 80% or less, more preferably 60% or less, more preferably 20% or less, and further containing 0.02% or more of ammonia gas as necessary, with the balance being oxygen gas, hydrogen gas, carbon dioxide gas, Hydrocarbon gas or Are various inert gases.
- ammonia gas is highly effective for increasing the nitriding efficiency, and a predetermined amount of nitriding can be obtained in a short time. Therefore, diffusion of N to the center of the steel sheet can be suppressed, and a favorable effect can be obtained for the present invention. .
- This effect is sufficient even if it is 0.02% or less, but preferably 0.1% or more, more preferably 0.2% or more, more preferably 1.0% or more, more preferably 5% or more, 10% or more.
- a sufficient effect can be obtained even with a nitriding treatment in 5 seconds or less, and if it is 20% or more and 40% or more, depending on the nitriding temperature and the plate thickness, it takes 1 second or less.
- a clear effect can be obtained even in a short time.
- the volume (nitrogen gas) / (hydrogen gas) is 1 or more.
- annealing is performed under conditions that do not nitride in an atmosphere mainly composed of nitrogen gas and hydrogen gas.
- those skilled in the art are not limited to the above-mentioned mixing of ammonia gas, and the dew point is not limited. It is possible to change to a condition that causes nitriding by changing, mixing a slight amount of gas, or changing the gas ratio after an appropriate trial.
- the object of the present invention is that nitriding by at least heat treatment including annealing can be detected by the current analytical ability.
- the holding time in the nitriding atmosphere is not particularly limited, but considering the steel sheet thickness of 0.400 mm at the maximum in consideration of the temperature condition of the present invention of 550 ° C or more, nitriding is caused by diffusion in the holding steel. It is desirable to set the upper limit to 360 seconds, considering that N entering from the surface of the steel sheet reaches the central layer of the steel sheet and the N distribution or nitride distribution intended by the present invention cannot be obtained. Further, even if the nitriding efficiency is improved, 0.1 second is necessary to obtain the nitriding amount and the nitrogen and hardness distribution in the thickness direction of the steel sheet required by the present invention. It is preferably 1 to 60 seconds, more preferably 2 to 20 seconds, and further preferably 3 to 10 seconds.
- the thermal history of the steel sheet after nitriding is also important. Considering the thickness of the target steel sheet and the diffusion and nitridation / growth of nitrogen in the steel, holding at a high temperature for a long time is not preferable.
- the effect of the present invention can be achieved by appropriately smoothing the nitrogen distribution by this heat treatment. It is also possible to make the fruit more prominent.
- history in a temperature range of 550 ° C or higher is important, and the product of temperature and time in this temperature range is preferably 48000 or less. This corresponds to 80 seconds at 600 ° C and 60 seconds at 800 ° C, but when the temperature changes continuously, the temperature is divided into time zones of about 5 seconds so that the effect can be properly evaluated. It can also be evaluated by recording the change and calculating the sum of the product of temperature and time for each region.
- the nitriding conditions are set so that the distribution of nitrogen in the steel is almost determined at the end of nitriding, and is preferably nitrided in the subsequent cooling process. It is preferable to control the production of the product.
- the nitriding targeted by the present invention is mainly performed in a state where a large amount of N is in a solid solution, and a large amount of nitride occurs with a subsequent temperature drop, so control of the cooling process after nitriding is important.
- the cooling rate after nitridation greatly affects the effect of the invention in connection with the thermal history in this cooling process.
- the state of nitride formation during the cooling process may change significantly even at low temperatures and short periods when the nitrogen distribution hardly changes.
- the average cooling rate from 550 ° C to 300 ° C to 10 ° C / s or more, there are many fine nitrides in the surface layer where the N concentration is relatively high and the cooling rate is high compared to the central layer. Can be generated.
- it is 20 ° C / s or more, more preferably 50 ° C / s or more.
- re-rolling may be performed after recrystallization annealing to adjust the hardness and thickness.
- the rolling reduction has been put to practical use from a few percent, which is close to the skin path used for shape adjustment, to over 50%, which is the same as cold rolling.
- re-cold rolling similar to conventional steel can be applied.
- the hardness distribution in the thickness direction which is a feature of the present invention, is changed. It may seem to disappear, but the fact is contrary to this.
- the re-rolling ratio is a normal level, the N content is rather increased by re-rolling.
- the higher and harder surface layer portion becomes harder preferentially, and the hardness difference of the inner surface layer, which is a feature of the present invention, becomes clearer.
- the surface layer is easy to work harden due to the large amount of solute N and nitride, while the inner layer is constrained by the surface layer, so it cannot be preferentially deformed and greatly exceeds the surface layer. This is because it does not cure selectively.
- the rolling reduction is preferably up to about 70%.
- the re-rolling time is after nitriding in the process of continuous recrystallization annealing and nitriding, which is preferable from the viewpoint of productivity, but when recrystallization annealing and nitriding are performed in separate processes. It is also possible to carry out before the nitriding treatment.
- the present invention is applied to a steel plate having a thickness of 0.400 mm or less. This is because deformation of the formed member is less likely to be a problem with a steel plate having a thickness greater than this. In addition, when the plate thickness is large, the thickness of the surface layer hardened layer by nitriding becomes relatively small, and the effect of the invention is hardly exhibited.
- the target is preferably a steel plate of 0.300 mm or less, more preferably 0.240 mm or less, and a steel plate of 0.190 mm or less, more preferably 0.160 mm or less, can obtain a very remarkable effect.
- the state of nitride after nitriding is mainly controlled by distinguishing the surface layer from the center layer and taking into account the distribution in the thickness direction, for the purpose of merely making steel containing N and surface hardness.
- the mechanism by which the steel of the present invention, which is not found in nitrided steel, has a specific material is not clear, but it is thought that the resistance to bending deformation of the steel sheet surface layer accompanying deformation of the can is effectively increased by nitride. It is done.
- This effect is based on the difference between the surface layer and the center layer in combination with the external force when the plate thickness or deformation of the target material occurs, the stress state involving conditions such as the shape of the container, and the nitriding conditions specified in the present invention. It is presumed that deformation resistance can be realized very effectively depending on the size and number density of nitrides.
- the effect of the present invention does not depend on the heat history before the annealing after the component adjustment and the manufacturing history.
- the slab for hot rolling is not limited to manufacturing methods such as the ingot method and continuous forging method, and it does not depend on the heat history until hot rolling, so the slab reheating method or forged slab is used.
- the effect of the present invention can also be obtained by CC-DR method in which hot rolling is directly performed without reheating, and further by thin slab fabrication in which rough rolling or the like is omitted.
- the effect of the present invention can also be obtained by two-phase rolling in which the finishing temperature is a two-phase region of + T or continuous hot rolling in which a rough bar is joined and rolled regardless of hot rolling conditions.
- the steel of the present invention when used as a container material having a welded portion, it suppresses softening of the heat-affected zone, particularly when the surface layer portion having a large amount of nitride is rapidly heated and rapidly cooled, the nitride is dissolved, and further It reprecipitates as fine nitride, and part of it remains as solute N and hardens, so it has the effect of improving the strength of the weld. This becomes even more pronounced when elements such as B and Nb that normally suppress the softening of the heat-affected zone are added.
- the plate surface is hardened so that the coefficient of friction with the molding die is lowered and the moldability is improved. Furthermore, since the surface layer is hardened and the resistance to bending deformation is increased, bending buckling of the steel sheet during forming becomes difficult to occur, that is, an effect of suppressing the generation of wrinkles is exhibited.
- the steel sheet of the present invention is used as an original sheet for a surface-treated steel sheet, but the effect of the present invention is not impaired by the surface treatment.
- it can be used without deteriorating the effects of the present invention as an original sheet for a laminated steel sheet coated with an organic film that has recently been used.
- Example 1 In a three-piece can that was formed by welding the can body part, a three-piece can body was manufactured using a steel plate in which nitriding conditions were changed and nitride was controlled. The deformation resistance when the body of this can was pushed with a cylindrical mold of 10mm ⁇ and length of 40 thighs was measured, and the end of the can was flange-molded in the same way as a normal lid was wrapped.
- the correlation between the indentation amount and the indentation load is shown in Fig. 2, and an inflection point is generated at a certain load.
- the load serving as the inflection point was used as an index of deformation resistance. The higher this value, the smaller the deformation due to external force and the better the deformation resistance.
- Table 1 shows hot rolling, cold rolling, annealing, and nitriding conditions.
- the amount of N in Table 1 is the average amount of N before nitriding. Since the steel sheet is manufactured by a usual method, the elemental change in the thickness direction and the change of the nitride state are negligible before nitriding, and are negligible for the effect of the present invention. In other words, regarding the composition, nitride size, and number density of the steel sheet before nitriding, the values of the surface layer 120 thickness, the surface layer 1-8 thickness, and the center layer 1Z4 thickness are the same.
- Table 2 shows the materials for these steels. It can be confirmed that the method according to the present invention has both good deformation resistance and flange formability.
- A is the highest number density in (plate thickness 1/8 thickness)
- B is (number density in surface layer 1/20 thickness) 4 is the number density at the surface layer 1/20 thickness after nitriding treatment
- I is the number density at the surface layer 1/20 thickness before nitriding treatment.
- C 0.02%, Si: 0.02%, Mn: 0.2%, P: 0.01%, S: 0.01%, A1: 0.04%, N: 0.0.
- Some materials were subjected to nitriding treatment by passing through a nitriding furnace filled with an ammonia-containing atmosphere continuously in an annealing furnace of a continuous annealing line. No heating equipment was installed in the nitriding furnace, and nitriding was performed by allowing the plate that had been heated in the recrystallization annealing furnace to enter the nitriding furnace at 650 ° C. Since the atmosphere in the nitriding furnace is heated by the heat brought in by the steel sheet, the temperature drop during the nitriding process is not so large. The temperature of the plate coming out of the nitriding furnace depends on the nitriding time, but 600 It was about ° C.
- A is ammonia concentration 4%
- B is ammonia concentration 4%
- C is ammonia concentration 10%
- the cooling rate after nitriding is 20 ° CZ seconds
- D is the ammonia concentration 20%
- the cooling rate after nitriding is 20 ° CZ seconds.
- the cooling rate after nitriding is from 55 ° C to 30 ° C.
- the average cooling rate is 0 ° C.
- the can strength is organized by (number density at (surface layer 1Z20 thickness) of steel sheet after nitriding) Z (number density at (surface layer 1/20 thickness) of steel sheet before nitriding) Figure 4.
- the can strength can be significantly increased by the present invention.
- the figure also shows the strength of cans of materials with different thicknesses manufactured by changing only the cold rolling ratio before recrystallization annealing with the same steel composition. It can be seen that the present invention makes it possible to reduce the thickness of the material while maintaining the desired can strength.
- Table 1-1 Table 1-1
- the present invention makes it possible to obtain an ultrathin container steel plate with high productivity, which can be remarkably improved without sacrificing one of the deformation resistance and can moldability of the container.
- the material in a can having a can body formed with a bead, for example, the material can be thinned and the amount of uneven processing can be reduced, so that not only can weight reduction but also corrosion resistance can be improved. It becomes. For this reason, it can be applied as a steel plate for containers typified by beverage cans and food cans.
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Abstract
Description
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PCT/JP2004/013493 WO2006027854A1 (ja) | 2004-09-09 | 2004-09-09 | 極薄容器用の鋼板およびその製造方法 |
CNA2004800439390A CN101014727A (zh) | 2004-09-09 | 2004-09-09 | 极薄容器用钢板及其制造方法 |
EP04773152A EP1806420A4 (en) | 2004-09-09 | 2004-09-09 | STEEL PLATE FOR EXTREMELY THIN CONTAINERS AND RELATED MANUFACTURING METHOD |
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PCT/JP2004/013493 WO2006027854A1 (ja) | 2004-09-09 | 2004-09-09 | 極薄容器用の鋼板およびその製造方法 |
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Cited By (4)
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EP2003221A1 (en) * | 2006-04-04 | 2008-12-17 | Nippon Steel Corporation | Very thin hard steel sheet and method for producing the same |
EP2050834A1 (en) * | 2006-08-11 | 2009-04-22 | Nippon Steel Corporation | Dr steel sheet and process for manufacturing the same |
US9689052B2 (en) | 2009-05-18 | 2017-06-27 | Nippon Steel & Sumitomo Metal Corporation | Very thin steel sheet and production method thereof |
JP2021139046A (ja) * | 2020-03-06 | 2021-09-16 | ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー | 包装用板金製品 |
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CN101591755B (zh) * | 2009-07-14 | 2011-06-15 | 武汉钢铁(集团)公司 | 酸性食品罐用镀锡原板及其制造方法 |
DE102015122453B4 (de) * | 2015-12-21 | 2019-01-24 | Thyssenkrupp Ag | Verfahren zur Erzeugung einer feinkörnigen Oberflächenschicht in einem Stahlflachprodukt und Stahlflachprodukt mit einer feinkörnigen Oberflächenschicht |
CN106086643B (zh) * | 2016-06-23 | 2018-03-30 | 宝山钢铁股份有限公司 | 一种高强高延伸率的镀锡原板及其二次冷轧方法 |
KR102045654B1 (ko) | 2017-12-26 | 2019-11-15 | 주식회사 포스코 | 고온 특성과 상온 가공성이 우수한 냉연강판 및 그 제조방법 |
US20220074031A1 (en) * | 2018-12-20 | 2022-03-10 | Jfe Steel Corporation | Steel sheet for cans and method of producing same |
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- 2004-09-09 CN CNA2004800439390A patent/CN101014727A/zh active Pending
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EP2003221A1 (en) * | 2006-04-04 | 2008-12-17 | Nippon Steel Corporation | Very thin hard steel sheet and method for producing the same |
EP2003221A4 (en) * | 2006-04-04 | 2014-12-03 | Nippon Steel & Sumitomo Metal Corp | VERY THIN STEEL OF HARD STEEL AND METHOD FOR MANUFACTURING THE SAME |
EP2050834A1 (en) * | 2006-08-11 | 2009-04-22 | Nippon Steel Corporation | Dr steel sheet and process for manufacturing the same |
EP2050834A4 (en) * | 2006-08-11 | 2010-09-29 | Nippon Steel Corp | DR STEEL PLATE AND MANUFACTURING METHOD THEREFOR |
US9689052B2 (en) | 2009-05-18 | 2017-06-27 | Nippon Steel & Sumitomo Metal Corporation | Very thin steel sheet and production method thereof |
JP2021139046A (ja) * | 2020-03-06 | 2021-09-16 | ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー | 包装用板金製品 |
JP7303234B2 (ja) | 2020-03-06 | 2023-07-04 | ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー | 包装用板金製品 |
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EP1806420A4 (en) | 2008-04-23 |
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