PLATED STEEL
20230407448 ยท 2023-12-21
Inventors
Cpc classification
B32B15/011
PERFORMING OPERATIONS; TRANSPORTING
C21D1/74
CHEMISTRY; METALLURGY
C21D9/00
CHEMISTRY; METALLURGY
B32B15/012
PERFORMING OPERATIONS; TRANSPORTING
C22C21/06
CHEMISTRY; METALLURGY
C23C30/00
CHEMISTRY; METALLURGY
C21D1/18
CHEMISTRY; METALLURGY
International classification
C21D1/74
CHEMISTRY; METALLURGY
Abstract
This plated steel includes: a steel; and a plating layer formed on the steel, in which the plating layer contains, as a chemical composition, by mass %, Zn: 1.0% to 30.0%, Mg: 0% to 10.0%, Si: 0.05% to 10.0%, Fe: 0 to 10.0%, 0% to 5.00% in total of one or two or more selected from Ca: 0% to 3.00%, Sb: 0% to 0.50%, Pb: 0% to 0.50%, Sr: 0% to 0.50%, Sn: 0% to 1.00%, Cu: 0% to 1.00%, Ti: 0% to 1.00%, Ni: 0% to 1.00%, Mn: 0% to 1.00%, Cr: 0% to 1.00%, La: 0% to 1.00%, Ce: 0% to 1.00%, Zr: 0% to 1.00%, and Hf: 0% to 1.00%, and a remainder of Al and impurities, a microstructure of the plating layer contains an phase which is a solid solution of Al and Zn, and the phase contains a Zn phase having a grain size of 10 to 200 nm in a number density of 10/100 m.sup.2 or more.
Claims
1. A plated steel comprising: a steel; and a plating layer formed on the steel, wherein the plating layer contains, as a chemical composition, by mass %, Zn: 1.0% to 30.0%, Mg: 0% to 10.0%, Si: 0.05% to 10.0%, Fe: 0 to 10.0%, 0% to 5.00% in total of one or two or more selected from Ca: 0% to 3.00%, Sb: 0% to 0.50%, Pb: 0% to 0.50%, Sr: 0% to 0.50%, Sn: 0% to 1.00%, Cu: 0% to 1.00%, Ti: 0% to 1.00%, Ni: 0% to 1.00%, Mn: 0% to 1.00%, Cr: 0% to 1.00%, La: 0% to 1.00%, Ce: 0% to 1.00%, Zr: 0% to 1.00%, and Hf: 0% to 1.00%, and a remainder of Al and impurities, a microstructure of the plating layer contains an phase which is a solid solution of Al and Zn, and the phase contains a Zn phase having a grain size of 10 to 200 nm in a number density of 10/100 m.sup.2 or more.
2. The plated steel according to claim 1, wherein, in the chemical composition, by mass %, Mg: 0.5% to 10.0% is satisfied.
3. The plated steel according to claim 1, wherein, in the chemical composition, by mass %, Mg: 3.0% to 7.0%, and Zn: 7.0% to 18.0% are satisfied.
4. The plated steel according to claim 1, wherein an FeAl-based alloy layer is formed between the steel and the plating layer, and an average thickness of the FeAl-based alloy layer is 1.0 to 10.0 m.
5. The plated steel according to claim 1, wherein the Zn phase is contained in the phase in a number density of 30/100 m.sup.2 or more.
6. The plated steel according to claim 2, wherein an FeAl-based alloy layer is formed between the steel and the plating layer, and an average thickness of the FeAl-based alloy layer is 1.0 to 10.0 m.
7. The plated steel according to claim 2, wherein the Zn phase is contained in the phase in a number density of 30/100 m.sup.2 or more.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0029]
[0030]
EMBODIMENTS OF THE INVENTION
[0031] As shown in
[0032] In addition, the plating layer 2 has a predetermined chemical composition, a microstructure thereof has an phase 21, and the phase 21 contains a Zn phase 22 having a grain size of 10 to 200 nm in a number density of 10/100 m.sup.2 or more.
[0033] <Steel>
[0034] The plating layer 2 is important for the plated steel according to the present embodiment, and the kind of the steel 1 is not particularly limited. The kind of the steel 1 may be determined depending on an applicable product, a required strength, a sheet thickness, and the like. For example, a steel sheet such as a hot-rolled steel sheet described in JIS G 3131:2018 or a cold-rolled steel sheet described in JIS G 3141:2017 can be used.
[0035] <Plating Layer>
[0036] The plated steel according to the present embodiment includes the plating layer 2 on the steel 1 (for example, on a surface of the steel 1, or in a case where an FeAl-based alloy layer 3 is formed between the steel 1 and the plating layer 2, on a surface of the FeAl-based alloy layer 3). The plating layer 2 may be formed on one surface of the steel 1 or may be formed on both surfaces.
[0037] [Chemical Composition]
[0038] Regarding the chemical composition of the plating layer 2 included in the plated steel according to the present embodiment, the reason for limiting each element included will be described. % regarding the amount of each element is mass %.
[0039] Zn: 1.0% to 30.0%
[0040] Zn is an element that forms a Zn oxide on the surface of the steel by hot stamping. In a case where the Zn oxide is present on the surface of steel after hot stamping, chemical convertibility is improved. In addition, Zn is also an element that contributes to an improvement in corrosion resistance of the plating layer by an improvement in sacrificial protection properties. In order to obtain these effects, a Zn content is set to 1.0% or more. The Zn content is preferably 5.0% or more, and more preferably 7.0% or more.
[0041] On the other hand, when the Zn content exceeds 30.0%, it becomes difficult to suppress LME. Therefore, the Zn content is set to 30.0% or less. The Zn content is preferably 18.0% or less, and more preferably 15.0% or less.
[0042] Mg: 0% to 10.0%
[0043] Mg is an element having an effect of forming a ZnMg oxide together with Zn on the surface of the steel during hot stamping and enhancing the chemical convertibility of the steel after hot stamping. In terms of improving the chemical convertibility, the ZnMg oxide has a greater effect than the Zn oxide. Mg does not necessarily need to be contained, but may be contained in order to obtain the above-mentioned effects. In a case of sufficiently obtaining the above effects, a Mg content is preferably set to 0.5% or more. The Mg content is more preferably 3.0% or more.
[0044] On the other hand, when the Mg content exceeds 10.0%, there arises a manufacturing problem such as an increase in the amount of dross generated in a plating bath. Therefore, the Mg content is set to 10.0% or less. The Mg content is preferably 7.0% or less.
[0045] Si: 0.05% to 10.0%
[0046] Si is an element having an effect of suppressing the formation of an excessively thick alloy layer formed between the steel sheet and the plating layer in forming the plating layer on the steel sheet and enhancing the adhesion between the steel sheet and the plating layer. In addition, in a case where Si is included together with Mg, Si is also an element that forms a compound with Mg and contributes to an improvement in corrosion resistance after coating. In order to obtain the above effects, a Si content is set to 0.05% or more. The Si content is preferably 0.1% or more, and more preferably 1.0% or more.
[0047] On the other hand, when the Si content exceeds 10.0%, workability of the plating layer decreases. Therefore, the Si content is set to 10.0% or less.
[0048] Fe: 0% to 10.0%
[0049] When the plating layer is formed, Fe diffuses from the steel to the plating layer and is thus incorporated into the plating layer. When the Fe content is 10.0% or less, an adverse effect on properties of the plated steel according to the present embodiment is small. Therefore, an Fe content is set to 10.0% or less.
[0050] On the other hand, as described above, Fe is incorporated into the plating layer in a process of forming the plating layer. It is significantly costly to completely prevent the incorporation of Fe. Therefore, the Fe content may be set to 0.5% or more.
[0051] 0% to 5.00% in Total of One or Two or More Selected from Ca: 0% to 3.00%, Sb: 0% to 0.50%, Pb: 0% to 0.50%, Sr: 0% to 0.50%, Sn: 0% to 1.00%, Cu: 0% to 1.00%, Ti: 0% to 1.00%, Ni: 0% to 1.00%, Mn: 0% to 1.00%, Cr: 0% to 1.00%, La: 0% to 1.00%, Ce: 0% to 1.00%, Zr: 0% to 1.00%, and Hf: 0% to 1.00%
[0052] The plating layer of the plated steel according to the present embodiment includes one or two or more of Ca, Sb, Pb, Sr, Sn, Cu, Ti, Ni, Mn, Cr, La, Ce, Zr, and Hf as impurities or by intentional addition within the above ranges.
[0053] When a Ca content is high. Ca-based intermetallic compounds such as a CaZn.sub.11 phase are formed, and the corrosion resistance decreases. Therefore, the Ca content is set to 3.00% or less.
[0054] On the other hand, when Ca is contained in the plating layer, the amount of dross that is likely to be formed during plating as the Mg content increases, decreases, so that plating manufacturability is improved. Therefore, Ca may be contained in a range of 3.00% or less.
[0055] When a Sb content, a Sr content, or a Pb content are excessive, a viscosity of the plating bath increases, and it is often difficult to build the plating bath itself. In this case, a plated steel sheet having good plating properties cannot be manufactured. Therefore, the Sr content is set to 0.50% or less, the Sb content is set to 0.50% or less, and the Pb content is set to 0.50% or less.
[0056] When Sr, Sb, or Pb are contained in the plating layer, an external appearance of the plating layer changes, spangles are formed, and an improvement in metallic gloss is confirmed. Therefore, each of these elements may be contained in a range of 0.50% or less.
[0057] Sn is an element that increases a Mg elution rate in the plating layer containing Zn, Al, and Mg. When the elution rate of Mg increases, the corrosion resistance of a flat portion deteriorates. Therefore, a Sn content is set to 1.00% or less.
[0058] When a Cu content, a Ti content, a Ni content, or a Mn content are excessive, the viscosity of the plating bath increases, and it is often difficult to build the plating bath itself. In this case, a plated steel sheet having good plating properties cannot be manufactured. Therefore, the amount of each element is preferably set to 1.00% or less.
[0059] On the other hand, these elements are elements that contribute to the improvement in corrosion resistance. Therefore, these elements may be contained in a range of 1.00% or less.
[0060] When a La content or a Ce content are excessive, the viscosity of the plating bath increases, and it is often difficult to build the plating bath itself. In this case, a plated steel having good plating properties cannot be manufactured. Therefore, each of the La content and the Ce content is set to 1.00% or less.
[0061] When a Zr content or a Hf content are excessive, the corrosion resistance may decrease. Therefore, the Zr content and the Hf content are each set to 1.00% or less.
[0062] The chemical composition of the plating layer of the plated steel sheet according to the present embodiment has the above-mentioned chemical composition, and a remainder of Al and impurities. An Al content is 35.0% or more, preferably 50.0% or more, and more preferably 70.0% or more.
[0063] The chemical composition of the plating layer is measured by the following method.
[0064] First, an acid solution is obtained by peeling and dissolving the plating layer with an acid containing an inhibitor that suppresses corrosion of the base metal (steel). Next, the chemical composition of the plating layer can be obtained by measuring the obtained acid solution by an ICP analysis. The kind of the acid is not particularly limited as long as the acid is an acid capable of dissolving the plating layer. The chemical composition is measured as an average chemical composition.
[0065] [Microstructure]
[0066] The microstructure of the plating layer of the steel according to the present embodiment includes an phase which is a solid solution of Al and Zn, and in this phase, a Zn phase having a grain size of 10 to 200 nm is present in a number density of 10/100 m.sup.2 (10 m10 m) or more.
[0067] In a case where the plating layer has the above-described microstructure, the plating layer is excellent in chemical convertibility and in LME resistance during spot welding after hot stamping.
[0068] The present inventors consider the reason as follows.
[0069] In a case where the plated steel according to the present embodiment is heated for hot stamping, in the plating layer, the Zn phase dispersed in the plating layer, particularly in the phase, becomes a liquid phase. Then, the infiltration of oxygen into the plating layer is promoted by using this liquid phase as an infiltration path. As a result, a Zn oxide (in a case where the plating layer contains Mg, a ZnMg oxide is also included) is efficiently formed on the surface layer of the plating layer. In the steel after hot stamping, due to the formation of this Zn oxide (and/or the ZnMg oxide), the chemical convertibility is improved.
[0070] In addition, in a case where the Zn phase 22 is finely dispersed as described above, the oxidation of Zn is promoted during heating for the hot stamping, so that remaining of a metal Zn phase is suppressed in the steel after hot stamping. Since the metal Zn phase in the steel causes LME during spot welding, the plated steel according to the present embodiment in which the metal Zn phase is not present or is suppressed to a very small amount even if the metal Zn phase is present, is excellent in LME resistance during spot welding of the steel after hot stamping.
[0071] In a case where the number density of the Zn phase 22 in the phase 21 is low, the oxidation of Zn does not proceed sufficiently and Zn remains as a metal phase even after hot stamping, which causes LME to occur during spot welding. Therefore, the number density of the Zn phase 22 is set to 10 or more in an area of (10 m10 m). An upper limit of the number density does not need to be limited, but may be 70/100 m.sup.2 or less.
[0072] The reason for limiting the number density of the Zn phase having a grain size of 10 to 200 nm is that when a grain size of Zn is less than 10 nm, the oxidation promotion effect is insufficient, and when a grain size of Zn is more than 200 nm, the infiltration path of oxygen is localized, making it difficult to uniformly oxidize Zn in the plating layer.
[0073] An area ratio of the phase 21 in the plating layer is preferably 80.0% to 95.0%. When the area ratio of the phase 21 is less than 80.0%, there is concern that a coarse Zn phase is formed and causes LME during hot stamping. On the other hand, when the area ratio of the phase 21 exceeds 95.0%, there is concern that it becomes difficult to obtain sufficient chemical convertibility after heating for hot stamping.
[0074] In addition, in the microstructure of the plating layer 2 of the plated steel according to the present embodiment, examples of the remainder include a MgZn.sub.2 phase 23, a Mg.sub.2Zn.sub.3 phase, a MgZn phase, and a Mg.sub.2Si phase 24 which are Mg-based intermetallic compounds (IMC), a bulky Zn phase 25, a Si phase 26, and other intermetallic compound phases. From the viewpoint of improving the corrosion resistance, an area ratio of the Mg-based intermetallic compounds may be set to 2.0% or more.
[0075] In the present embodiment, an area ratio of each phase in the plating layer is obtained by the following method.
[0076] First, a prepared sample is cut into a size of 25 mm25 mm, is embedded in a resin, and is then polished to a mirror finish. Thereafter, a SEM-EDS element map image is obtained from a cross section of the plating layer in a thickness direction at a magnification of 1500-fold. The element map image is taken so that the entire thickness of the hot-dip plating layer is included in a visual field. Photographing positions are randomly selected. The photographing positions should not be reselected according to a calculation result of the area ratio.
[0077] Each microstructure and each phase are specified from the element map image. Then, by a computer image analysis, total cross-sectional areas of each microstructure and each phase appearing in the cross-sectional photograph of the entirety are measured, and this is divided by a cross-sectional area of the hot-dip plating layer appearing in the cross-sectional photograph of the entirety, whereby the area ratios of each microstructure and each phase are calculated.
[0078] In addition, the number density of the Zn phase having a grain size of 10 to 200 nm in the phase is obtained by the following method.
[0079] Similar to the case where the area ratio of each phase is obtained, a sample is embedded in a resin and is then polished to a mirror finish. Thereafter, a cross section of the plating layer is photographed at a magnification of 10,000-fold to obtain a SEM-BSE (backscattered electrons) image of the phase in the plating layer. Thereafter, the number of Zn phases having a grain size of 10 to 200 nm observed in the phase are counted, and the total number thereof is divided by the area of the phase in an observed visual field, thereby calculating the number density of the Zn phase having a grain size of 10 to 200 nm.
[0080] In the plated steel according to the present embodiment, as shown in
[0081] The alloy layer 3 is formed of an FeAl-based intermetallic compound (for example, an FeAl alloy layer or, in a case where the plating layer contains Si, an FeAlSi alloy layer, collectively referred to as an FeAl-based alloy layer).
[0082] The presence or absence and the thickness of the FeAl-based alloy layer can be obtained by measuring a thickness of the FeAl-based intermetallic compound from an element distribution image obtained from an EDS measurement.
[0083] The thickness of the plating layer 2 is not limited, but is preferably 7 to 50 m. Within this range, sufficient corrosion resistance can be obtained and sufficient workability can be secured.
[0084] By performing hot stamping on the plated steel according to the present embodiment described above, a hot stamped member excellent in chemical convertibility and LME resistance during spot welding can be obtained. Here, hot stamping conditions are not limited, and known conditions can be adopted.
[0085] <Manufacturing Method>
[0086] Next, a preferred manufacturing method of the plated steel according to the present embodiment will be described. The effects of the plated steel according to the present embodiment can be obtained as long as the plated steel has the above-described characteristics regardless of the manufacturing method. However, a method including the following steps is preferable because stable manufacturing can be achieved, the method including: [0087] (I) a plating step of immersing a steel in a plating bath to obtain a plated base sheet; [0088] (II) a cooling step of cooling the plated base sheet to a temperature range of 200 C. or lower; and [0089] (III) a holding step of reheating the plated base sheet after the cooling step, as necessary, and holding the plated base sheet in a temperature range of 100 C. to 200 C. for 100 seconds or longer.
[0090] [Plating Step]
[0091] In the plating step, a steel such as a steel sheet is immersed in a plating bath to form a plating layer on a surface of the steel to obtain a plated base sheet.
[0092] A composition of the plating layer to be formed can be assumed from a composition of the plating bath, so that the composition of the plating bath may be adjusted according to the desired chemical composition of the plating layer.
[0093] The steel provided for the plating step is not particularly limited, and for example, a hot-rolled steel sheet described in JIS G 3131:2018 or a cold-rolled steel sheet described in JIS G 3141:2017 can be used.
[0094] In addition, reduction annealing may be performed on the steel prior to the plating step. As annealing conditions, known conditions may be used. For example, the steel may be heated to 750 C. to 900 C. in a 5% H.sub.2N.sub.2 gas atmosphere having a dew point of 10 C. or higher and be held for 30 to 240 seconds.
[0095] [Cooling Step]
[0096] In the cooling step, the plated base sheet after the plating step (pulled up from the plating bath) is cooled after adjusting a plating adhesion amount with a wiping gas such as N.sub.2.
[0097] During the cooling, after pulling up from the plating bath, cooling (first cooling) is performed so that an average cooling rate down to 380 C. is 20 C./s or faster and slower than 40 C./s, and thereafter cooling to 200 C. or lower (second cooling) is performed so that the average cooling rate between 380 C., and 200 C. is 40 C./s or faster.
[0098] By setting the average cooling rate (of the first cooling) down to 380 C. to 20 C./s or faster and slower than 40 C./s. Zn is solid-solubilized in an phase. Accordingly, in the subsequent holding step, the formation of a Zn phase having a size of 10 to 200 nm in the phase is promoted. After pulling up from the plating bath, when the average cooling rate down to 380 C. is 40 C./s or faster, Zn cannot be sufficiently solid-solubilized. On the other hand, when the average cooling rate is slower than 20 C./s, Zn is precipitated at a high temperature, and a fine Zn phase cannot be precipitated in the phase in the subsequent holding step.
[0099] By the cooling to 200 C. or lower (second cooling) in which the average cooling rate in a temperature range of 380 C. to 200 C. is limited, the solid-solubilized Zn phase is cooled to a temperature range of 200 C. or lower in a state of being in a supersaturated state. Accordingly, the formation of the Zn phase having a size of 10 to 200 nm in the phase is promoted in the subsequent holding step. When the average cooling rate in this temperature range is slower than 40 C./s, a fine Zn phase cannot be precipitated in the phase in the subsequent holding step. The average cooling rate of the second cooling is preferably 60 C./s or faster, more preferably 70 C./s or faster, and even more preferably 80 C./s or faster.
[0100] A cooling start temperature (a temperature for switching from the first cooling to the second cooling) for cooling to 380 C. to 200 C. is preferably close to 380 C., but may be between 300 C. and 380 C. as long as the average cooling rate down to 200 C. is 40 C./s or faster.
[0101] [Holding Step]
[0102] In the holding step, the plated base sheet after the cooling step is held in a temperature range of 100 C. to 200 C. for 100 seconds or longer. During the holding, reheating may be performed as necessary, such as in a case where cooling to 100 C. or lower is performed in the cooling step.
[0103] After the above cooling, by performing holding in a temperature range of 100 C. to 200 C. for 100 seconds or longer, the Zn phase having a grain size of 10 to 200 nm is sufficiently precipitated in the phase.
[0104] In a case where a holding temperature is low or a holding time is short, a precipitation amount is insufficient.
[0105] On the other hand, in a case where the holding temperature is high, it becomes difficult to form the Zn phase having a size of 10 to 200 nm in the phase. In addition, since a long holding time causes the Zn phase precipitated in the phase to grow coarsely, the holding time is set to 1000 seconds or shorter.
[0106] In addition, the holding step is preferably performed within 5 minutes after the cooling step (the first cooling and the second cooling) is completed. The cooling step is completed is set to a time when the temperature of the steel reaches 200 C.
[0107] When the time from the completion of the cooling step to the start of the holding step exceeds 5 minutes, precipitation of an .sub.R phase, which is a metastable phase, starts, and it becomes difficult to satisfy the number density of the Zn phase in the phase.
[0108] The time from the completion of the cooling step to the start of the holding step is preferably within 1 minute.
EXAMPLES
[0109] As a steel sheet to be subjected to plating, a cold-rolled steel sheet (0.2% C-2.0% Si-2.3% Mn) having a sheet thickness of 1.6 mm was prepared.
[0110] After cutting this steel sheet into 100 mm200 mm, annealing and hot-dip plating were continuously performed using a batch-type hot-dip plating tester.
[0111] During the annealing, the annealing was performed at 860 C. for 120 seconds in an atmosphere containing 5% of H.sub.2 gas and a remainder consisting of N.sub.2 and having a dew point of 0 C. in a furnace having an oxygen concentration of 20 ppm or less.
[0112] After the annealing, the steel sheet was subjected to air cooling with N.sub.2 gas, and when a temperature of the steel sheet reached a bath temperature+20 C., the steel sheet was immersed in a plating bath having the bath temperature shown in Tables 1A and 1B for about 3 seconds.
[0113] A plated base sheet on which a plating layer was formed was cooled under the conditions shown in Tables 1A and 1B after adjusting a plating adhesion amount to 40 to 80 g/m.sup.2 with N.sub.2 gas. Thereafter, reheating was performed as necessary, and holding was performed under the conditions shown in Tables 1A and 1B. The temperature of the steel sheet was measured using a thermocouple spot-welded to a central part of the plated base sheet.
[0114] A composition of the formed plating layer was as shown in Tables 1A and 1B.
[0115] In addition, for an obtained plated steel, an area ratio and a number density of each phase contained in the plating layer were measured by the above-described methods.
[0116] In addition, for the obtained plated steel, the plated steel was inserted into a muffle furnace in an air atmosphere set to 900 C., was taken out after 4 minutes had passed, and was subjected to hot stamping in which pressing with a flat sheet die and rapid cooling were performed, thereby obtaining a hot stamped member.
[0117] In addition, spot welding was performed on the hot stamped member under the following conditions, a cross section of a welded part was observed, and LME resistance was evaluated with a length of a crack (LME crack).
[0118] That is, samples of 50 mm50 mm were collected from hot stamped members obtained by using plated steels Nos. 1 to 26 shown in the tables, and were overlapped on a commercially available hot-dip galvannealed steel sheet having the same size, and were subjected to spot welding by pressing an energizing electrode to cause a hitting angle (a difference between a direction perpendicular to the surface of the steel sheet and an axial direction of the electrode) to be 7 and a load to be 400 kgf and setting a current pattern to cause a nugget diameter to be 3.5t to 5.5t (t: sheet thickness). A DR6 type CuCr electrode according to the JIS standard was used as the energizing electrode.
[0119] After the spot welding, the steel sheet was cut in parallel to the direction in which the hitting angle was provided so that a sheet thickness direction cross section could be observed. After the cutting, the cross section of the welded part mirror-polished and finished by mechanical polishing and chemical polishing was observed with an optical microscope, and an LME crack length of an internal crack was measured.
[0120] Determination was made as follows depending on the presence or absence and a length of a crack, and excellent LME resistance was determined in a case of AA or A.
[0121] (Evaluation) [0122] AA: No crack [0123] A: Crack length 100 m or less [0124] B: Crack length more than 100 m and 300 m or less [0125] C: Crack length more than 300 m
[0126] In addition, a sample of 50 mm100 mm (sheet thickness) was collected from the hot stamped member, and this sample was subjected to a zinc phosphate treatment according to (SD5350 system: a standard manufactured by Nipponpaint Industrial Coatings Co., LTD.) to form a chemical conversion film.
[0127] By observing the surface of the plated steel sheet on which the chemical conversion film was formed by SEM, a ratio (area %) of lack of phosphate coating of the chemical conversion film was measured.
[0128] Determination was made as follows according to the ratio of lack of phosphate coating, and excellent chemical convertibility was determined in a case of AA or A. [0129] AA: 5% or less [0130] A: More than 5% and 10% or less [0131] B: More than 10% and 20% or less [0132] C: More than 20%
TABLE-US-00001 TABLE 1A Plating layer chemical composition (remainder: Al and impurities) Others Bath Zn Mg Si Fe Total temperature Classification No. (mass %) (mass %) (mass %) (mass %) Kind (mass %) ( C.) Comparative 1 0.0 1.0 8.0 10.0 0 700 Example Invention 2 1.0 3.0 1.5 9.4 Sb 0.01 700 Example Invention 3 5.0 3.0 8.0 9.5 Sn 0.1 700 Example Invention 4 5.0 0.5 2.0 10.0 0 690 Example Invention 5 7.0 1.5 8.0 7.3 Cr 0.001 690 Example Invention 6 7.0 0.5 8.0 8.4 Mn 0.001 670 Example Invention 7 10.0 5.0 8.0 5.1 Pb 0.02 670 Example Comparative 8 10.0 5.0 8.0 5.5 0 670 Example Invention 9 15.0 5.0 8.0 5.5 0 670 Example Invention 10 15.0 1.5 2.0 6.6 0 680 Example Invention 11 15.0 1.5 2.0 6.6 Ti 0.001 680 Example Invention 12 18.0 1.5 8.0 5.1 0 660 Example Invention 13 18.0 1.5 8.0 4.5 0 660 Example Invention 14 18.0 1.5 8.0 5.1 Ni 0.1 660 Example Invention 15 18.0 2.0 8.0 5.2 Cu 0.001 660 Example Cooling step Average Average cooling rate cooling rate Time between bath between Cooling until temperature 380 C. and stop holding Holding step and 380 C. 200 C. temperature step Temperature Time Classification No. ( C./s) ( C./s) ( C.) (min) ( C.) (s) Comparative 1 20 80 70 <1 100 500 Example Invention 2 20 80 70 <1 100 500 Example Invention 3 20 80 70 <1 100 500 Example Invention 4 20 80 70 <1 100 500 Example Invention 5 20 80 70 <1 100 500 Example Invention 6 20 80 70 <1 100 500 Example Invention 7 20 80 70 <1 100 500 Example Comparative 8 20 80 70 <1 Example Invention 9 20 40 70 <1 100 500 Example Invention 10 20 80 70 <1 100 500 Example Invention 11 20 80 70 <1 100 500 Example Invention 12 20 80 70 <1 100 500 Example Invention 13 20 80 70 5 100 500 Example Invention 14 20 80 70 <1 100 500 Example Invention 15 20 80 70 <1 100 500 Example
TABLE-US-00002 TABLE 1B Plating layer chemical composition (remainder: Al and impurities) Others Bath Zn Mg Si Fe Total temperature Classification No. (mass %) (mass %) (mass %) (mass %) Kind (mass %) ( C.) Invention 16 22.0 8.0 8.0 4.6 Zr 0.01 660 Example Invention 17 22.0 8.0 8.0 4.6 Hf 0.001 660 Example Invention 18 22.0 8.0 8.0 4.6 Sr 0.001 660 Example Invention 19 24.0 6.0 1.0 4.3 Ca 0.001 660 Example Invention 20 27.0 6.0 8.0 2.1 Ce: 0.0002 650 Example 0.0001, La: 0.0001 Invention 21 30.0 10.0 10.0 0.8 0 630 Example Comparative 22 35.0 1.0 7.0 3.1 0 670 Example Comparative 23 15.0 0.5 8.0 4.5 0 680 Example Comparative 24 15.0 1.5 8.0 4.5 0 680 Example Comparative 25 15.0 3.0 8.0 4.5 0 680 Example Comparative 26 15.0 2.0 8.0 4.5 0 680 Example Comparative 27 14.0 1.0 7.0 4.0 0 680 Example Comparative 28 15.0 1.0 7.5 4.0 0 680 Example Comparative 29 16.0 1.0 7.0 4.0 0 680 Example Comparative 30 15.0 1.0 7.0 3.5 0 680 Example Comparative 31 15.0 1.0 7.0 3.5 0 680 Example Cooling step Average Average cooling rate cooling rate Time between bath between Cooling until temperature 380 C. and stop holding Holding step and 380 C. 200 C. temperature step Temperature Time Classification No. ( C./s) ( C./s) ( C.) (min) ( C.) (s) Invention 16 20 80 70 <1 150 300 Example Invention 17 20 80 70 <1 150 300 Example Invention 18 20 80 70 <1 150 300 Example Invention 19 20 80 70 <1 150 300 Example Invention 20 20 80 70 <1 200 100 Example Invention 21 20 80 70 <1 100 500 Example Comparative 22 20 80 70 <1 100 500 Example Comparative 23 20 80 20 <1 20 500 Example Comparative 24 20 80 70 <1 290 500 Example Comparative 25 20 80 70 <1 290 10 Example Comparative 26 20 80 70 <1 290 10 Example Comparative 27 20 80 70 <1 100 1100 Example Comparative 28 60 80 70 <1 100 500 Example Comparative 29 10 80 70 <1 100 500 Example Comparative 30 30 30 70 <1 100 500 Example Comparative 31 20 80 205 <1 100 500 Example
TABLE-US-00003 TABLE 2A Average thickness Microstructure of plating layer of phase Mg-based Bulky Other FeAl- Number density of IMC in MgZn.sub.2 Mg.sub.2Si Zn Si intermetallic Thickness based Zn phase having total phase phase phase phase compounds of plating alloy Area grain size of 10 Area Area Area Area Area Area layer layer ratio to 200 mm ratio ratio ratio ratio ratio ratio LME Chemical No. (m) (m) (%) (/(10 m 10 m)) (%) (%) (%) (%) (%) (%) resistance convertibility 1 20 7.0 91.0 0 4.0 0.0 4.0 0.0 5.0 0.0 AA C 2 23 6.9 95.0 10 4.7 0.0 4.7 0.0 0.0 0.3 A AA 3 25 6.7 84.6 17 7.2 3.4 3.8 0.0 7.8 0.4 A AA 4 25 6.6 94.9 30 2.1 0.0 2.1 0.0 3.0 0.0 A A 5 50 6.4 88.0 35 4.5 0.0 4.5 0.0 7.0 0.5 AA A 6 26 6.6 90.3 48 3.0 0.0 3.0 0.0 6.4 0.3 AA A 7 25 5.8 87.9 59 8.9 4.9 4.0 0.0 3.0 0.2 AA AA 8 25 6.5 89.0 0 8.0 5.0 3.0 0.0 3.0 0.0 B AA 9 25 6.5 88.7 10 8.0 5.0 3.0 0.0 3.3 0.0 A A 10 26 5.6 92.3 53 5.1 5.1 0.0 0.0 2.0 0.6 AA A 11 27 5.6 92.3 55 5.0 5.0 0.0 0.0 2.1 0.6 AA A 12 23 6.2 86.9 55 5.1 0.0 5.1 3.0 5.0 0.0 A A 13 44 6.2 86.9 20 5.1 0.0 5.1 3.0 5.0 0.0 A A 14 31 6.2 87.3 55 5.0 0.0 5.0 3.0 4.7 0.0 A A 15 25 5.6 83.2 58 7.0 0.0 7.0 5.0 4.6 0.2 A A
TABLE-US-00004 TABLE 2B Average thickness Microstructure of plating layer of phase Mg-based Bulky Other FeAl- Number density of IMC in MgZn.sub.2 Mg.sub.2Si Zn Si intermetallic Thickness based Zn phase having total phase phase phase phase compounds of plating alloy Area grain size of 10 Area Area Area Area Area Area layer layer ratio to 200 mm ratio ratio ratio ratio ratio ratio LME Chemical No. (m) (m) (%) (/(10 m 10 m)) (%) (%) (%) (%) (%) (%) resistance convertibility 16 29 5.4 86.8 40 9.9 6.9 3.0 0.0 3.0 0.3 A A 17 25 5.4 86.9 37 10.2 7.2 3.0 0.0 2.6 0.3 A A 18 14 5.4 86.6 35 10.0 7.0 3.0 0.0 3.1 0.3 A A 19 25 5.3 85.9 43 11.7 11.7 0.0 0.0 2.0 0.4 A AA 20 10 2.9 84.0 10 12.4 9.7 2.7 0.0 3.5 0.1 A A 21 25 1.0 70.5 66 25.0 15.9 9.1 0.0 4.5 0.0 A A 22 22 5.0 75.0 55 6.0 4.0 2.0 11.0 8.0 0.0 C A 23 24 6.5 89.8 0 2.0 2.0 0.0 0.0 8.2 0.0 B A 24 25 6.4 89.6 0 5.4 5.0 0.4 0.0 5.0 0.0 B A 25 25 6.5 85.0 5 10.5 7.1 3.4 0.0 4.6 0.0 B A 26 24 6.0 86.0 5 6.7 5.0 1.7 0.0 7.3 0.0 B A 27 22 6.5 88.0 0 5.4 4.2 1.2 0.0 6.6 0.0 B A 28 24 6.1 89.4 0 4.2 3.4 0.8 0.0 6.4 0.0 B A 29 25 6.0 88.2 0 5.1 4.1 1.0 0.0 6.7 0.0 B A 30 28 6.2 89.3 0 4.6 3.5 1.1 0.0 6.1 0.0 B A 31 23 6.0 89.1 0 4.9 3.7 1.2 0.0 6.0 0.0 B A
[0133] As can be seen from Tables 1A to 2B, in Nos. 2 to 7 and Nos. 9 to 21 in which a predetermined chemical composition is provided, the microstructure of the plating layer contained an phase, and the phase contained a Zn phase having a grain size of 10 to 200 nm in a number density of 10/100 m or more, chemical convertibility after hot stamping and LME resistance during spot welding were excellent. Contrary to this, in Comparative Example Nos. 1, 8, and 22 to 31 in which one or more of the chemical composition of the plating layer and the number density of the Zn phase in the phase were outside of the range of the present invention, chemical convertibility after hot stamping or LME resistance during spot welding was inferior.
BRIEF DESCRIPTION OF THE REFERENCE SYMBOLS
[0134] 1: steel [0135] 2: plating layer [0136] 3: FeAl-based alloy layer [0137] 21: a phase [0138] 22: Zn phase [0139] 23: MgZn.sub.2 phase [0140] 24: Mg.sub.2Si phase [0141] 25: bulky Zn phase [0142] 26: Si phase