METHOD FOR MANUFACTURING HIGH-STRENGTH GALVANIZED STEEL SHEET

Information

  • Patent Application
  • 20170159151
  • Publication Number
    20170159151
  • Date Filed
    June 15, 2015
    9 years ago
  • Date Published
    June 08, 2017
    7 years ago
Abstract
A method for manufacturing a high-strength galvanized steel sheet. The method includes a first heating step of holding the steel sheet in a temperature range of 750° C. to 880° C. for 20 s to 600 s in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −45° C. to −10° C., a cooling step, a rolling step of rolling the steel sheet with a rolling reduction of 0.3% to 2.0%, a pickling step of pickling the steel sheet with a pickling weight loss of 0.02 gram/m2 to 5 gram/m2 in terms of Fe, a second heating step of holding the steel sheet in a temperature range of 720° C. to 860° C. for 20 sec. to 300 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −10° C. or lower, and a galvanizing step.
Description
TECHNICAL FIELD

The present disclosure relates to a method for manufacturing a high-strength galvanized steel sheet suitable for use in automotive parts applications.


BACKGROUND ART

In recent years, with the rising awareness of global environmental protection, improvements in fuel efficiency have been strongly required for reducing automobile CO2 emissions. This has led to active attempts to reduce the thickness of automotive parts by strengthening steel sheets, which are materials for automobile body parts, to reduce automobile weight.


In order to strengthen steel sheets, solid solution-strengthening elements such as Si and Mn are added. However, these elements are more oxidizable than Fe. Therefore, in the case of manufacturing galvanized steel sheets and galvannealed steel sheets from high-strength steel sheets containing large amounts of these elements, there are problems below.


In usual, in order to manufacture a galvanized steel sheet, after a steel sheet is heated and annealed at a temperature of about 600° C. to 900° C. a non-oxidizing atmosphere or a reducing atmosphere, the steel sheet is galvanized. Oxidizable elements in steel are selectively oxidized in a non-oxidizing atmosphere or reducing atmosphere generally used and concentrate on surfaces to form oxides on surfaces of the steel sheet. The oxides reduce the wettability between the steel sheet surfaces and molten zinc to cause bare spots. The increase in concentration of each oxidizable element in steel sharply reduces the wettability to cause many bare spots. Even in the case where no bare spots are caused, the oxides are present between the steel sheet and a coating and therefore the adhesion of the coating is deteriorated. In particular, the addition of even a small amount of Si significantly reduces the wettability with molten zinc. Therefore, in galvanized steel sheets, Mn, which has a small influence on wettability, is often added. However, Mn oxides also reduce the wettability with molten zinc. Therefore, in the case of the addition of a large amount of Mn, a problem with the above bare spots is significant.


In order to cope with the problem, Patent Literature 1 proposes a method for improving the wettability of a surface of a steel sheet with molten zinc in such a manner that the steel sheet is heated in an oxidizing atmosphere in advance, the oxidation of an added element on the steel sheet surface by rapidly forming an Fe oxide film on the surface at a predetermined oxidation rate or more, and the Fe oxide film is then reductively annealed. However, when the oxidation of the steel sheet is significant, there is a problem in that iron oxide adheres to a roll in a furnace to cause scratches on the steel sheet. In addition, Mn forms a solid solution in the Fe oxide film and therefore is likely to form Mn oxides on the steel sheet surface during reductive annealing; hence, the effect of oxidation treatment is small.


Patent Literature 2 proposes a method in which a steel sheet is pickled after annealing, surface oxides are thereby removed, and the steel sheet is annealed again and is then galvanized. However, when the amount of an added alloying element is large, surface oxides are formed again during re-annealing. Therefore, even in the case where no bare spots are caused, there is a problem in that the adhesion of a coating is deteriorated.


CITATION LIST
Patent Literature

[PTL 1] Japanese Patent No. 2587724 (Japanese Unexamined Patent Application Publication No. 4-202630)


[PTL 2] Japanese Patent No. 3956550 (Japanese Unexamined Patent Application Publication No. 2000-290730)


SUMMARY
Technical Problem

In view of the above circumstances, it is an object of the present disclosure to provide a method for manufacturing a high-strength galvanized steel sheet excellent in coating adhesion and surface appearance.


Solution to Problem

The inventors have conducted intensive investigations to manufacture a steel sheet which contains Mn and which is excellent in surface appearance and coat adhesion and have found the following.


The following method is effective in improving the surface appearance of a steel sheet containing Mn: a method in which pickling is performed after annealing, re-annealing performed, and galvanizing is then performed as described in Patent Literature 2. However, when a large amount of Mn is contained, it is difficult to completely suppress the formation of oxides during re-annealing as described above and therefore the adhesion of a coating is poor in some cases. Thus, a means for enhancing the coating adhesion is necessary.


In order to enhance the coating adhesion, a technique for forming fine irregularities by roughening a surface of a steel sheet is used. Examples of the technique for forming the fine irregularities include a method for grinding a surface of a steel sheet and a shot-blasting method. These methods require a new facility in a manufacturing line and therefore cost significantly. As a result of investigating methods for imparting fine irregularities to surfaces of steel sheets at low cost using an existing facility, a method below has been established. When a steel sheet containing Mn is annealed, spherical or massive oxides containing Mn are formed on a surface of the steel sheet. The oxides containing Mn are pushed into the steel sheet by rolling and are then removed, whereby a steel sheet having fine irregularities formed on a surface thereof can be obtained.


The present disclosure is based on the above finding. Exemplary disclosed embodiments include as follows.


(1) A method for manufacturing a high-strength galvanized steel sheet includes a first heating step of holding a steel sheet containing 0.040% to 0.500% C, 0.80% or less Si, 1.80% to 4.00% Mn, 0.100% or less P, 0.0100 or less S, 0.100% or less Al, and 0.0100% or less N as a composition on a mass basis, the remainder being Fe and inevitable impurities, in a temperature range of 750° C. to 880° C. for 20 sec. to 600 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −45° C. to −10° C., a cooling step of cooling the steel sheet after the first heating step, a rolling step of rolling the steel sheet with a rolling reduction of 0.3% to 2.0% after the cooling step, a pickling step of pickling the steel sheet with a pickling weight loss of 0.02 gram/m2 to 5 gram/m2 in terms of Fe after the rolling step, a second heating step of holding the steel sheet in a temperature range of 720° C. to 860° C. for 20 sec. to 300 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −10° C. or lower after the pickling step, and a galvanizing step of galvanizing the steel sheet after the second heating step.


(2) in the method for manufacturing the high-strength galvanized steel sheet specified in item (1), at least one element selected from 0.010% to 0.100% Ti, 0.010% to 0.100% Nb, and 0.0001% to 0.0050% 3 on a mass basis is further contained as a composition.


(3) In the method for manufacturing the high-strength galvanized steel sheet specified in Item (1) or (2), at least one element selected from 0.01% to 0.50% Mo, 0.30% or less 0.50% or less Ni, 1.00% or less Cu, 0.500% or less V, 0.10% or less Sb, 0.10% or less Sn, 0.0100% or less Ca, and 0.010% or less of a REM on a mass basis is further contained as a composition.


(4) In the method for manufacturing the high-strength galvanized steel sheet specified in any one of Items (1) to (3), in the manufacture of the steel sheet subjected to the first heating step, after a steel slab is hot-rolled and is then descaled by pickling, a heat treatment step is performed in such a manner that the steel sheet is held at a temperature of 600° C. or higher for 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the sheet is exposed to the atmosphere.


(5) The method for manufacturing the high-strength galvanized steel sheet specified in any one of Items (1) to (4) further includes an alloying treatment step of alloying the steel sheet after the galvanizing step.


In the present disclosure, the term “high-strength galvanized steel sheet” refers to a steel sheet with a tensile strength (TS) of 780 MPa or more and the term “galvanized steel sheet” includes a plated steel sheet (hereinafter referred to as “GI” in some cases) not alloyed after galvanizing and a plated steel sheet (hereinafter referred to as “GA” in some cases) alloyed after galvanizing.


Advantageous Effects

According to the present disclosure, a high-strength galvanized steel sheet excellent in surface appearance and coating adhesion is obtained. Applying a high-strength galvanized steel sheet according to the present disclosure to, for example, automobile structural parts enables the improvement in fuel consumption due to the reduction of automobile weight to be achieved.







DESCRIPTION OF EMBODIMENTS

Embodiments of the present disclosure are as described below. The present disclosure is not limited to the embodiments. The unit “%” used to express the content of each component refers to “mass percent”.


First, the composition is described. The following components are contained, the remainder being Fe and inevitable impurities: 0.040% to 0.500% C, 0.80% or less Si, 1.80% to 4.00% Mn, 0.100% or less P, 0.0100% or less S, 0.100% or less Al, and 0.0100% or less N. In addition to the above components, at least one element selected from 0.010% to 0.100% Ti, 0.010% to 0.100% Nb, and 0.0001% to 0.0050% B may be further contained. In addition to the above components, at least one element selected from 0.01% to 0.50% Mo, 0.30% or less Cr, 0.50% or less Ni, 1.00% or less Cu, 0,500% or less V, 0.10% or less Sb, 0.10% or less Sn, 0.0100% or less Ca, and 0.010% or less of a REM may be further contained. The components are described below.


C: 0.040% to 0.500%


C is an austenite-producing element and is also an element which is effective in multiplexing the microstructure of an annealed steel sheet to increase the strength and ductility thereof. In order to increase the strength and the ductility, the content of C is set to 0.040% or more. However, when the content of C is more than 0.500%, the hardening of a weld and a heat-affected zone is significant, mechanical characteristics of the weld are deteriorated, and spot weldability and arc weldability are reduced. Therefore, the content of C is set to 0.500% or less.


Si: 0.80% or Less


Si is a ferrite-producing element and is also an element effect ive in enhancing the solid solution strengthening and work hardenability of ferrite in an annealed steel sheet. When the content of Si is more than 0.80%, Si forms an oxide on a surface of a steel sheet during annealing to deteriorate the wettability of a coating. Thus, the content of Si is set to 0.80% or less.


Mn: 1.80% to 4.00%


Mn is an austenite-producing element and is also an element effective ensuring the strength of an annealed steel sheet. In order to ensure the strength thereof, the content of Mn is set to 1.80% or more. However, when the content of Mn is more than 4.00%, a surface layer containing large amounts of oxides formed on a surface of a steel sheet during annealing deteriorates the appearance of a coating. Therefore, the content of Mn is set to 4.00% or less.


P: 0.100% or Less


P is an element effective in strengthening steel. From the viewpoint of strengthening steel, the content of P is preferably 0.001% or more. However, the content of P is re than 0.100%, intergranular segregation causes embrittlement to deteriorate crashworthiness. Thus, the content of P is set to 0.100% or less.


S: 0.0100% or Less


S forms inclusions such as MnS to cause the deterioration of crashworthiness or cracks along metal flows in welds. Therefore, the content of S is preferably as low as possible. Thus, the content of S is set to 0.0100% or less.


Al: 0.100% or Less


The excessive addition of Al increases the amounts of oxide inclusions to cause the deterioration of surface quality and formability and leads to high costs. Therefore, the content of Al is preferably set to 100 or less and more preferably 0.050% or less.


N: 0.0100% or Less


N is an element deteriorating the aging resistance of steel and is preferably small in amount. When the content of N is more than 0.0100%, the deterioration of aging resistance is significant. Thus, the content of N is set to 0.0100% or less.


The remainder are Fe and the inevitable impurities. A high-strength galvanized steel sheet according to the present disclosure may contain elements below as required for the purpose of achieving high strength and the like.


Ti: 0.010% to 0.100%


Ti is an element which forms fine carbides or nitrides with C or N, respectively, in a steel sheet to contribute to the increase in strength of the steel sheet. In order to obtain this effect, the content of Ti is preferably 0.010% or more. However, when the content of Ti is more than 0.100%, this effect is saturated. Therefore, the content of Ti is preferably 0.100% or less.


Nb: 0.010% to 0.100%


Nb is an element, contributing to the increase of strength by solid solution strengthening or precipitation strengthening. In order to obtain this effect, the content of Nb is preferably 0.010% or more. However, when the content of Nb is more than 0.100%, the ductility of a steel sheet is reduced and the workability thereof is deteriorated in some cases. Therefore, the content of Nb is preferably 0.100% or less.


B: 0.0001% to 0.0050%


B is an element which increases the hardenability of a steel sheet to contribute to the increase in strength of the steel sheet. In order to obtain this effect, the content of B is preferably 0.0001% or more. However, containing an excessive amount of B causes a reduction in ductility to deteriorate workability in some cases. Furthermore, containing an excessive amount of B causes cost increases. Therefore, the content of B is preferably 0.0050% or less.


Mo: 0.01% to 0.50%


Mo is an austenite-producing element and is also an element effective in ensuring the strength of an annealed steel sheet. From the viewpoint of ensuring the strength thereof, the content of Mo is preferably 0.01% or more. However, Mo is high in alloying cost and therefore a high Mo content causes cost increases. Therefore, the content of Mo is preferably 0.50% or less.


Cr: 0.30% or Less


Cr is an austenite-producing element and is also an element effective in ensuring the strength of an annealed steel sheet. Then the content of Cr is more than 0.30%, oxides are formed on a surface of a steel sheet during annealing to deteriorate the appearance of a coating in some cases. Therefore, the content of Cr is preferably 0.30% or less.


Ni: 0.50% or Less, Cu: 1.00% or Less, V: 0.500% or Less


Ni, Cu, and V are elements effective in strengthening steel and may be used to strengthen steel within a range specified in the present disclosure. In order to strengthen steel, the content of Ni is preferably 0.05% or more, the content of Cu is preferably 0.05% or more, and the content of V is preferably 0.005% or more. However, the excessive addition of more than 0.50% Ni, more than 1.00% Cu, and more than 0.500% V causes concerns about a reduction in ductility due to a significant increase in strength in some cases. Furthermore, containing excessive amounts of these elements causes cost increases. Thus, when these elements are contained, the content of Ni is preferably 0.50% or less, the content of Cu is preferably 1.00% or less, and the content of V is preferably 0.500% or less.


Sb: 0.10% or Less, Sn: 0.10% or Less


Sb and Sn have the ability to suppress nitrogenation near a surface of a steel sheet. In order to suppress nitrogenation, the content of Sb is preferably 0.005% or more and the content of Sn is preferably 0.005% or more. However, when the content of Sb and the content of Sn are more than 0.10%, the above effect is saturated. Thus, when these elements are contained, the content of Sb is preferably 0.10% or less and the content of Sn is preferably 0.10% or less.


Ca: 0.0100% or Less


Ca has the effect of enhancing ductility by controlling the shape of sulfides such as MnS. In order to obtain this effect, the content of Ca is preferably 0.0010% or more. However, when the content of Ca is more than 0.0100%, this effect is saturated. Therefore, when Ca is contained, the content of Ca is preferably 0.0100% or less.


REM: 0.010% or Less


The REM controls the morphology of sulfide inclusions to contribute to the enhancement of workability. In order to obtain the effect of enhancing workability, the content of the REM is preferably 0.001% or more. When the content of the REM is more than 0.010%, the amounts of inclusions are increased and workability is deteriorated in some cases. Thus, when the REM is contained, the content of the REM is preferably 0.010% or less.


A method for manufacturing the high-strength galvanized steel sheet according to the present disclosure is described below.


A steel slab having the above composition is subjected to rough rolling and finish rolling in a hot rolling step. Thereafter, a surface layer of a hot-rolled plate is descaled in a pickling step and the hot-rolled plate is cold-rolled. Herein, conditions of the hot rolling step, conditions of the pickling step, and conditions of a cold rolling step are not particularly limited and may be appropriately set. Manufacturing may be performed by thin strip casting in such a manner that a portion or the whole of the hot rolling step is omitted. In a period which follows the pickling step and which is prior to the cold rolling step, a heat treatment step may be performed as required in such a manner that the steel sheet is held at a temperature of 600° C. or higher for 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the steel sheet is exposed to the atmosphere (for example, a tight coil state). Herein, the unit for the holding time means “second or sec.”.


The heat treatment step is described below in detail.


The heating step is a step in which the steel sheet subjected to the pickling step is held at a temperature of 600° C. or higher for a time of 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the steel sheet is exposed to the atmosphere.


The heat treatment step is performed for the purpose of concentrating Mn in an austenite phase in the steel sheet after hot rolling. In general, hot-rolled steel sheets have a microstructure composed of a plurality of phases such as a ferrite phase, an austenite phase, a pearlite phase, a bainite phase, and a cementite phase. Concentrating Mn in the austenite phase is expected to enhance the ductility of a galvanized steel sheet which is a final product.


When the temperature or holding time in the heat treatment step is lower than 600° C. or 600 sec, respectively, the concentration of Mn in the austenite phase may not possibly proceed. The upper limit of the temperature is not particularly limited. When the temperature is higher than 850° C., the concentration of Mn in the austenite phase is saturated and cost increases arise. Thus, the temperature is preferably 850° C. or lower. On the other hand, when the steel sheet is held for more than 21,600 sec, the concentration of Mn in the austenite phase is saturated, an effect on the ductility of a final product is small, and cost increases arise. Thus, heat treatment is preferably performed at a temperature of 600° C. or higher for a holding time of 600 sec. to 21,600 sec.


In the heat treatment step, in order to avoid influences on a first heating step and second heating step following the heat treatment step, the surface oxidation of the steel sheet is suppressed during heat treatment for a long time. Therefore, no surface of the steel sheet is preferably exposed to any atmosphere. The expression “no surface of the steel sheet is exposed to any atmosphere” includes not only a state in which both surfaces of the steel sheet are not exposed to any atmosphere but also a state in which a surface of the steel sheet is not exposed to any atmosphere. Thickness surfaces of the steel sheet are end surfaces thereof and do not correspond to the above surface. In order to maintain a state in which no surface of the steel sheet is exposed to any atmosphere, for example, the following method is cited: a method, such as vacuum annealing, for completely blocking an atmosphere. This method has a significant problem with cost. On the basis of a usual step, the ingress of an atmosphere between portions of the steel sheet can be suppressed in such a manner that the coiled sheet steel is tightly coiled such that a so-called tight coil is formed. Incidentally, the outermost peripheral surface of a coil is usually near a weld during heating in a downstream step and is removed from a product. In the case where heating is not performed in a continuous line, the outermost peripheral surface is removed, whereby a product is obtained.


Even in the case where the tight coil is formed, an end surface of the coil is oxidized in an atmosphere in which Fe is oxidized, an inner portion of the coil is corroded, and therefore the coating appearance of a final product may possibly be impaired. Thus, in order to suppress the oxidation of Fe during heat treatment for a long time, the concentration of H2 is preferably 1.0% by volume or more, which is a sufficient level. An H2 concentration of more than 25.0% by volume leads to cost increases. Thus, the concentration of H2 is preferably 1.0% to 25.0% by volume. The remainder other than H2 are N2, H2O, and inevitable impurities.


Likewise, when the dew point is higher than 10° C., be in an end surface of the coil may possibly be oxidized. Therefore, the dew point is preferably 10° C. or lower.


Next, steps which are important requirements for the present disclosure are performed as described below. The following steps are performed: a first heating step of holding the steel sheet in a temperature range of 750° C. to 880° C. for 20 sec. to 600 ec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −45° C. to −10° C., a cooling step of cooling the steel sheet after the first heating step, a rolling step of rolling the steel sheet with a rolling reduction of 0.3% to 2.0% after the cooling step, a pickling step of pickling the steel sheet with a pickling weight loss of 0.02 gram/m2 to 5 gram/m2 in terms of Fe after the rolling step, a second heating step of holding the steel sheet at an arbitrary temperature of 720° C. to 860° C. or in a temperature range of 720° C. to 860° C. for 20 sec. to 300 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −10° C. or lower after the pickling step, and a galvanizing step of galvanizing the steel sheet after the second heating step. The unit “s” for the holding time in the first and second heating steps means “seconds”. The first heating step, the cooling step, the rolling step, the pickling step, the second heating step, and the galvanizing step may be performed in a continuous line or separate lines. The steps are described below in detail.


First Heating Step


The first heating step is a step of holding the steel sheet in a temperature range of 750° C. to 880° C. for 0.0 sec. to 600 sec, in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −45° C. to −10° C. in the first heating step, Mn is oxidized on a surface of the steel sheet without oxidizing Fe.


The H2 concentration needs to be a level sufficient to suppress the oxidation of Fe and is set to 0.05% by volume or more. However, when the H2 concentration is more than 25.0% by volume, cost increases arise. Therefore, the H2 concentration is set to 25.0% by volume or less. The remainder are N2, H2O, and inevitable impurities.


When the dew point is lower than −45° C., the oxidation of Mn is suppressed. When the dew point is higher than −10° C., Fe is oxidized. Thus, the dew point is set to a temperature of −45° C. to −10° C.


When the temperature of the steel sheet is lower than 750° C., Mn is not sufficiently oxidized. When the temperature of the steel sheet is higher than 880° C., heat costs are high. Thus, the heating temperature of the held steel sheet (the temperature of the steel sheet) is set to a temperature range of 750° C. to 880° C. In the first heating step, the steel sheet may be held at a constant temperature steel sheet is varied in a temperature range of 750° C. to 880° C.


When the holding time is less than 20 sec, Mn oxides are not sufficiently formed on a surface. When the holding time is more than 600 sec, the excessive formation of Mn oxides reduces the efficiency of pickling to reduce the manufacturing efficiency. Thus, the holding time is set to 20 sec. to 600 sec.


Cooling Step


The steel sheet is cooled to a temperature at which the steel sheet can be rolled.


Rolling Step


The cooled steel sheet is rolled with a rolling reduction of 0.3% to 2.0%. This step is performed for the purpose of increasing the coating adhesion in such a manner that the steel sheet is lightly rolled after the first heating step and oxides formed on surfaces of the steel sheet are thereby pushed into the steel sheet surfaces such that fine irregularities are imparted to the steel sheet surfaces. When the rolling reduction is less than 0.3% or less, irregularities cannot be sufficiently imparted to the steel sheet surfaces in some cases. When the rolling reduction is more than 2.0%, a lot of strain introduced into the steel sheet, pickling is promoted in the next pickling step, and therefore irregularities formed in the rolling step are eliminated in some cases. Thus, the rolling reduction is set to 0.3% to 2.0%.


Pickling Step


Surfaces of the steel sheet are pickled with a pickling weight loss of 0.02 gram/m2 to 5 gram/m2 in terms of Fe after the rolling step. This step is performed for the purpose of cleaning the steel sheet surfaces and the purpose of removing oxides, formed on the steel sheet surfaces in the first heating step, soluble in acid.


When the pickling weight loss is less than 0.02 gram/m2 in terms of Fe, the oxides are not sufficiently removed in some cases. When the pickling weight loss is more than 5 gram m2, not only the oxides on the steel sheet surfaces but also an inner portion of the steel sheet that has a reduced Mn concentration are dissolved in some cases and the formation of Mn oxides cannot be suppressed in the second heating step in some cases. Thus, the pickling weight loss is set to 0.02 gram/m2 to 5 gram/m2 in terms of Fe.


The Fe conversion value of the pickling weight loss is determined from the change in concentration of Fe in a pickling solution before and after processing and the area of a processed sheet.


Second Heating Step


The pickled steel sheet is held in a temperature range of 720° C. to 860° C. for 20 sec, to 300 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −10° C. or lower. The second heating step is performed for the purpose of activating surfaces of the steel sheet to plate the steel sheet.


The H2 concentration needs to be a level sufficient to suppress the oxidation of Fe and is set to 0.05% by volume or more. However, when the H2 concentration is more than 25.0% by volume, cost increases arise. Therefore, the H2 concentration is set to 25.0% by volume or less. The remainder are N2, H2O, and inevitable impurities.


When the dew point is higher than −10° C., Fe is oxidized. Therefore, the dew point is set to −10° C. or lower.


When the temperature of the steel sheet is lower than 720° C., surfaces of the steel sheet are not activated and therefore have low wettability with molten zinc. However, when the temperature of the steel sheet is higher than 860° C., Mn forms oxides on the surfaces during annealing to form surface layers containing Mn oxides and therefore reduces the wettability of the steel sheet with molten zinc. Thus, the heating temperature of the held steel sheet (the temperature of the steel sheet) is set to a temperature range of 720° C. to 860° C. the second heating step, the steel sheet may be held at a constant temperature or may be held in such a manner that the temperature of the steel sheet is varied.


When the holding time is less than 20 sec, the steel sheet surfaces are not sufficiently activated. When the holding time is more than 300 sec, Mn forms oxides on the surfaces again to form surface layers containing Mn oxides and therefore reduces the wettability with molten zinc. Thus, the holding time is set to 20 sec. to 300 sec.


Galvanizing Step


The galvanizing step is a step in which after being treated as described above, the steel sheet is cooled, is immersed in a zinc molten, bath, and is thereby galvanized.


In the case of manufacturing a galvanized steel sheet, a zinc molten bath having a temperature of 440° C. to 550° C. and an Al concentration of 0.14% to 0.24% is preferably used.


When the temperature of the bath is lower than 440° C., Zn may possibly be solidified by temperature changes in a low-temperature portion in the bath, resulting in inadequacy. When the bath temperature is higher than 550° C., the vaporization of the bath is significant and evaporated Zn adheres to the inside of a furnace to cause operational problems in some cases. Furthermore, alloying proceeds during galvanizing and therefore over alloying is likely to occur.


When the concentration of Al in the bath is less than 0.14% in the course of manufacturing the galvanized steel sheet, the alloying of Fe—Zn proceeds to impair coating adhesion in some cases. When the concentration of Al is more than 0.248, defects are caused by Al oxides in some cases.


In the case of performing alloying after galvanizing, a zinc molten bath with an Al concentration of 0.10% to 0.20% is preferably used. When the concentration of Al in the bath is less than 0.10%, a large amount of a Γ phase is produced to impair powdering properties in some cases. When the concentration of Al is more than 0.200 the alloying of Fe—Zn does not proceed in some cases.


Alloying Treatment Step


The steel sheet is alloyed after the galvanizing step as required. Conditions for alloying are not particularly limited. The alloying temperature is preferably higher than 460° C. to lower than 580° C. When the alloying temperature is 460° C. or lower, alloying proceeds slowly. When the alloying temperature is 580° C. or higher, hard brittle Fe—Zn alloy layers are excessively produced by over-alloying at base metal interfaces to deteriorate coating adhesion in some cases.


Examples

Each steel containing components shown in Table 1, the remainder being Fe and inevitable impurities, was produced in a converter and was then formed into a slab by a continuous casting process. The obtained slab was heated to 1,200° C. and was hot-rolled to a thickness of 2.3 mm to 4.5 mm, followed by coiling. Next, an obtained hot-rolled plate was pickled, was heat-treated as required, and was then cold-rolled. Thereafter, a first heating step, a cooling step, a rolling step, a pickling step, and a second heating step were performed in an atmosphere-adjustable furnace under conditions shown in Tables 2 to 6. Cooling to 100° C. or lower was performed. Subsequently, a galvanizing step was performed. Galvanizing was performed in a Zn bath containing 0.14% to 0.24% Al under conditions shown in Tables 2 to 6, whereby a galvanized steel sheet was obtained. Some of steel sheets were plated in a Zn bath containing 0.10% to 2.0% Al and were then alloyed under conditions shown in Tables 2 to 6.


The galvanized steel sheets obtained as described above were investigated for strength, total elongation, surface appearance, and coating adhesion by methods below.


<Tensile Strength and Total Elongation>


A tensile test was performed in accordance with JIS Z 2241 using a JIS No. 5 test specimen that was sampled such that tensile directions were perpendicular to the rolling direction of each steel sheet, whereby TS (tensile strength) and EL (total elongation) were measured.


<Surface Appearance>


Whether appearance defects such as pinholes and bare spots were present was visually checked. The case where no appearance defect was present was judged to be good (A). The case where a few appearance defects were present was judged to be almost good (B). The case where appearance defects were present was judged to be (C).


<Coating Adhesion>


Galvannealed steel sheets (GA) were evaluated for coating adhesion by evaluating powdering resistance. In particular, a cellophane tape was stuck to each galvannealed steel sheet, a surface of the tape was bent to 90 degrees and was then bent back, a cellophane tape with a width of 24 mm was pressed against the inside (compressed side) of a worked portion in parallel to the worked portion and was separated therefrom, and the amount of zinc attached to a 40 mm long portion of this cellophane tape was measured as the number of Zn counts using a fluorescent X-ray. On the basis of a value converted from the number of Zn counts per unit length (1 mm), those ranked 2 or lower were rated particularly good (A), those ranked 3 were rated good (B), and those ranked 4 or higher were rated poor (C) in the light of standards below.
















Number of fluorescent X-ray counts
Rank









0 to less than 2,000
1 (good)



2,000 to less than 5,000
2



5,000 to less than 8,000
3



8,000 to less than 10,000
4



10,000 or more
5 (poor)










For GI, a ball impact test was performed, a cellophane tape was peeled from a worked portion, and whether a coating layer was peeled off was visually checked, whereby coating adhesion was evaluated. Incidentally, the ball impact test was performed with a ball mass of 1.8 kg and a drop height of 100 cm.


A: no peeled coating layer


B: peeled coating layer


Results obtained from the above evaluation are shown in Tables 2 to 6 together with conditions.




















TABLE 1







Steel













symbol
C
Si
Mn
P
S
Al
N
Ti
Nb
B
Mo





A
0.082
0.21
3.15
0.007
0.0010
0.031
0.0038
0.021
0.045
0.0012



B
0.146
0.12
3.09
0.005
0.0007
0.043
0.0030
0.034
0.039
0.0015



C
0.079
0.23
2.58
0.008
0.0008
0.024
0.0035
0.018
0.040
0.0010
0.19


D
0.151
0.12
2.64
0.007
0.0012
0.033
0.0040
0.023
0.042
0.0015
0.17


E
0.095
0.13
3.41
0.007
0.0008
0.029
0.0034
0.025
0.051




F
0.165
0.19
1.84
0.006
0.0016
0.037
0.0029
0.033
0.027




G
0.153
0.51
3.24
0.004
0.0011
0.041
0.0038
0.027
0.038




H
0.144
0.48
2.61
0.004
0.0009
0.034
0.0031
0.018
0.043

0.12


I
0.097
0.22
2.42
0.008
0.0023
0.084
0.0035
0.031
0.040
0.0030



J
0.089
0.18
2.59
0.007
0.0015
0.025
0.0027
0.023
0.032




K
0.142
0.15
2.94
0.005
0.0007
0.035
0.0042
0.027
0.044

0.26


L
0.089
0.24
2.48
0.009
0.0009
0.044
0.0034
0.035
0.027




M
0.094
0.07
3.31
0.012
0.0005
0.021
0.0029
0.043
0.038




N
0.128
0.11
3.24
0.008
0.0012
0.053
0.0033
0.022
0.033




O
0.106
0.19
2.74
0.009
0.0010
0.036
0.0037
0.025
0.042




P
0.149
0.23
2.59
0.005
0.0008
0.043
0.0024
0.019
0.050




Q
0.103
0.02
3.72
0.006
0.0008
0.035
0.0031
0.021
0.033




R
0.094
0.04
3.54
0.008
0.0070
0.033
0.0029






S
0.085
0.11

4.50

0.007
0.0024
0.034
0.0041
0.034
0.037




T
0.095

1.24

2.23
0.006
0.0015
0.027
0.0038
0.024
0.035




U
0.152
0.02
3.56
0.015
0.0020
0.041
0.0038
0.042





V
0.149
0.01
3.92
0.003
0.0007
0.037
0.0032






W
0.163
0.52
3.45
0.005
0.0008
0.039
0.0041














(mass percent)


















Steel












symbol
Cr
Ni
Cu
V
Sb
Sn
Ca
REM
Remarks







A








Inventive steel



B








Inventive steel



C








Inventive steel



D








Inventive steel



E








Inventive steel



F








Inventive steel



G








Inventive steel



H








Inventive steel



I



0.058




Inventive steel



J


0.05





Inventive steel



K
0.15







Inventive steel



L





0.03


Inventive steel



M

0.22






Inventive steel



N






0.0018

Inventive steel



O







0.003
Inventive steel



P




0.02



Inventive steel



Q








Inventive steel



R








Inventive steel



S








Comparative steel



T








Comparative steel



U








Inventive steel



V








Inventive steel



W








Inventive steel
























TABLE 2









Cold rolling

Cooling
Rolling
Pickling
Second















Heat treatment step
step
First heating step
step
step
step
heating
























Dew
Heating
Holding
Rolling

Dew
Heating
Holding
Cooling
Rolling
Weight
step




H2
point
temperature
time
reduction
H2
point
temperature
time
temperature
reduction
loss
H2


No.
Steel
(%)
(° C.)
(° C.)
(s)
(%)
(%)
(° C.)
(° C.)
(s)
(° C.)
(%)
(g/m2)
(%)





1
A




50
8.0
−40
850
150
100
0.5
0.05
5.0


2
A




50
8.0
−40
850
150
100
0.9
0.07
5.0


3
A




50
5.0
−35
760
200
50
0.7
0.08
10.0


4
A




50
10.0
−40
870
200
50
0.7
0.05
10.0


5
A




50
8.0
−45
830
100
50
0.9
0.08
10.0


6
A




50
5.0
−35
830
150
50
1.8
0.12
8.0


7
A




50
10.0
−35
790
150
100
0.4
0.06
10.0


8
A




50
10.0
−35
830
150
100
1.2
0.48
10.0


9
A




50
8.0
−40
860
150
100
0.7
0.57
5.0


10
A




50
7.0
−15
810
150
100
0.7
0.19
15.0


11
B




50
10.0
−35
820
150
100
0.5
0.05
5.0


12
B




50
10.0
−30
810
150
100
0.9
0.12
5.0


13
B




50
5.0
−40
800
500
100
0.7
2.38
15.0


14
B




50
5.0
−15
850
150
100
1.1
1.44
10.0


15
B




50
5.0
−20
830
250
100
1.4
1.08
10.0


16
B




50
15.0
−35
820
100
100
1.1
4.5
5.0


17
B




50
10.0
−35
810
100
100
0.8
0.03
15.0


18
B




50
10.0
−30
820
150
100
0.8
0.29
5.0


19
B




50
15.0
−40
850
100
50
0.7
0.17
10.0


20
B




50
10.0
−35
800
200
100
1.0
0.62
15.0


21
C




50
10.0
−40
790
150
50
0.5
0.05
5.0


22
C




50
10.0
−30
820
150
50
0.9
0.09
5.0


23
C




50
5.0
−30
830
50
50
0.7
0.18
10.0


24
C




50
5.0
−35
830
250
50
1.7
0.31
15.0


25
C




50
8.0
−40
860
100
50
0.9
0.28
15.0


26
C




50
10.0
−40
840
200
50
0.7
0.55
10.0


27
C




50
15.0
−30
790
150
50
1.1
0.07
8.0


28
C




50
10.0
−35
810
200
100
0.4
0.94
15.0


29
C




50
15.0
−30
820
100
100
1.1
0.18
5.0


30
C




50
5.0
−30
810
100
100
1.3
0.22
5.0


31
D




50
10.0
−35
820
150
100
0.5
0.05
5.0


32
D




50
10.0
−35
840
150
50
0.9
0.13
5.0


33
D




50
5.0
−45
820
200
100
1.1
0.54
10.0


34
D




50
10.0
−30
860
150
100
1.3
0.29
8.0


35
D




50
10.0
−35
800
200
50
0.5
0.11
10.0


36
D




50
5.0
−35
790
100
50
0.8
0.61
10.0


37
D




50
10.0
−30
830
100
50
0.8
0.22
5.0


38
D




50
10.0
−40
860
200
50
0.6
0.19
15.0


39
D




50
8.0
−35
850
150
50
0.7
0.06
10.0


40
D




50
5.0
−40
820
100
50
1.4
0.07
10.0
























Alloying











Galvanizing
treatment




Second heating step
step
step





















Dew
Heating
Holding
Al
Alloying
Tensile
Total








point
temperature
time
concentration
temperature
strength
elongation
Surface



No.
(° C.)
(° C.)
(s)
(%)
(° C.)
(MPa)
(%)
appearance
Adhesion
Product
Remarks







1
−35
800
100
0.193

823
22.4
A
A
GI
Inventive steel



2
−35
800
50
0.137
520
826
21.8
A
A
GA
Inventive steel



3
−40
750
100
0.134
540
796
23.4
B
A
GA
Inventive steel



4
−30
820
150
0.142
550
869
19.4
A
A
GA
Inventive steel



5
−35
790
200
0.195

994
16.8
A
A
GI
Inventive steel



6
−35
750
100
0.210

802
21.9
A
A
GI
Inventive steel



7
−40
750
200
0.138
520
795
21.5
A
A
GA
Inventive steel



8
−30
730
100
0.189

789
22.6
A
A
GI
Inventive steel



9
−45
850
50
0.192

1009
17.2
B
A
GI
Inventive steel



10
−10
740
100
0.129
480
879
20.4
A
A
GA
Inventive steel



11
−35
780
100
0.192

1123
13.8
A
A
GI
Inventive steel



12
−35
780
100
0.137
520
1205
11.9
A
A
GA
Inventive steel



13
−30
790
100
0.132
510
1193
12.3
B
A
GA
Inventive steel



14
−40
820
200
0.130
520
1238
10.6
A
A
GA
Inventive steel



15
−40
750
280
0.141
550
1241
10.8
A
A
GA
Inventive steel



16
−35
800
100
0.149

1187
12.4
B
A
GI
Inventive steel



17
−35
800
100
0.184

1192
12.1
A
A
GI
Inventive steel



18
−25
760
200
0.192

1225
11.1
A
A
GI
Inventive steel



19
−30
810
150
0.135
510
1216
11.5
A
A
GA
Inventive steel



20
−30
800
50
0.197

1187
12.3
A
A
GI
Inventive steel



21
−35
780
50
0.198

820
22.1
A
A
GI
Inventive steel



22
−35
780
80
0.137
520
894
20.4
A
A
GA
Inventive steel



23
−35
790
50
0.128
510
975
17.9
B
A
GA
Inventive steel



24
−30
800
150
0.187

1008
16.8
A
A
GI
Inventive steel



25
−40
720
200
0.191

986
17.2
A
A
GI
Inventive steel



26
−40
750
150
0.205

1012
16.1
A
A
GI
Inventive steel



27
−40
750
150
0.128
480
1034
16.2
A
A
GA
Inventive steel



28
−35
810
50
0.135
540
995
17.4
A
A
GA
Inventive steel



29
−40
800
120
0.193

892
20.5
A
A
GI
Inventive steel



30
−30
800
100
0.133
500
967
18.9
A
A
GA
Inventive steel



31
−35
790
50
0.148

1254
11.5
A
A
GI
Inventive steel



32
−35
780
100
0.137
520
1305
10.9
A
A
GA
Inventive steel



33
−30
760
50
0.139
520
1175
11.6
A
A
GA
Inventive steel



34
−30
800
150
0.130
500
1208
11.8
A
A
GA
Inventive steel



35
−35
830
100
0.184

1225
11.7
A
A
GI
Inventive steel



36
−40
780
30
0.189

1190
12.4
A
A
GI
Inventive steel



37
−40
830
50
0.130
510
1176
12.9
A
A
GA
Inventive steel



38
−30
800
150
0.192

1219
10.9
A
A
GI
Inventive steel



39
−35
820
100
0.194

1243
10.6
A
A
GI
Inventive steel



40
−35
790
100
0.129
520
1227
11.4
A
A
GA
Inventive steel







In the units of Table 2 to 6, “S” means “Sec.” and “g/mm2 means “gram/mm2




















TABLE 3









Cold rolling

Cooling
Rolling
Pickling
Second















Heat treamtent step
step
First heating step
step
step
step
heating
























Dew
Heating
Holding
Rolling

Dew
Heating
Holding
Cooling
Rolling
Weight
step




H2
point
temperature
time
reduction
H2
point
temperature
time
temperature
reduction
loss
H2


No.
Steel
(%)
(° C.)
(° C.)
(s)
(%)
(%)
(° C.)
(° C.)
(s)
(° C.)
(%)
(g/m2)
(%)





41
E




50
15.0
−30
810
100
50
0.9
0.08
5.0


42
E




50
5.0
−30
840
450
50
0.9
0.64
10.0


43
E




50
5.0
−35
820
150
100
1.2
0.29
10.0


44
E




50
10.0
−40
830
150
50
0.7
0.16
5.0


45
F




50
15.0
−30
850
100
100
0.8
0.84
5.0


46
F




50
10.0
−35
810
100
50
1.5
0.53
10.0


47
F




50
5.0
−35
820
100
50
1.5
0.14
15.0


48
F




50
15.0
−40
800
250
100
0.7
0.49
8.0


49
G




50
5.0
−40
850
150
50
0.8
0.34
5.0


50
G




50
5.0
−30
830
150
50
0.8
0.18
10.0


51
G




50
15.0
−35
840
200
100
1.4
0.41
10.0


52
G




50
10.0
−25
820
80
100
1.1
0.27
5.0


53
G




50
8.0
−35
860
50
50
1.2
1.22
15.0


54
H




50
7.0
−30
810
150
50
0.7
0.23
15.0


55
H




50
8.0
−30
860
150
100
0.9
0.64
10.0


56
H




50
10.0
−25
780
100
50
0.6
0.59
8.0


57
H




50
5.0
−35
800
250
100
1.1
2.37
8.0


58
H




50
5.0
−30
840
100
50
1.5
0.39
10.0


59
I




50
5.0
−30
820
100
100
1.4
0.34
5.0


60
I




50
10.0
−35
850
150
50
0.7
0.18
5.0


61
I




50
5.0
−35
850
80
100
0.9
0.09
15.0


62
J




50
15.0
−35
860
100
100
0.8
0.54
12.0


63
K




50
5.0
−40
800
200
100
0.7
0.52
15.0


64
K




50
10.0
−30
810
250
50
0.9
0.46
8.0


65
K




50
8.0
−40
800
300
100
1.1
0.27
8.0


66
L




50
12.0
−35
860
150
50
0.8
0.63
10.0


67
M




50
15.0
−35
830
150
100
1.0
0.18
15.0


68
N




50
10.0
−40
800
200
100
0.7
0.22
10.0


69
O




50
10.0
−40
810
100
50
1.3
0.24
10.0


70
P




50
10.0
−35
850
100
50
0.9
0.08
10.0


71
Q




50
10.0
−35
850
100
50
0.9
0.15
10.0


72
R




50
10.0
−35
850
50
50
0.8
0.08
15.0
























Alloying











Galvanizing
treatment




Second heating step
step
step





















Dew
Heating
Holding
Al
Alloying
Tensile
Total








point
temperature
time
concentration
temperature
strength
elongation
Surface



No.
(° C.)
(° C.)
(s)
(%)
(° C.)
(MPa)
(%)
appearance
Adhesion
Product
Remarks







41
−40
820
80
0.138
530
1286
10.5
A
A
GA
Inventive steel



42
−40
850
250
0.142
550
1255
11.1
A
A
GA
Inventive steel



43
−30
800
150
0.176

1219
10.8
A
A
GI
Inventive steel



44
−35
760
200
0.191

1194
11.8
A
A
GI
Inventive steel



45
−35
840
100
0.134
500
791
22.1
A
A
GA
Inventive steel



46
−35
750
150
0.189

807
21.9
A
A
GI
Inventive steel



47
−35
800
100
0.131
500
819
20.9
A
A
GA
Inventive steel



48
−35
780
50
0.195

821
21.8
A
A
GI
Inventive steel



49
−40
820
150
0.210

1108
12.8
A
A
GI
Inventive steel



50
−30
800
80
0.193

1216
10.8
A
A
GI
Inventive steel



51
−35
840
100
0.137
540
1109
11.8
A
A
GA
Inventive steel



52
−30
800
100
0.205

1201
11.1
A
A
GI
Inventive steel



53
−35
790
150
0.133
560
1194
12.3
A
A
GA
Inventive steel



54
−40
800
100
0.197

1322
10.7
A
A
GI
Inventive steel



55
−30
840
100
0.132
550
1279
10.4
A
A
GA
Inventive steel



56
−35
850
120
0.149

1249
10.5
A
A
GI
Inventive steel



57
−35
760
200
0.130
550
1208
10.8
A
A
GA
Inventive steel



58
−40
820
100
0.127
540
1187
12.4
A
A
GA
Inventive steel



59
−30
760
150
0.194

806
21.2
A
A
GI
Inventive steel



60
−35
760
100
0.137
510
814
21.8
A
A
GA
Inventive steel



61
−35
810
50
0.137
520
791
22.4
A
A
GA
Inventive steel



62
−40
820
100
0.132
490
994
17.4
A
A
GA
Inventive steel



63
−30
760
150
0.189

895
20.5
A
A
GI
Inventive steel



64
−30
840
50
0.189

905
17.8
A
A
GI
Inventive steel



65
−25
750
100
0.132
490
924
16.5
A
A
GA
Inventive steel



66
−35
850
50
0.138
490
791
20.8
A
A
GA
Inventive steel



67
−30
800
100
0.178

1004
17.2
A
A
GI
Inventive steel



68
−30
830
50
0.124
480
1197
12.2
A
A
GA
Inventive steel



69
−40
800
100
0.195

995
17.4
A
A
GI
Inventive steel



70
−35
820
150
0.190

1254
11.2
A
A
GI
Inventive steel



71
−35
820
150
0.190

1207
11.8
A
A
GI
Inventive steel



72
−35
800
150
0.137
540
880
20.8
A
A
GA
Inventive steel
























TABLE 4









Cold rolling

Cooling
Rolling
Pickling
Second















Heat treatment step
step
First heating step
step
step
step
heating
























Dew
Heating
Holding
Rolling

Dew
Heating
Holding
Cooling
Rolling
Weight
step




H2
point
temperature
time
reduction
H2
point
temperature
time
temperature
reduction
loss
H2


No.
Steel
(%)
(° C.)
(° C.)
(s)
(%)
(%)
(° C.)
(° C.)
(s)
(° C.)
(%)
(g/m2)
(%)





73
A




50
10.0
−30
790
50
100
3.4
3.82
5.0


74
A




50
5.0
−30
840
150
100
3.5
4.35
5.0


75
A




50
8.0
−35
850
150
50
0.1
0.05
10.0


76
A




50
10.0
−35
800
100
50
0.0
0.11
8.0


77
A




50
5.0
−35
720
100
50
0.5
0.05
10.0


78
A




50
5.0
−40
850
50
100
0.9
0.08
10.0


79
B




50
5.0
−40
830
200
50
1.3
0.06
5.0


80
B




50
5.0
−40
860
200
100
2.9
0.18
15.0


81
B




50
10.0
−35
850
200
100
0.0
0.12
15.0


82
B




50
8.0
−35
820
5
100
0.7
0.28
10.0


83
B




50
10.0
−35
800
150
100
0.7
2.18
8.0


84
B




50
10.0
−40
900
50
50
0.5
3.55
10.0


85
C




50
5.0
−35
790
150
100
3.0
1.07
10.0


86
C




50
5.0
−35
850
150
50
0.1
0.54
5.0


87
C




50
15.0
−40
800
120
100
1.2
6.8 
5.0


88
C




50
5.0
−30
820
80
100
0.9
0.27
15.0


89
C




50
5.0
−30
850
50
50
0.9

15.0


90
C




50
10.0
−35
700
50
100
0.8
0.46
8.0


91
D




50
10.0
−50
850
100
50
1.5
0.61
5.0


92
D




50
10.0
−40
850
100
50
0.7
0.49
8.0


93
D




50
8.0
−40
830
100
50
0.7
1.14
8.0


94
D




50
5.0
−30
790
80
50
3.1
2.05
10.0


95
D




50
5.0
−35
800
150
50
0.0
1.11
10.0


96
D




50
10.0
−40
860
200
100
0.5
10.1 
10.0


97
E




50
15.0
−25
820
5
100
0.9
0.87
15.0


98
F




50
15.0
−30
800
50
100
0.9
2.12
5.0


99
Q




50
10.0
−50
800
100
50
0.4
1.25
5.0


100
R




50
5.0
−35
710
5
50
0.5
0.84
5.0


101
S




50
10.0
−30
800
100
100
0.6
0.50
5.0


102
S




50
10.0
−30
850
100
50
0.9
1.60
5.0


103
T




50
10.0
−35
860
150
100
1.4
1.20
5.0


104
T




50
10.0
−40
820
150
100
0.7
0.90
5.0


























Alloying












Galvanizing
treatment





Second heating step
step
step





















Dew
Heating
Holding
Al
Alloying
Tensile
Total








point
temperature
time
concentration
temperature
strength
elongation
Surface



No.
(° C.)
(° C.)
(s)
(%)
(° C.)
(MPa)
(%)
appearance
Adhesion
Product
Remarks







73
−30
800
100
0.195

991
17.4
B
C
GI
Comparative steel



74
−35
820
100
0.134
490
1004
16.8
B
C
GA
Comparative steel



75
−35
800
150
0.190

1016
16.5
A
C
GI
Comparative steel



76
−35
850
150
0.139
520
994
17.2
A
C
GA
Comparative steel



77
−30
820
100
0.141
500
1010
16.6
C
C
GA
Comparative steel



78
−30
890
200
0.139
540
1021
16.4
C
C
GA
Comparative steel



79
−25
820
600
0.189

1218
13.2
C
C
GI
Comparative steel



80
−35
800
50
0.134
520
1352
11.1
B
C
GA
Comparative steel



81
−35
820
100
0.190

1109
14.8
A
C
GI
Comparative steel



82
−30
750
100
0.190

1194
12.8
C
C
GI
Comparative steel



83
5
750
100
0.137
520
1212
11.6
C
C
GA
Comparative steel



84
−40
830
200
0.131
530
1204
11.8
C
C
GA
Comparative steel



85
−40
750
50
0.185

809
22.1
B
C
GI
Comparative steel



86
−30
800
50
0.126
490
795
23.4
B
C
GA
Comparative steel



87
−35
760
100
0.129
480
821
21.9
C
C
GA
Comparative steel



88
−35
650
100
0.137
500
817
22.8
C
C
GA
Comparative steel



89
−35
800
100
0.191

806
21.8
C
C
GI
Comparative steel



90
−30
850
150
0.189

824
21.9
C
C
GI
Comparative steel



91
−10
750
50
0.134
530
1207
12.1
C
C
GA
Comparative steel



92
5
800
50
0.129
560
1191
13.4
C
C
GA
Comparative steel



93
−20
900
100
0.148

1004
17.4
C
C
GI
Comparative steel



94
−30
750
100
0130
540
1018
17.1
A
C
GA
Comparative steel



95
−30
800
100
0.181

1027
17.5
A
C
GI
Comparative steel



96
−35
850
200
0.213

1128
14.9
C
C
GI
Comparative steel



97
−35
800
150
0.139
510
1197
13.8
C
C
GA
Comparative steel



98
−20
840
500
0.182

811
21.5
C
C
GI
Comparative steel



99
−35
820
100
0.135
520
1244
11.9
C
C
GA
Comparative steel



100
−30
850
100
0.132
540
971
18.6
C
C
GA
Comparative steel



101
−30
790
200
0.192

812
22.1
B
C
GI
Comparative steel



102
−30
820
100
0.130
500
792
21.5
C
C
GA
Comparative steel



103
−30
800
50
0.189

997
17.5
C
C
GI
Comparative steel



104
−30
800
100
0.132
560
957
17.9
C
C
GA
Comparative steel
























TABLE 5









Cold rolling

Cooling
Rolling
Pickling
Second















Heat treatment step
step
First heating step
step
step
step
heating
























Dew
Heating
Holding
Rolling

Dew
Heating
Holding
Cooling
Rolling
Weight
step




H2
point
temperature
time
reduction
H2
point
temperature
time
temperature
reduction
loss
H2


No.
Steel
(%)
(° C.)
(° C.)
(s)
(%)
(%)
(° C.)
(° C.)
(s)
(° C.)
(%)
(g/m2)
(%)





105
A
5
−30
690
18000
50
8.0
−40
850
150
100
0.5
0.05
5.0


106
A
5
−20
640
18000
50
8.0
−40
850
150
100
0.5
0.05
5.0


107
A
10
−30
720
3600
50
8.0
−40
850
150
100
0.5
0.05
5.0


108
A
10
−30
680
7200
50
8.0
−40
850
150
100
0.9
0.07
5.0


109
A
5
−30
750
15000
80
8.0
−40
850
150
100
0.9
0.07
5.0


110
A
5
−30
700
20000
35
8.0
−40
850
150
100
0.9
0.07
5.0


111
A
5
−30
800
7200
50
8.0
−40
850
150
100
0.9
0.07
5.0


112
B
5
−20
680
18000
50
10.0
−35
820
150
100
0.5
0.05
5.0


113
B
5
−30
690
11000
65
10.0
−35
820
150
100
0.5
0.05
5.0


114
B
5
−30
650
7200
50
10.0
−35
820
150
100
0.5
0.05
5.0


115
B
5
−30
680
18000
50
10.0
−30
810
150
100
0.9
0.12
5.0


116
B
10
−30
680
1200
50
10.0
−30
810
150
100
0.9
0.12
5.0


117
B
5
−30
700
14400
45
10.0
−30
810
150
100
0.9
0.12
5.0


118
B
5
−40
780
11000
50
10.0
−30
810
150
100
0.9
0.12
5.0


119
C
5
−30
670
18000
50
10.0
−30
820
150
50
0.9
0.09
5.0


120
C
5
−30
700
7200
60
10.0
−30
820
150
50
0.9
0.09
5.0


121
C
5
−30
800
7200
45
10.0
−30
820
150
50
0.9
0.09
5.0


122
D
5
−20
820
15000
70
10.0
−35
820
150
100
0.5
0.05
5.0


123
D
5
−30
700
20000
40
10.0
−35
820
150
100
0.5
0.05
5.0


124
D
15
−30
690
18000
50
10.0
−35
820
150
100
0.5
0.05
5.0


125
E
5
−30
700
11000
50
5.0
−30
840
450
50
0.9
0.64
10.0


126
E
5
−30
740
10000
50
5.0
−35
820
150
100
1.2
0.29
10.0


127
F
5
0
740
15000
50
15.0
−30
850
100
100
0.8
0.84
5.0


128
F
5
−30
680
12000
50
10.0
−35
810
100
50
1.5
0.53
10.0


129
G
5
−30
690
12000
50
8.0
−35
860
50
50
1.2
1.22
15.0


130
H
5
−30
720
12000
50
7.0
−30
810
150
50
0.7
0.23
15.0


131
I
5
−20
720
12000
50
5.0
−30
820
100
100
1.4
0.34
5.0


132
J
5
−30
700
12000
50
15.0
−35
860
100
100
0.8
0.54
12.0


133
K
5
−30
750
12000
50
5.0
−40
800
200
100
0.7
0.52
15.0


134
L
5
−30
720
12000
50
12.0
−35
860
150
50
0.8
0.63
10.0


135
M
5
−30
690
12000
50
15.0
−35
830
150
100
1.0
0.18
15.0


136
N
5
−30
650
12000
50
10.0
−40
800
200
100
0.7
0.22
10.0


137
O
5
−30
700
12000
50
10.0
−40
810
100
50
1.3
0.24
10.0


138
P
5
−30
700
12000
50
10.0
−35
850
100
50
0.9
0.08
10.0


139
Q
5
−30
720
12000
50
10.0
−35
850
100
50
0.9
0.15
10.0


140
R
5
−30
690
12000
50
10.0
−35
850
50
50
0.8
0.08
15.0


141
U
5
−30


50
5.0
−40
780
150
100
0.5
0.09
10.0


142
U
10
−30
700
3600
70
5.0
−40
780
150
100
0.5
0.09
10.0


143
U
5
−40
670
18000
50
5.0
−40
780
150
100
0.5
0.09
10.0


144
U
5
−30
670
18000
50
5.0
−40
780
150
100
0.5
0.09
10.0


145
U
15
−10
670
18000
50
5.0
−40
780
150
100
0.5
0.09
10.0


146
U
5
−30
690
8000
40
5.0
−40
780
150
100
0.5
0.09
10.0


147
U
5
−30
760
21000
50
5.0
−40
780
150
100
0.5
0.09
10.0


148
V
5
−30


50
5.0
−35
790
100
100
0.4
0.14
15.0


149
V
5
−30
690
3600
50
5.0
−35
790
100
100
0.4
0.14
15.0


150
V
5
−10
740
10000
50
10.0
−35
810
50
80
0.4
0.12
15.0


151
V
10
−30
740
10000
50
10.0
−35
810
50
80
0.4
0.12
15.0


152
V
5
−30
700
18000
50
10.0
−40
810
50
80
0.4
0.11
5.0


153
V
5
−30
690
21000
50
10.0
−35
810
50
80
0.4
0.07
15.0


154
W
5
−30


50
10.0
−40
780
150
100
0.7
0.08
10.0


155
W
5
−30
690
3600
50
10.0
−40
780
150
100
0.7
0.08
10.0


156
W
5
−10
740
9000
50
10.0
−40
780
150
100
0.7
0.08
10.0


157
W
10
−30
700
18000
50
10.0
−40
780
150
100
0.7
0.08
10.0


158
W
5
−40
690
21000
50
10.0
−40
780
150
100
0.7
0.08
10.0
























Alloying











Galvanizing
treatment




Second heating step
step
step





















Dew
Heating
Holding
Al
Alloying
Tensile
Total








point
temperature
time
concentration
temperature
strength
elongation
Surface



No.
(° C.)
(° C.)
(s)
(%)
(° C.)
(MPa)
(%)
appearance
Adhesion
Product
Remarks







105
−35
800
100
0.193

823
28.7
A
A
GI
Inventive steel



106
−35
800
100
0.193

835
27.5
A
A
GI
Inventive steel



107
−35
800
100
0.193

830
28.4
A
A
GI
Inventive steel



108
−35
800
50
0.137
520
826
27.6
A
A
GA
Inventive steel



109
−35
800
50
0.137
520
821
28.7
A
A
GA
Inventive steel



110
−35
800
50
0.137
520
830
28.1
A
A
GA
Inventive steel



111
−35
800
50
0.137
520
824
28.3
A
A
GA
Inventive steel



112
−35
780
100
0.192

1123
16.7
A
A
GI
Inventive steel



113
−35
780
100
0.192

1134
16.4
A
A
GI
Inventive steel



114
−35
780
100
0.192

1129
16.4
A
A
GI
Inventive steel



115
−35
780
100
0.137
520
1205
15.4
A
A
GA
Inventive steel



116
−35
780
100
0.137
520
1198
15.1
A
A
GA
Inventive steel



117
−35
780
100
0.137
520
1208
15.2
A
A
GA
Inventive steel



118
−35
780
100
0.137
520
1195
15.6
A
A
GA
Inventive steel



119
−35
780
80
0.137
520
894
26.4
A
A
GA
Inventive steel



120
−35
780
80
0.137
520
859
26.7
A
A
GA
Inventive steel



121
−35
780
80
0.137
520
873
25.8
A
A
GA
Inventive steel



122
−35
790
50
0.148

1254
13.4
A
A
GI
Inventive steel



123
−35
790
50
0.148

1249
13.3
A
A
GI
Inventive steel



124
−35
790
50
0.148

1257
13.1
A
A
GI
Inventive steel



125
−40
850
250
0.142
550
1255
13.5
A
A
GA
Inventive steel



126
−30
800
150
0.176

1219
13.7
A
A
GI
Inventive steel



127
−35
840
100
0.134
500
791
29.4
A
A
GA
Inventive steel



128
−35
750
150
0.189

807
29.8
A
A
GI
Inventive steel



129
−35
790
150
0.133
560
1194
13.4
A
A
GA
Inventive steel



130
−40
800
100
0.197

1322
12.8
A
A
GI
Inventive steel



131
−30
760
150
0.194

806
28.4
A
A
GI
Inventive steel



132
−40
820
100
0.132
490
994
22.4
A
A
GA
Inventive steel



133
−30
760
150
0.189

895
24.6
A
A
GI
Inventive steel



134
−35
850
50
0.138
490
791
28.5
A
A
GA
Inventive steel



135
−30
800
100
0.178

1004
21.9
A
A
GI
Inventive steel



136
−30
830
50
0.124
480
1197
15.2
A
A
GA
Inventive steel



137
−40
800
100
0.195

995
21.7
A
A
GI
Inventive steel



138
−35
820
150
0.190

1254
12.8
A
A
GI
Inventive steel



139
−35
820
150
0.190

1207
13.1
A
A
GI
Inventive steel



140
−35
800
150
0.137
540
880
28.6
A
A
GA
Inventive steel



141
−40
740
100
0.134
520
1158
14.4
A
A
GA
Inventive steel



142
−30
740
100
0.134
520
1028
24.1
A
A
GA
Inventive steel



143
−50
740
100
0.134
520
1036
23.4
A
A
GA
Inventive steel



144
−40
730
150
0.189

1008
25.2
A
A
GI
Inventive steel



145
−40
730
150
0.189

1016
24.7
A
A
GI
Inventive steel



146
−40
740
100
0.134
520
1035
23.7
A
A
GA
Inventive steel



147
−35
740
100
0.134
520
1024
23.8
A
A
GA
Inventive steel



148
−45
800
100
0.132
500
1236
13.5
A
A
GA
Inventive steel



149
−50
800
100
0.132
500
1186
15.2
A
A
GA
Inventive steel



150
−40
730
50
0.141
540
1058
24.5
A
A
GA
Inventive steel



151
−40
730
50
0.194

1067
24.1
A
A
GI
Inventive steel



152
−45
740
50
0.137
500
1071
23.5
A
A
GA
Inventive steel



153
−50
800
150
0.135
500
1179
16.1
A
A
GA
Inventive steel



154
−40
730
100
0.131
510
991
15.4
A
A
GA
Inventive steel



155
−40
730
100
0.131
510
1002
24.9
A
A
GA
Inventive steel



156
−50
750
150
0.138
520
1032
20.5
A
A
GA
Inventive steel



157
−40
750
150
0.137
520
1028
19.8
A
A
GA
Inventive steel



158
−40
750
150
0.132
500
1038
21.2
A
A
GA
Inventive steel
























TABLE 6









Cold rolling

Cooling
Rolling
Pickling
Second















Heat treatment step
step
First heating step
step
step
step
heating
























Dew
Heating
Holding
Rolling

Dew
Heating
Holding
Cooling
Rolling
Weight
step




H2
point
temperature
time
reduction
H2
point
temperature
time
temperature
reduction
loss
H2


No.
Steel
(%)
(° C.)
(° C.)
(s)
(%)
(%)
(° C.)
(° C.)
(s)
(° C.)
(%)
(g/m2)
(%)





159
U
0.01
−30
690
18000
50
5.0
−35
790
100
100
0.4
0.14
15.0


160
U
5
20
670
18000
50
5.0
−40
780
150
100
0.5
0.08
10.0


161
U
0.01
−10
760
21000
50
5.0
−40
780
150
100
0.5
0.09
10.0


162
U
5
30
700
3600
70
5.0
−40
780
150
100
0.5
0.09
10.0


163
V
5
30
690
3600
50
5.0
−35
790
100
100
0.4
0.14
15.0


164
V
0.01
−30
740
10000
50
10.0
−35
810
50
80
0.4
0.12
15.0


165
V
15
25
700
18000
50
10.0
−40
810
50
80
0.4
0.11
5.0


166
V
5
20
740
10000
50
10.0
−35
810
50
80
0.4
0.12
15.0


167
W
0.01
−30
690
3600
50
10.0
−40
780
150
100
0.7
0.08
10.0


168
W
5
30
740
9000
50
10.0
−40
780
150
100
0.7
0.08
10.0


169
W
0.01
−40
690
21000
50
10.0
−40
780
150
100
0.7
0.08
10.0


170
W
5
20
700
18000
50
10.0
−40
780
150
100
0.7
0.08
10.0
























Alloying











Galvanizing
treatment




Second heating step
step
step





















Dew
Heating
Holding
Al
Alloying
Tensile
Total








point
temperature
time
concentration
temperature
strength
elongation
Surface



No.
(° C.)
(° C.)
(s)
(%)
(° C.)
(MPa)
(%)
appearance
Adhesion
Product
Remarks







159
−50
800
100
0.132
500
1186
15.1
A
A
GA
Inventive steel



160
−40
730
150
0.189

1008
18.9
A
A
GI
Inventive steel



161
−35
740
100
0.134
520
1024
19.2
A
A
GA
Inventive steel



162
−30
740
100
0.134
520
1028
19.5
A
A
GA
Inventive steel



163
−50
800
100
0.132
500
1186
15.0
A
A
GA
Inventive steel



164
−40
730
50
0.141
540
1058
13.9
A
A
GA
Inventive steel



165
−45
740
50
0.137
500
1071
14.9
A
A
GA
Inventive steel



166
−40
730
50
0.194

1067
14.9
A
A
GI
Inventive steel



167
−40
730
100
0.131
510
1002
17.9
A
A
GA
Inventive steel



168
−50
750
150
0.138
520
1032
15.8
A
A
GA
Inventive steel



169
−40
750
150
0.132
500
1038
15.9
A
A
GA
Inventive steel



170
−40
750
150
0.137
520
1028
15.1
A
A
GA
Inventive steel










High-strength galvanized steel sheets of examples of the present disclosure have a TS of 780 MPa or more and are excellent in surface appearance and coating adhesion. However, in comparative examples, one or more of surface appearance and coating adhesion are poor.


High-strength galvanized steel sheets of examples of the present disclosure are increased in total elongation by performing the heat treatment step. For example, in comparisons between the total elongation of Nos. 1 to 10, in which A steel is used, and the total elongation of Nos. 105 to 111, the total elongation of Nos. 105 to 111, in which the heat treatment step was performed, is high. For Nos. 141 to 147, in which U steel is used, the total elongation of Nos. 142 to 147, in which the heat treatment step was performed, is high.

Claims
  • 1. A method for manufacturing a high-strength galvanized steel sheet, the method comprising: a first heating step of holding a steel sheet in a temperature range of 750° C. to 880° C. for 20 sec. to 600 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −45° C. to −10° C., the steel sheet including: 0.040% to 0.500% C, by mass %,0.80% or less Si, by mass %,1.80% to 4.00% Mn, mass %,0.100% or less P, by mass %,0.0100% or less S, by mass %,0.100% or less Al, by mass %, and0.0100% or less N, by mass %,the remainder being Fe and inevitable impurities,a cooling step of cooling the steel sheet after the first heating step;a rolling step of rolling the steel sheet with a rolling reduction of 0.3% to 2.0% after the cooling step;a pickling step of pickling the steel sheet with a pickling weight loss of 0.02 gram/m2 to 5 gram/m2 in terms of Fe after the rolling step;a second heating step of holding the steel sheet in a temperature range of 720° C. to 860° C. for 20 sec. to 300 sec. in an atmosphere having an H2 concentration of 0.05% to 25.0% by volume and a dew point of −10° C. or lower after the pickling step; anda galvanizing step of galvanizing the steel sheet after the second heating step.
  • 2. The method for manufacturing the high-strength galvanized steel sheet according to claim 1, wherein the steel sheet further includes at least one element selected from 0.010% to 0.100% Ti, by mass %, 0.010% to 0.100% Nb, by mass %, and 0.0001% to 0.0050% B, by mass %.
  • 3. The method for manufacturing the high-strength galvanized steel sheet according to claim 1, wherein the steel sheet further includes at least one element selected from 0.01% to 0.50% Mo, by mass %, 0.30% or less Cr, by mass %, 0.50% or less Ni, by mass %, 1.00% or less Cu, by mass %, 0.500% or less V, by mass %, 0.10% or less Sb, by mass %, 0.10% or less Sn, by mass %, 0.0100% or less Ca, by mass %, and 0.010% or less of a REM, by mass %.
  • 4. The method for manufacturing the high-strength galvanized steel sheet according to claim 2, wherein the steel sheet further includes at least one element selected from 0.01% to 0.50% Mo, by mass %, 0.30% or less Cr, by mass %, 0.50% or less Ni, by mass %, 1.00% or less Cu, by mass %, 0.500% or less V, by mass %, 0.10% or less Sb, by mass %, 0.10% or less Sn, by mass %, 0.0100% or less Ca, by mass %, and 0.010% or less of a REM, by mass %.
  • 5. The method for manufacturing the high-strength galvanized steel sheet according to claim 1, wherein in the manufacture of the steel sheet subjected to the first heating step, after the steel sheet is hot-rolled and is then descaled by a pickling, a heat treatment step is performed in such a manner that the steel sheet is held at a temperature of 600° C. or higher for 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the steel sheet is exposed to the atmosphere.
  • 6. The method for manufacturing the high-strength galvanized steel sheet according to claim 2, wherein in the manufacture of the steel sheet subjected to the first heating step, after the steel sheet is hot-rolled and is then descaled by a pickling, a heat treatment step is performed in such a manner that the steel sheet is held at a temperature of 600° C. or higher for 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the steel sheet is exposed to the atmosphere.
  • 7. The method for manufacturing the high-strength galvanized steel sheet according to claim 3, wherein in the manufacture of the steel sheet subjected to the first heating step, after the steel sheet is hot-rolled and is then descaled by a pickling, a heat treatment step is performed in such a manner that the steel sheet is held at a temperature of 600° C. or higher for 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the steel sheet is exposed to the atmosphere.
  • 8. The method for manufacturing the high-strength galvanized steel sheet according to claim 4, wherein in the manufacture of the steel sheet subjected to the first heating step, after the steel sheet is hot-rolled and is then descaled by a pickling, a heat treatment step is performed in such a manner that the steel sheet is held at a temperature of 600° C. or higher for 600 sec. to 21,600 sec. in an atmosphere having an H2 concentration of 1.0% to 25.0% by volume and a dew point of 10° C. or lower in such a state that no surface of the steel sheet is exposed to the atmosphere.
  • 9. The method for manufacturing the high-strength galvanized steel sheet according to any one of claims 1-8, further comprising an alloying treatment step of alloying the steel sheet after the galvanizing step.
Priority Claims (1)
Number Date Country Kind
2014-136461 Jul 2014 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2015/002976 6/15/2015 WO 00