WO2012043776A1 - 高強度鋼板およびその製造方法 - Google Patents
高強度鋼板およびその製造方法 Download PDFInfo
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- WO2012043776A1 WO2012043776A1 PCT/JP2011/072491 JP2011072491W WO2012043776A1 WO 2012043776 A1 WO2012043776 A1 WO 2012043776A1 JP 2011072491 W JP2011072491 W JP 2011072491W WO 2012043776 A1 WO2012043776 A1 WO 2012043776A1
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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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
- C21D1/72—Temporary coatings or embedding materials applied before or during heat treatment during chemical change of surfaces
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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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
- C22C38/02—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
-
- 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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
Definitions
- the present invention relates to a high-strength steel sheet having excellent chemical conversion properties and corrosion resistance after electrodeposition coating even when the Si content is large, and a method for producing the same.
- Si is oxidized even when annealing is performed in a reducing N 2 + H 2 gas atmosphere in which Fe does not oxidize (reducing Fe oxide), and Si oxide is formed on the outermost layer of the steel sheet. (SiO 2 ) is formed. Since this SiO 2 inhibits the formation reaction of the chemical conversion film during the chemical conversion treatment, a minute region (hereinafter also referred to as “ske”) where the chemical conversion film is not formed is formed, and the chemical conversion treatment performance is lowered.
- Patent Document 1 discloses a method of forming an iron coating layer of 20 to 1500 mg / m 2 on a steel sheet using an electroplating method.
- this method there is a problem that the cost is increased due to the additional steps required for the electroplating equipment.
- Patent Document 2 the Mn / Si ratio is defined, and in Patent Document 3, Ni is added to improve the phosphate processability.
- the effect depends on the Si content in the steel sheet, and it is considered that further improvement is necessary for the steel sheet having a high Si content.
- Patent Document 4 by setting the dew point during annealing to ⁇ 25 to 0 ° C., an internal oxide layer made of an Si-containing oxide is formed within a depth of 1 ⁇ m from the surface of the steel sheet substrate, and the steel sheet surface length is 10 ⁇ m. A method is disclosed in which the proportion of the Si-containing oxide is 80% or less.
- the area for controlling the dew point since the area for controlling the dew point is premised on the entire inside of the furnace, the controllability of the dew point is difficult and stable operation is difficult.
- Patent Document 5 describes a method in which a steel sheet temperature reaches 350 to 650 ° C. in an oxidizing atmosphere to form an oxide film on the steel sheet surface, and then heated and cooled to a recrystallization temperature in a reducing atmosphere.
- the thickness of the oxide film formed on the steel sheet surface varies depending on the oxidation method. In some cases, oxidation does not occur sufficiently, and in other cases, the oxide film becomes too thick to cause the oxide film to remain or peel off during subsequent annealing in a reducing atmosphere, resulting in deterioration of the surface properties.
- a technique for oxidizing in the air is described, but oxidation in the air generates a thick oxide and subsequent reduction is difficult, or a reducing atmosphere with a high hydrogen concentration is required. There are problems such as.
- Patent Document 6 a cold-rolled steel sheet containing 0.1% or more of Si and / or 1.0% or more of Mn by mass%, the steel sheet surface in an iron oxidizing atmosphere at a steel sheet temperature of 400 ° C. or more. Describes a method in which an oxide film is formed, and then the oxide film on the surface of the steel sheet is reduced in an iron reducing atmosphere. Specifically, after oxidizing Fe on the steel sheet surface using a direct fire burner at 400 ° C. or higher and an air ratio of 0.93 or higher and 1.10 or lower, annealing is performed in an N 2 + H 2 gas atmosphere that reduces Fe oxide.
- Patent Document 6 does not specifically describe the heating temperature of an open flame burner, but when it contains a large amount of Si (approximately 0.6% or more), the amount of oxidation of Si that is easier to oxidize than Fe. As a result, the oxidation of Fe is suppressed, and the oxidation of Fe itself becomes too small. As a result, the formation of the surface Fe reduction layer after reduction may be insufficient, or SiO 2 may be present on the steel sheet surface after reduction, resulting in the occurrence of a conversion coating.
- JP-A-5-320952 JP 2004-323969 A Japanese Patent Application Laid-Open No. 6-10096 JP 2003-113441 A JP 55-145122 A JP 2006-45615 A
- the present invention has been made in view of such circumstances, and provides a high-strength steel sheet having excellent chemical conversion property and corrosion resistance after electrodeposition coating, and a method for producing the same, even when the Si content is high. Objective.
- the inside of the steel sheet has been actively oxidized for the purpose of improving the chemical conversion processability.
- the corrosion resistance after electrodeposition coating deteriorates. Therefore, the present inventors have studied a method for solving the problem by a new method not confined to the conventional idea.
- the temperature range in the annealing furnace 820 ° C. or more and 1000 ° C. or less is the dew point of the atmosphere: ⁇ 45 ° C.
- the temperature in the annealing furnace temperature range of 750 ° C. or more. Is controlled such that the dew point of the atmosphere is ⁇ 45 ° C. or lower, and annealing and chemical conversion treatment are performed. By performing such a treatment, the reducing ability in the atmosphere is increased, and oxides of oxidizable elements such as Si and Mn that are selectively surface oxidized (hereinafter referred to as surface concentration) on the steel sheet surface are reduced. Can do.
- the dew point of the annealing atmosphere of the steel sheet is higher than ⁇ 40 ° C.
- moisture in the annealing atmosphere must be removed in order to obtain a dew point of ⁇ 45 ° C. or lower, and the atmosphere of the entire annealing furnace is ⁇ 45 ° C.
- the temperature in the annealing furnace in the soaking process is 820 ° C. or more and 1000 ° C. or less
- the temperature in the annealing furnace in the cooling process is 750 ° C. or more. Since predetermined characteristics can be obtained by controlling the temperature range so that the dew point of the atmosphere is ⁇ 45 ° C. or lower, there is a feature that equipment costs and operation costs can be reduced.
- the high-strength steel sheet reduces surface concentrate without forming internal oxidation, and has excellent scum and chemical conversion treatment properties without unevenness and corrosion resistance after electrodeposition coating. Will be obtained.
- having excellent chemical conversion property means having a non-scaling and uneven appearance after chemical conversion treatment.
- the dew point other than the region where the dew point is set to ⁇ 45 ° C. or lower may be higher than ⁇ 45 ° C.
- the normal dew point may be above ⁇ 40 ° C. to ⁇ 10 ° C.
- the high-strength steel plate obtained by the above method is Fe, Si, Mn, Al, P, and also B, Nb, Ti, Cr, Mo, Cu, Ni in the steel plate surface layer portion within 100 ⁇ m from the steel plate surface.
- the formation of one or more oxides selected from among the above is suppressed, and the total amount thereof is suppressed to 0.060 g / m 2 or less per side. Thereby, it is excellent in chemical conversion property and the corrosion resistance after electrodeposition coating improves remarkably.
- the present invention is based on the above findings, and features are as follows.
- a method for producing a high-strength steel sheet by mass%, C: 0.01 to 0.18%, Si: 0.4 to 2.0%, Mn: 1.0 to 3.0%, Al: 0.001 to 1.0% , P:
- the steel sheet has a component composition by mass%, and B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005 ⁇ 0.05%, Cr: 0.001 to 1.0%, Mo: 0.05 to 1.0%, Cu: 0.05 to 1.0%, Ni: 0.05 to 1.0%
- B 0.001 to 0.005%
- Nb 0.005 to 0.05%
- Ti 0.005 ⁇ 0.05%
- Cr 0.001 to 1.0%
- Mo 0.05 to 1.0%
- Cu 0.05 to 1.0%
- Ni 0.05 to 1.0%
- the high strength means that the tensile strength TS is 340 MPa or more.
- the high-strength steel sheet of the present invention includes both cold-rolled steel sheets and hot-rolled steel sheets.
- the corrosion resistance is improved.
- the temperature in the annealing furnace is set to a temperature range of 820 ° C. or more and 1000 ° C. or less, and the dew point of the atmosphere is ⁇ 45 ° C. or less. It is obtained by controlling the temperature in the annealing furnace: 750 ° C. or higher so that the dew point of the atmosphere is ⁇ 45 ° C. or lower. By controlling in this way, the surface concentrate formed in the heating process is reduced, and the oxide on the surface layer of the steel sheet is reduced. In addition, since the annealing atmosphere has a low oxygen potential, excellent chemical conversion treatment with no scaling and unevenness and higher corrosion resistance can be obtained with little formation of internal oxidation.
- the reason why the temperature range of the annealing furnace temperature in the soaking process is 820 ° C. or more and 1000 ° C. or less is as follows. In the temperature range below 820 ° C., even if the dew point is lowered to ⁇ 45 ° C. or less and the reduction ability is increased, the surface concentrate such as Si and Mn cannot be sufficiently reduced. Moreover, the reason for setting it as 1000 degrees C or less becomes disadvantageous from a viewpoint of deterioration of the equipment (roll etc.) in an annealing furnace, and a cost increase when it exceeds 1000 degreeC.
- the dew point control temperature range of the annealing furnace temperature in the cooling process is set to 750 ° C. or more.
- the temperature range of 750 ° C. or higher the surface concentration of components in the steel begins. If the dew point of the atmosphere is not controlled to ⁇ 45 ° C. or lower in this temperature range, surface concentration of the components in the steel occurs. However, if the dew point of the atmosphere is controlled to ⁇ 45 ° C. or lower, the surface concentration can be suppressed. Further, if the temperature is lower than 750 ° C., the surface concentrate cannot be reduced because the temperature is low even if the dew point of the atmosphere is lowered. Therefore, the temperature range (dew point control region) of the annealing furnace temperature in the cooling process is set to 750 ° C. or higher.
- C 0.01 to 0.18% C improves workability by forming martensite or the like as a steel structure. For that purpose, 0.01% or more is necessary. On the other hand, if it exceeds 0.18%, the elongation is reduced, the material is deteriorated, and the weldability is further deteriorated. Therefore, the C content is 0.01% or more and 0.18% or less.
- Si 0.4 to 2.0% Si is an element effective for strengthening steel and improving elongation to obtain a good material, and 0.4% or more is necessary to obtain the intended strength of the present invention. If Si is less than 0.4%, the strength within the scope of the present invention cannot be obtained, and there is no particular problem with chemical conversion treatment. On the other hand, when it exceeds 2.0%, the steel strengthening ability and the effect of improving elongation become saturated. Furthermore, it becomes difficult to improve the chemical conversion processability. Therefore, the Si amount is set to 0.4% or more and 2.0% or less.
- Mn 1.0 to 3.0% Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is necessary to contain 1.0% or more. On the other hand, if it exceeds 3.0%, it becomes difficult to secure weldability and the balance between strength and ductility. Therefore, the Mn content is 1.0% or more and 3.0% or less.
- Al 0.001 to 1.0% Al is added for the purpose of deoxidizing molten steel, but if the content is less than 0.001%, the purpose is not achieved. The effect of deoxidation of molten steel is obtained at 0.001% or more. On the other hand, if it exceeds 1.0%, the cost increases. Furthermore, the surface concentration of Al increases and it becomes difficult to improve chemical conversion properties. Therefore, the Al content is 0.001% or more and 1.0% or less.
- P 0.005 to 0.060% or less
- P is an element inevitably contained, and in order to make it less than 0.005%, there is a concern about an increase in cost, so 0.005% or more
- P exceeds 0.060% weldability deteriorates.
- the chemical conversion processability is greatly deteriorated, and even with the present invention, it is difficult to improve the chemical conversion processability. Therefore, the P content is 0.005% or more and 0.060% or less.
- S 0.01% S is one of the elements inevitably contained.
- the lower limit is not specified, but if it is contained in a large amount, the weldability and corrosion resistance deteriorate, so the content is made 0.01% or less.
- B 0.001 to 0.005%
- Nb 0.005 to 0.05%
- Ti 0.005 to 0.05%
- Cr 0.001
- B 0.001 to 0.005%
- B amount shall be 0.001% or more and 0.005% or less. Needless to say, however, it is not necessary to add when it is judged that it is not necessary to improve the mechanical properties.
- Nb 0.005 to 0.05% If Nb is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, the cost increases. Therefore, when it contains, Nb amount shall be 0.005% or more and 0.05% or less.
- Ti 0.005 to 0.05% If Ti is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, chemical conversion processability is deteriorated. Therefore, when it contains, Ti amount shall be 0.005% or more and 0.05% or less.
- Cr 0.001 to 1.0%
- Cr 0.001 to 1.0%
- Mo 0.05 to 1.0% If Mo is less than 0.05%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Mo content is 0.05% or more and 1.0% or less.
- Cu 0.05 to 1.0% If Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual ⁇ phase. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Cu content is 0.05% or more and 1.0% or less.
- Ni 0.05 to 1.0% If Ni is less than 0.05%, the effect of promoting the formation of residual ⁇ phase is difficult to obtain. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when it contains, Ni amount shall be 0.05% or more and 1.0% or less.
- the remainder other than the above is Fe and inevitable impurities.
- the manufacturing method of the high strength steel plate of the present invention and the reason for limitation will be described.
- steel having the above chemical components is hot-rolled, it is cold-rolled into a steel plate, and then annealed in a continuous annealing facility.
- the temperature range in the annealing furnace 820 ° C. or more and 1000 ° C. or less is set to the dew point of the atmosphere: ⁇ 45 ° C. or less
- a temperature range of °C or higher is performed at the dew point of the atmosphere: -45 °C or lower. This is the most important requirement in the present invention.
- annealing may be performed as it is without performing cold rolling.
- Hot rolling Usually, it can be performed on the conditions performed.
- the pickling treatment is preferable to perform a pickling treatment after hot pickling.
- the black scale formed on the surface in the pickling process is removed, and then cold-rolled.
- the pickling conditions are not particularly limited.
- Cold rolling is preferably performed at a rolling reduction of 40% to 80%. If the rolling reduction is less than 40%, the recrystallization temperature is lowered, and the mechanical characteristics are likely to deteriorate. On the other hand, if the rolling reduction exceeds 80%, the steel sheet is a high-strength steel plate, so that not only the rolling cost is increased, but also the surface concentration during annealing is increased, so that the chemical conversion property may be deteriorated.
- Cold-rolled steel sheets or hot-rolled steel sheets are annealed and then subjected to chemical conversion treatment.
- a heating step of heating the steel sheet to a predetermined temperature is performed in the heating zone in the previous stage, a soaking step in which the steel plate is maintained at a predetermined temperature for a predetermined time in a soaking zone in the subsequent stage, and then a cooling step is performed.
- the temperature in the annealing furnace is set to 820 ° C. or more and 1000 ° C. or less, and the dew point of the atmosphere is ⁇ 45 ° C. or less.
- the annealing furnace temperature is 750 ° C. or more.
- Annealing and chemical conversion treatment are performed by controlling the temperature range so that the dew point of the atmosphere is ⁇ 45 ° C. or lower. Since the normal dew point is higher than ⁇ 40 ° C., the dew point of ⁇ 45 ° C. or lower is obtained by absorbing and removing moisture in the furnace with an absorbent.
- the volume fraction of hydrogen gas in the atmosphere is less than 1 vol%, the activation effect by reduction cannot be obtained, and the chemical conversion treatment performance deteriorates.
- the upper limit is not particularly specified, but if it exceeds 50 vol%, the cost increases and the effect is saturated. Therefore, the volume fraction of hydrogen gas is preferably 1 vol% or more and 50 vol% or less.
- the gaseous component in an annealing furnace consists of nitrogen gas and an unavoidable impurity gas other than hydrogen gas. Other gas components may be included as long as the effects of the present invention are not impaired.
- tempering is preferably performed at a temperature of 150 to 400 ° C. This is because the elongation tends to deteriorate when the temperature is less than 150 ° C., and the hardness tends to decrease when the temperature exceeds 400 ° C.
- the present invention good chemical conversion treatment can be ensured without carrying out electrolytic pickling, but a small amount of surface condensate inevitably generated during annealing is removed to ensure better chemical conversion treatment.
- the conditions of the electrolytic pickling are not particularly limited, but in order to efficiently remove the inevitably surface-enriched Si and Mn oxides formed after annealing, an alternating electrolysis with a current density of 1 A / dm 2 or more is used. It is desirable.
- the reason for alternating electrolysis is that the pickling effect is small when the steel plate is held at the cathode, and conversely, Fe that is eluted during electrolysis accumulates in the pickling solution while the steel plate is held at the anode. This is because if the Fe concentration increases and adheres to the surface of the steel sheet, problems such as dry dirt occur.
- the pickling solution used for the electrolytic pickling is not particularly limited, but nitric acid and hydrofluoric acid are not preferable because they are highly corrosive to equipment and require careful handling. Hydrochloric acid is not preferred because it may generate chlorine gas from the cathode. For this reason, use of sulfuric acid is preferable in consideration of corrosivity and environment.
- the sulfuric acid concentration is preferably 5% by mass or more and 20% by mass or less. If the sulfuric acid concentration is less than 5% by mass, the electrical conductivity will be low, so that the bath voltage during electrolysis will rise and the power load may become large. On the other hand, if it exceeds 20% by mass, a loss due to drag-out is large, which causes a problem in cost.
- the temperature of the electrolytic solution is preferably 40 ° C. or higher and 70 ° C. or lower. Since the bath temperature rises due to heat generated by continuous electrolysis, the pickling effect may be reduced at less than 40 ° C. Moreover, it may be difficult to maintain the temperature below 40 ° C. Moreover, it is not preferable that temperature exceeds 70 degreeC from a durable viewpoint of the lining of an electrolytic cell.
- the high-strength steel sheet of the present invention is obtained. And it has the characteristic in the structure of the steel plate surface as follows. Formation of one or more oxides selected from Fe, Si, Mn, Al, P, and further B, Nb, Ti, Cr, Mo, Cu, and Ni in the steel sheet surface layer within 100 ⁇ m from the steel sheet surface Are suppressed to 0.060 g / m 2 or less per side in total. In a high-strength steel sheet in which Si and a large amount of Mn are added to steel, in order to satisfy the corrosion resistance, it is required to minimize the internal oxidation of the steel sheet surface layer that may be a starting point of corrosion.
- the activity in the surface layer portion of the iron base such as Si or Mn, which is an easily oxidizable element is reduced by reducing the oxygen potential in the annealing process in order to ensure chemical conversion treatment. And the external oxidation of these elements is suppressed and chemical conversion processability is improved as a result. Furthermore, the internal oxidation formed in the steel plate surface layer portion is also suppressed, and the corrosion resistance is improved.
- Such an effect is a kind selected from Fe, Si, Mn, Al, P, and further B, Nb, Ti, Cr, Mo, Cu, Ni on the surface layer portion of the steel plate within 100 ⁇ m from the surface of the base steel plate.
- the hot-rolled steel sheet having the steel composition shown in Table 1 was pickled, and after removing the black scale, it was cold-rolled to obtain a cold-rolled steel sheet having a thickness of 1.0 mm. In addition, some did not carry out cold rolling, but prepared the hot-rolled steel plate (thickness 2.0 mm) after removing the black scale.
- the cold-rolled steel plate and hot-rolled steel plate obtained above were charged into a continuous annealing facility.
- the annealing equipment as shown in Table 2, the dew point in the temperature range of 820 ° C to 1000 ° C in the annealing furnace in the soaking process and the temperature range of 750 ° C in the annealing furnace in the cooling process is controlled and passed.
- tempering at 300 ° C. ⁇ 140 s was performed after water quenching.
- electrolytic pickling was performed by alternating electrolysis in which the test material was in the order of anode and cathode for 3 seconds each in the order of the current density conditions shown in Table 2 in a sulfuric acid aqueous solution of 5% by mass at 40 ° C. Obtained.
- region which controlled the said dew point was based on -35 degreeC.
- the atmospheric gas components were nitrogen gas, hydrogen gas, and inevitable impurity gas, and the dew point was controlled by absorbing and removing moisture in the atmosphere.
- the hydrogen concentration in the atmosphere was basically 10 vol%.
- TS and El were measured according to the JIS Z 2241 metal material tensile test method with respect to the obtained test material. Moreover, the chemical conversion property and corrosion resistance were investigated with respect to the obtained test material. The amount of oxide (internal oxidation amount) present in the steel sheet surface layer up to 100 ⁇ m just below the steel sheet surface layer was measured. The measurement method and evaluation criteria are shown below.
- Corrosion resistance after electrodeposition coating A test piece having a size of 70 mm x 150 mm was cut out from the test material subjected to chemical conversion treatment obtained by the above method, and cation electrodeposition was performed using PN-150G (registered trademark) manufactured by Nippon Paint Co., Ltd. Coating (baking conditions: 170 ° C. ⁇ 20 minutes, film thickness 25 ⁇ m) was performed. Thereafter, the end surface and the side not evaluated were sealed with Al tape, and a cross cut (cross angle 60 °) reaching the ground iron with a cutter knife was used as a test material.
- PN-150G registered trademark
- Coating (baking conditions: 170 ° C. ⁇ 20 minutes, film thickness 25 ⁇ m) was performed. Thereafter, the end surface and the side not evaluated were sealed with Al tape, and a cross cut (cross angle 60 °) reaching the ground iron with a cutter knife was used as a test material.
- a JIS No. 5 tensile test piece is taken from the sample in a direction of 90 ° with respect to the rolling direction, and a tensile test is performed at a constant crosshead speed of 10 mm / min in accordance with the provisions of JIS Z 2241.
- (TS / MPa) and elongation (El%) were measured, and when TS was less than 650 MPa, TS ⁇ El ⁇ 22000 was judged good and TS ⁇ El ⁇ 22000 was judged poor.
- TS was 650 MPa or more and 900 MPa
- TS ⁇ El ⁇ 20000 was judged good, and TS ⁇ El ⁇ 20000 was judged poor.
- TS was 900 MPa or more, TS ⁇ El ⁇ 18000 was judged good, and TS ⁇ El ⁇ 18000 was judged poor.
- the amount of internal oxidation in the region of the steel sheet surface layer of up to 100 ⁇ m was measured by “impulse furnace melting-infrared absorption method”. However, since it is necessary to subtract the amount of oxygen contained in the material (that is, the high-strength steel plate before annealing), in the present invention, the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 ⁇ m or more in the steel. Measure the oxygen concentration, set the measured value as the amount of oxygen OH contained in the material, measure the oxygen concentration in the steel in the entire thickness direction of the high-strength steel sheet after continuous annealing, and measure the measured value internally. The subsequent oxygen amount OI was used.
- the high-strength steel sheet produced by the method of the present invention is a high-strength steel sheet containing a large amount of easily oxidizable elements such as Si and Mn, but the chemical conversion treatment property, electrodeposition It can be seen that it has excellent corrosion resistance and workability after painting. On the other hand, in the comparative example, any one or more of chemical conversion property, corrosion resistance after electrodeposition coating, and workability is inferior.
- the high-strength steel sheet of the present invention is excellent in chemical conversion property, corrosion resistance, and workability, and can be used as a surface-treated steel sheet for reducing the weight and strength of an automobile body.
- the steel sheet can be applied in a wide range of fields such as home appliances and building materials as a surface-treated steel sheet provided with rust prevention.
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Abstract
Description
一般に自動車用鋼板は塗装して使用されており、その塗装の前処理として、リン酸塩処理と呼ばれる化成処理が施される。鋼板の化成処理は塗装後の耐食性を確保するための重要な処理の一つである。
[1]質量%で、C:0.01~0.18%、Si:0.4~2.0%、Mn:1.0~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含有し、残部がFeおよび不可避的不純物からなる鋼板に、連続焼鈍を施す際に、均熱過程では焼鈍炉内温度:820℃以上1000℃以下の温度域を雰囲気の露点:−45℃以下とし、かつ、冷却過程では焼鈍炉内温度:750℃以上の温度域を雰囲気の露点:−45℃以下とすることを特徴とする高強度鋼板の製造方法。
鋼中に多量のSiおよびMnが添加された高強度鋼板において、耐食性を満足させるためには、腐食の起点となる可能性がある鋼板表層の内部酸化を極力少なくすることが求められる。
C:0.01~0.18%
Cは、鋼組織としてマルテンサイトなどを形成させることで加工性を向上させる。そのためには0.01%以上必要である。一方、0.18%を超えると伸びが低下し材質が劣化し、さらに溶接性が劣化する。したがって、C量は0.01%以上0.18%以下とする。
Siは鋼を強化し伸びを向上させ良好な材質を得るのに有効な元素であり、本発明の目的とする強度を得るためには0.4%以上が必要である。Siが0.4%未満では本発明の適用範囲とする強度が得られず、化成処理性についても特に問題とならない。一方、2.0%を超えると鋼の強化能や伸び向上効果が飽和してくる。さらに、化成処理性の改善が困難となってくる。したがって、Si量は0.4%以上2.0%以下とする。
Mnは鋼の高強度化に有効な元素である。機械特性や強度を確保するためは1.0%以上含有させることが必要である。一方、3.0%を超えると溶接性や、強度と延性のバランスの確保が困難になる。したがって、Mn量は1.0%以上3.0%以下とする。
Alは溶鋼の脱酸を目的に添加されるが、その含有量が0.001%未満の場合、その目的が達成されない。溶鋼の脱酸の効果は0.001%以上で得られる。一方、1.0%を超えるとコストアップになる。さらに、Alの表面濃化が多くなり、化成処理性の改善が困難になってくる。したがって、Al量は0.001%以上1.0%以下とする。
Pは不可避的に含有される元素のひとつであり、0.005%未満にするためには、コストの増大が懸念されるため、0.005%以上とする。一方、Pが0.060%を超えて含有されると溶接性が劣化する。さらに、化成処理性の劣化が激しくなり、本発明をもってしても化成処理性を向上させることが困難となる。したがって、P量は0.005%以上0.060%以下とする。
Sは不可避的に含有される元素のひとつである。下限は規定しないが、多量に含有されると溶接性及び耐食性が劣化するため0.01%以下とする。
これらの元素を添加する場合における適正添加量の限定理由は以下の通りである。
Bは0.001%未満では焼き入れ促進効果が得られにくい。一方、0.005%超えでは化成処理性が劣化する。よって、含有する場合、B量は0.001%以上0.005%以下とする。但しいうまでもなく機械的特性改善上添加する必要がないと判断される場合は添加する必要はない。
Nbは0.005%未満では強度調整の効果が得られにくい。一方、0.05%超えではコストアップを招く。よって、含有する場合、Nb量は0.005%以上0.05%以下とする。
Tiは0.005%未満では強度調整の効果が得られにくい。一方、0.05%超えでは化成処理性の劣化を招く。よって、含有する場合、Ti量は0.005%以上0.05%以下とする。
Crは0.001%未満では焼き入れ促進効果が得られにくい。一方、1.0%超えではCrが表面濃化するため、溶接性が劣化する。よって、含有する場合、Cr量は0.001%以上1.0%以下とする。
Moは0.05%未満では強度調整の効果が得られにくい。一方、1.0%超えではコストアップを招く。よって、含有する場合、Mo量は0.05%以上1.0%以下とする。
Cuは0.05%未満では残留γ相形成促進効果が得られにくい。一方、1.0%超えではコストアップを招く。よって、含有する場合、Cu量は0.05%以上1.0%以下とする。
Niは0.05%未満では残留γ相形成促進効果が得られにくい。一方、1.0%超えではコストアップを招く。よって、含有する場合、Ni量は0.05%以上1.0%以下とする。
例えば、上記化学成分を有する鋼を熱間圧延した後、冷間圧延し鋼板とし、次いで、連続焼鈍設備において焼鈍を行う。なお、焼鈍時、本発明においては、均熱過程では焼鈍炉内温度:820℃以上1000℃以下の温度域を雰囲気の露点:−45℃以下とし、かつ、冷却過程では焼鈍炉内温度:750℃以上の温度域を雰囲気の露点:−45℃以下で行うこととする。これは本発明において、最も重要な要件である。また、上記において、熱間圧延終了後、冷間圧延を施さずに、そのまま焼鈍を行う場合もある。
通常、行われる条件にて行うことができる。
熱間圧延後は酸洗処理を行うのが好ましい。酸洗工程で表面に生成した黒皮スケールを除去し、しかる後冷間圧延する。なお、酸洗条件は特に限定しない。
40%以上80%以下の圧下率で行うことが好ましい。圧下率が40%未満では再結晶温度が低温化するため、機械特性が劣化しやすい。一方、圧下率が80%超えでは高強度鋼板であるため、圧延コストがアップするだけでなく、焼鈍時の表面濃化が増加するため、化成処理性が劣化する場合がある。
焼鈍炉では、前段の加熱帯で鋼板を所定温度まで加熱する加熱工程を行い、後段の均熱帯で所定温度に所定時間保持する均熱工程を行い、次いで、冷却工程を行う。そして、上述したように、均熱過程では焼鈍炉内温度:820℃以上1000℃以下の温度域を雰囲気の露点:−45℃以下とし、かつ、冷却過程では焼鈍炉内温度:750℃以上の温度域を雰囲気の露点:−45℃以下となるように制御して焼鈍、化成処理を行う。通常の露点は−40℃より高いため、炉内の水分を吸収剤で吸収除去することにより−45℃以下の露点とする。
電解酸洗の条件は特に限定しないが、焼鈍後に形成された不可避的に表面濃化したSiやMnの酸化物を効率的に除去するため、電流密度が1A/dm2以上の交番電解とすることが望ましい。交番電解とする理由は、鋼板を陰極に保持したままでは酸洗効果が小さく、逆に鋼板を陽極に保持したままでは電解時に溶出するFeが酸洗液中に蓄積し、酸洗液中のFe濃度が増大してしまい、鋼板表面に付着すると乾き汚れ等の問題が発生してしまうためである。
そして、以下のように、鋼板表面の構造に特徴を有することになる。
鋼板表面から100μm以内の鋼板表層部では、Fe、Si、Mn、Al、P、さらには、B、Nb、Ti、Cr、Mo、Cu、Niの中から選ばれる1種以上の酸化物の形成が合計で片面あたり0.060g/m2以下に抑制される。
鋼中にSi及び多量のMnが添加された高強度鋼板において、耐食性を満足させるためには、腐食の起点になる可能性がある鋼板表層の内部酸化を極力少なくすることが求められる。
表1に示す鋼組成からなる熱延鋼板を酸洗し、黒皮スケールを除去した後、冷間圧延し、厚さ1.0mmの冷延鋼板を得た。なお、一部は冷間圧延を実施せず、黒皮スケール除去後の熱延鋼板(厚さ2.0mm)ままのものも用意した。
化成処理性の評価方法を以下に記載する。
化成処理液は日本パーカライジング(株)製の化成処理液(パルボンドL3080(登録商標))を用い、下記方法で化成処理を施した。
日本パーカライジング(株)製の脱脂液ファインクリーナー(登録商標)で脱脂したのち、水洗し、次に日本パーカライジング(株)製の表面調整液プレパレンZ(登録商標)で30s表面調整を行い、43℃の化成処理液(パルボンドL3080)に120s浸漬した後、水洗し、温風乾燥した。
化成処理後の供試材を走査型電子顕微鏡(SEM)で倍率500倍で無作為に5視野を観察し、化成処理皮膜のスケ面積率を画像処理により測定し、スケ面積率によって以下の評価を行った。○が合格レベルである。
○:10%以下
×:10%超
上記の方法で得られた化成処理を施した供試材より寸法70mm×150mmの試験片を切り出し、日本ペイント(株)製のPN−150G(登録商標)でカチオン電着塗装(焼付け条件:170℃×20分、膜厚25μm)を行った。その後、端部と評価しない側の面をAlテープでシールし、カッターナイフにて地鉄に達するクロスカット(クロス角度60°)を入れ、供試材とした。
次に、供試材を5%NaCl水溶液(55℃)中に、240時間浸漬後に取り出し、水洗、乾燥後にクロスカット部をテープ剥離し、剥離幅を測定し、以下の評価を行った。○は合格を表す。
○:剥離幅が片側2.5mm未満
×:剥離幅が片側2.5mm以上
加工性は、試料から圧延方向に対して90°方向にJIS5号引張試験片を採取し、JIS Z 2241の規定に準拠してクロスヘッド速度10mm/min一定で引張試験を行い、引張り強度(TS/MPa)と伸び(El%)を測定し、TSが650MPa未満の場合は、TS×El≧22000のものを良好、TS×El<22000のものを不良とした。TSが650MPa以上900MPaの場合は、TS×El≧20000のものを良好、TS×El<20000のものを不良とした。TSが900MPa以上の場合は、TS×El≧18000のものを良好、TS×El<18000のものを不良とした。
Claims (4)
- 質量%で、C:0.01~0.18%、Si:0.4~2.0%、Mn:1.0~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含有し、残部がFeおよび不可避的不純物からなる鋼板に、連続焼鈍を施す際に、
均熱過程では焼鈍炉内温度:820℃以上1000℃以下の温度域を雰囲気の露点:−45℃以下とし、かつ、冷却過程では焼鈍炉内温度:750℃以上の温度域を雰囲気の露点:−45℃以下とすることを特徴とする高強度鋼板の製造方法。 - 前記鋼板は、成分組成として、質量%で、さらに、B:0.001~0.005%、Nb:0.005~0.05%、Ti:0.005~0.05%、Cr:0.001~1.0%、Mo:0.05~1.0%、Cu:0.05~1.0%、Ni:0.05~1.0%の中から選ばれる1種以上の元素を含有することを特徴とする請求項1に記載の高強度鋼板の製造方法。
- 前記連続焼鈍を行った後、硫酸を含む水溶液中で電解酸洗を行うことを特徴とする請求項1または2に記載の高強度鋼板の製造方法。
- 請求項1~3のいずれか一項に記載の製造方法により製造され、鋼板表面から100μm以内の鋼板表層部に生成したFe、Si、Mn、Al、P、B、Nb、Ti、Cr、Mo、Cu、Niの中から選ばれる一種以上の酸化物が、片面あたり0.060g/m2以下
であることを特徴とする高強度鋼板。
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US9598743B2 (en) | 2010-09-29 | 2017-03-21 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
US9534270B2 (en) | 2010-09-30 | 2017-01-03 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
EP2623630B1 (en) * | 2010-09-30 | 2020-07-01 | JFE Steel Corporation | Method for producing high-strength steel sheet |
CN105188457A (zh) * | 2013-04-09 | 2015-12-23 | Ykk株式会社 | 拉链部件用合金及拉链部件 |
CN105188457B (zh) * | 2013-04-09 | 2017-12-01 | Ykk株式会社 | 拉链部件用合金及拉链部件 |
Also Published As
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BR112013007658B1 (pt) | 2019-07-16 |
CN103124799B (zh) | 2016-09-07 |
JP2012072447A (ja) | 2012-04-12 |
TW201219578A (en) | 2012-05-16 |
KR101538240B1 (ko) | 2015-07-20 |
US20130174946A1 (en) | 2013-07-11 |
US9598743B2 (en) | 2017-03-21 |
CA2812762C (en) | 2017-02-14 |
TWI510644B (zh) | 2015-12-01 |
EP2623618A4 (en) | 2017-09-20 |
EP2623618B1 (en) | 2019-01-16 |
CA2812762A1 (en) | 2012-04-05 |
CN103124799A (zh) | 2013-05-29 |
KR20130055696A (ko) | 2013-05-28 |
BR112013007658A2 (pt) | 2016-08-09 |
JP5609494B2 (ja) | 2014-10-22 |
EP2623618A1 (en) | 2013-08-07 |
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