Method of production of an aluminum plated steel sheet having excellent corrosion resistance with respect to alcohol or mixed gasoline of same and appearance

Abstract

The present invention relates to aluminum plated steel sheet which does not require coating after plating and is high in production flexibility enabling application of conventional production processes as they are or exhibits excellent corrosion resistance to flex fuels and further is excellent in appearance and to fuel tanks characterized by being produced using the steel sheet. The Si, Mg, Ca, and Ti ingredients in the aluminum plating layer are defined and the cooling method after hot dip aluminum coating is controlled to make Mg.sub.2Si particles with a long axis of 10 μm or less and an aspect ratio of 1 to 3 finely disperse in the plating layer. Due to the Mg.sub.2Si particles, it is possible to give an excellent corrosion resistance to flex fuels and suppress the deterioration in appearance due to MgO.

Claims

1. A method of production of aluminum plated steel sheet which is excellent in corrosion resistance and appearance comprising dipping and running steel sheet in a hot dip aluminum coating bath comprised of, by mass %, Si: 2% to 11%, Mg: 3% to 9%, Ca: 0.1% to 5%, Ti: 0.008% to 0.05%, and a balance of Al and unavoidable impurities and having a temperature of 670° C. or more, cooling in a first stage cooling process up to a temperature range of 600 to 640° C. by a cooling rate of 25° C./sec or more, then further cooling in a second stage cooling process up to a temperature range of 550 to 590° C. by a cooling rate of 16° C./sec or more, wherein a plating layer of the aluminum plated steel sheet contains clumps of Mg.sub.2Si particles with a long axis of greater than 0 μm and 10 μm or less, and a ratio of a long axis and a short axis, an aspect ratio, of 1 to 3, the long axis and the aspect ratio being measured by examining the vertical cross-section of the plating layer.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a view which shows the relationship of the long axis of Mg.sub.2Si which is contained in the plating layer of the present invention and the corrosion resistance with respect to alcohol-containing gasoline.

(2) FIG. 2 is a view which shows the relationship of the aspect ratio of Mg.sub.2Si which is contained in the plating layer of the present invention and the corrosion resistance with respect to alcohol-containing gasoline.

DESCRIPTION OF EMBODIMENTS

(3) Below, embodiments of the present invention will be explained. Note that, in the present invention, the steel sheet which forms the base material is not particularly limited. This is because the corrosion resistance and appearance are determined by the aluminum plating layer on the surface of the steel sheet. First, the reasons for numerical limitation of the ratios of the hot dip coating ingredients of the present invention will be explained. Here, the % in the ingredients mean mass %.

(4) Si: 2 to 11%,

(5) In the present invention, it is important to add Mg and Si in combination and make Mg.sub.2Si sufficiently precipitate in the plating layer. Si is an ingredient which is required for reacting with Mg to cause precipitation of Mg.sub.2Si. To make Mg.sub.2Si precipitate enough to contribute to the improvement of the corrosion resistance with respect to flex fuels, the content of Si has to be 2% or more. From the viewpoint of obtaining a sufficient amount of precipitation of Mg.sub.2Si, the lower limit of Si is preferably 4%, more preferably 6%.

(6) On the other hand, to include Si in over 11%, the plating bath has to be raised in melting point. This is disadvantageous economically. If the Si further increases, the workability is degraded, so 11% was made the upper limit. From the viewpoint of the operating stability of the plating bath (prevention of shortening of life of equipment inside high temperature bath), the upper limit of Si is preferably 10%, more preferably 8%.

(7) Mg: 3 to 9%

(8) Mg is an ingredient which is necessary for reacting with Si to cause precipitation of Mg.sub.2Si in the plating layer. To make Mg.sub.2Si sufficiently precipitate to contribute to improvement of the corrosion resistance, the content of Mg has to be 3% or more. From the viewpoint of obtaining a sufficient amount of precipitation of Mg.sub.2Si, the lower limit of Mg is preferably made 4%, more preferably 5%.

(9) On the other hand, to include Mg in more than 9%, the melting point of the plating bath has to be raised. This is disadvantageous economically. Furthermore, if Mg increases, excessive Mg causes serious wrinkling due to the oxide film and degrades the plating appearance, so the upper limit was made 9%. From the viewpoint of making the appearance of the plating layer more beautiful, the upper limit of Mg is more preferably made 7%.

(10) Ca: 0.1 to 5%,

(11) Ca is stronger in oxidizing power than even Mg, so is added to suppress the formation of an Mg oxide film and improve the plating appearance. The content of Ca to obtain this effect depends on the content of Mg. If in the above range of content of Mg, 0.1% or more is necessary. From the viewpoint of appearance, the lower limit of Ca is preferably 0.12%, more preferably 0.15%.

(12) On the other hand, if adding Ca in over 5%, the plating bath becomes higher in melting point and the plating rises in viscosity—which becomes disadvantageous economically, so the upper limit was made 5%. From the viewpoint of the stability of the operation, the upper limit of the concentration of Ca is preferably made 4.8%, more preferably 4.2%.

(13) Ti: 0.005 to 0.05%

(14) Ti causes a peritectic reaction of L (liquid phase (“L” means liquid phase metal))+TiAl.sub.3.fwdarw.(Al) at 665° C. TiAl.sub.3 forms the nuclei for formation of Mg.sub.2Si in the process of solidification of the plating layer, so if making the TiAl.sub.3 finely disperse, Mg.sub.2Si also finely disperses. Further, since TiAl.sub.3 becomes nuclei for formation of Mg.sub.2Si, the Mg.sub.2Si which easily grows into a plate shape easily becomes particles. To make the TiAl.sub.3 finely disperse in a plating bath of 665° C. or more, the Ti content has to be 0.005% or more. From the viewpoint of securing fine dispersion of Mg.sub.2Si, the lower limit is preferably made 0.008%, more preferably 0.01%.

(15) On the other hand, if adding Ti in 0.05% or more, the liquidus temperature of the Al—Si—Mg—Ca alloy is raised, so this is not preferable. Further, the reduction of dross by oxidation of Ti and other aspects of operational stability are also impaired. If considering the stability in operation, the upper limit of the Ti content is preferably 0.02%, more preferably 0.018%.

(16) [Si mass %]≧0.6×[Mg mass %]

(17) To prevent Mg from remaining in the Al plating layer alone and make it Mg.sub.2Si to suppress an alcoholate reaction, it is preferable to make [Si mass %]≧0.6×[Mg mass %]. Mg.sub.2Si suppresses the first stage reaction in the alcoholate reaction which is shown by the following formulas. Due to this, dissolution of the main ingredient Al in the plating is inhibited and the role of sacrificial corrosion prevention is performed.
2Al+6(R—OH).fwdarw.2(Al(OR).sub.3)+3H.sub.2
2(Al(OR).sub.3)+6H.sub.2.fwdarw.2Al(OH).sub.3+6(R—H)

(18) Further, if [Si mass %] becomes less than 0.6×[Mg mass %], Mg remains, so there is no effect of addition of Ca and the plating appearance is degraded.

(19) 0.6×[Mg mass %]≧[Ca mass %]≧0.03×[Mg mass %]

(20) Ca is an element which suppresses the oxidation of the remaining Mg. Ca suppresses the formation of MgO, which causes wrinkles, and improves the plating appearance. If [Ca mass %] becomes less than 0.03×[Mg mass %], the effect of suppression is not sufficiently obtained. This is because the remaining Mg oxidizes and forms an oxide film which becomes the cause of wrinkling. On the other hand, if [Ca mass %] exceeds 0.6×[Mg mass %], the plating melting point becomes higher, which is not economical, and the effect of improvement of the plating appearance becomes saturated. Therefore, the range of content of Ca is preferably made the range of the following formula: 0.6×[Mg mass %][Ca mass %]0.03×[Mg mass %]

(21) Long Axis of Mg.sub.2Si of 10 μm or Less

(22) An Mg.sub.2Si intermetallic compound is hard and brittle. For this reason, if there is an intermetallic compound with a large long axis present, the plating layer itself remarkably falls in workability. For this reason, cracks occur in the press forming of steel sheet and corrosion easily occurs at the cracked parts. The inventors ran a draw bead test (sheet thickness reduction rate 20%) on plated steel sheet different in the long axis of Mg.sub.2Si while envisioning press forming of a fuel tank and discovered that if the long axis of the Mg.sub.2Si exceeds 10 μm, cracks easily occur. Therefore, the long axis of the Mg.sub.2Si which causes precipitation dispersed in the plating layer was made 10 μm or less.

(23) If making the long axis of Mg.sub.2Si even finer, a larger amount of the Mg.sub.2Si finely disperses, the plating layer becomes more uniform in structure, and the corrosion resistance is further improved. Further, even if the plating layer corrodes, the corrosion products do not become coarser and clogging of the filter of the fuel circulation system is remarkably reduced. For this reason, the upper limit of the long axis of Mg.sub.2Si is preferably made 8 μm or less, more preferably 6 μm or less, if possible 5 μm or less. FIG. 1 shows the relationship between the long axis of Mg.sub.2Si and the indicator of the corrosion resistance constituted by the amount of corrosion products. It is learned that if the long axis of Mg.sub.2Si becomes larger, the corrosion products increase (that is, the corrosion resistance deteriorates).

(24) On the other hand, the lower limit of Mg.sub.2Si is not particularly limited. However, if too small, the specific surface area becomes larger, the dissolution speed of Mg.sub.2Si becomes larger, and the lifetime becomes shorter. Further, to make the Mg.sub.2Si size smaller, the cooling rate after plating has to be remarkably raised. This is also disadvantageous economically. From this, as the lower limit of the long axis of Mg.sub.2Si, it is preferable to secure 1 μm or more. The lower limit of the long axis of Mg.sub.2Si is preferably 1.5 μm, if possible 2 μm or more.

(25) Aspect Ratio of Mg.sub.2Si: 1 to 3

(26) As explained above, Mg.sub.2Si is hard and brittle, so easily forms starting points of crack propagation at the time of press forming. In particular, if there are pin-shaped particles two-dimensionally (planarly) with a long axis longer than the short axis, they induce cracks in the plating layer and cause deterioration of the corrosion resistance. For this reason, a smaller aspect ratio (ratio of long axis and short axis of Mg.sub.2Si particles (long axis/short axis)) is preferable. Ideally, the particles are spherical in shape and the aspect ratio is 1. This is the lower limit. To prevent any detrimental effect from being recognized in the corrosion resistance, from the experiments of the inventors, 3 is made the upper limit of the aspect ratio. Of course, the smaller the aspect ratio, the better. Making it 2.4 or less is preferable.

(27) Ordinary Mg.sub.2Si intermetallic compounds are elliptically shaped plates (pieces) under ordinary solidification conditions (cooling by standing). To make the Mg.sub.2Si intermetallic compounds ones with small aspect ratios, that is, as close to spherical shapes as possible, it is necessary to control the cooling conditions. For this reason, the inventors discovered that to prevent the Mg.sub.2Si particles from becoming coarser, it is possible to rapidly cool the sheet to a certain extent so as to cool it while the particles are fine and make the aspect ratio small. The cooling conditions will be explained later.

(28) The long axis and aspect ratio of the Mg.sub.2Si particles can be found by examining the cross-section of the plating layer by an EPMA. The EPMA is used to examine the Al—Mg—Si—Ca-based plating layer, the clumps of precipitates including Mg and Si in the plating layer are judged to be Mg.sub.2Si, and the precipitates are measured for their long axis and short axis. The aspect ratio is found by dividing the long axis by the short axis.

(29) Next, the method of making Mg.sub.2Si particles with a long axis of 10 μm or less and an aspect ratio of 1 to 3 disperse and precipitate in the plating layer in large numbers will be explained. To make Mg.sub.2Si with a long axis of 10 μm or less and an aspect ratio of 1 to 3 disperse in the plating layer in large numbers, as explained in the section on Ti, it is important to make TiAl.sub.3 finely disperse in the liquid phase in the process of solidification of the plating.

(30) The reason is that TiAl.sub.3 forms nuclei for formation of Mg.sub.2Si and, as a result, Mg.sub.2Si can be made to finely disperse uniformly in the plating layer. For this reason, the method of production of the plated steel sheet according to the present invention is characterized by two stages of cooling for precipitation of TiAl.sub.3 after hot dip coating and precipitation of Mg.sub.2Al after that.

(31) First, the hot dip aluminum coating process will be explained. The temperature of the plating bath, which has the same composition of ingredients as the plating layer, should be 670° C. or more. Therefore, the steel sheet is dipped and passed through the bath in the same way as an ordinary hot dip aluminum coating process to plate aluminum.

(32) The plating bath temperature is more preferably given a lower limit of 680° C. from the viewpoint of securing a margin from the peritectic reaction temperature (665° C.). Furthermore, 685° C. is more preferable. Further, if the plating bath temperature becomes too high, the sheet will be rapidly cooled before the TiAl.sub.3 precipitates after plating and the lifetime of the various equipment inside the bath will become shorter, so the upper limit should be made 700° C. or so. Making it 695° C. is more preferable. If possible, making it 690° C. is still more preferable. The temperature of the steel sheet at the time of entering the plating bath should be made slightly higher than the plating bath temperature (plating bath temperature to plating bath temperature+30° C. or so). More preferably, it is desirably made 5 to 15° C. higher than the plating bath temperature.

(33) Next, the aluminum plated steel sheet is cooled in the first stage of the cooling process. The first stage of the cooling process cools the hot dip coated steel sheet all at once down to the peritectic reaction temperature of L (liquid phase)+TiAl.sub.3.fwdarw.(Al) (665° C.) to 620° C. by a 25° C./sec or faster cooling rate. At this time, the plating layer has TiAl.sub.3 remaining in it due to the overcooling. The target temperature of the first stage of cooling is 620° C., but in the actual process, it is sufficient to cool down to 600 to 640° C. in range of temperature.

(34) After that, as the second stage of cooling, the plated steel sheet is cooled down to 570° C. by a cooling rate of 16° C./sec or more to make Mg.sub.2Si precipitate and grow. At this time, the larger the cooling rate, the smaller the aspect ratio of the Mg.sub.2Si particles tends to become. The target temperature of the second stage of cooling is 570° C., but in the actual process, it is sufficient to cool down to a temperature of 550 to 590° C. in range.

(35) Note that, the hot dip aluminum coating process, first stage cooling process, and second stage cooling process are preferably consecutive. This is to maintain the cooling rate in the process of solidification of the plating layer in the above range.

(36) The first stage of cooling, that is, the cooling when passing the peritectic reaction temperature (665° C.)., is necessary in order for the TiAl.sub.3 to finely disperse in the plating layer. At this time, the greater the cooling rate, the more the TiAl.sub.3 is finely dispersed, so the Mg.sub.2Si is also finely dispersed and precipitates. That is, it is important that the cooling rate from the temperature of the hot dip coating metal (670° C. or more) to 620° C. be 25° C./sec or more.

(37) This is because if the cooling rate during this time is 19° C./sec or so, the aspect ratio of the Mg.sub.2Si particles sometimes becomes 3 or less, but if made 25° C./sec or more, the aspect ratio of the Mg.sub.2Si particles reliably becomes 3 or less.

(38) The upper limit of the cooling rate need not be particularly set, but if the cooling rate becomes too large, for example, in the case of a jet cooler, the increase in the flow rate may cause patterns. In the case of mist cooling as well, similar patterns may form. Further, while inefficient economically as well, 35° C./sec or 40° C./sec or so may also be made the upper limit.

(39) The second stage cooling, that is, the cooling from when the plating metal is in the overcooling state (620° C.) to complete solidification (570° C.), is necessary for the Mg.sub.2Si to precipitate and grow. At this time, if the cooling rate is too slow, the Mg.sub.2Si grows, the particle size becomes larger, and the aspect ratio becomes greater. For this reason, it was learned that the cooling rate during this should be made 16° C./sec or more. Preferably, it is made 18° C./sec or more, if possible, it is made 20° C./sec or more.

(40) On the other hand, if the cooling rate is too fast, the particles become finer, the aspect ratio becomes smaller, and the Mg.sub.2Si sometimes does not sufficiently precipitate. However, the Mg.sub.2Si starts to precipitate after precipitation of TiAl.sub.3, so no upper limit need particularly be provided. If forced to say something, the first stage cooling rate should be made the upper limit.

(41) Further, the plated steel sheet according to the present invention is produced by running steel sheet in the hot dip coating bath in a similar ray to normal hot dip coated steel sheet, so inevitably, an alloy layer comprised of intermetallic compounds is formed between the plating layer and base iron. At this time, the composition of the alloy layer becomes Al—Si—Fe. If the amounts of addition of Mg and Ca increase, sometimes formation of intermetallic compounds in which these elements are included is observed.

(42) The thickness of the alloy layer is preferably 5 μm or less. The reason is that the alloy layer is hard and brittle, so if thick, the workability of the steel sheet is greatly impaired. Further, if the alloy layer is thick, cracks first occur in the alloy layer at the press forming etc. These are propagated through the plating layer. As a result, there is a possibility of causing the corrosion resistance to deteriorate.

(43) If the time of dipping in the plating bath is long, a thick alloy layer is formed. Therefore, it is necessary to adjust the time of dipping in the plating bath. Further, it is known that by adding Mg in the plating bath, the effect of reduction of the thickness of the alloy layer is also obtained.

(44) Note that, the Fe from the steel sheet enters the plating bath, so Fe unavoidably enters the plating layer. Further, the plating layer sometimes also includes Cu, Ni, Mn, etc. However, even if Fe, Cu, Ni, and Mn are included in a total of 2 mass % or less, the characteristics of the steel sheet according to the present invention are not affected.

(45) In hot dip coating, the wiping for controlling the amount of plating deposition is most generally gas wiping. The type of the wiping gas is usually N.sub.2, air, etc., but in addition, CO.sub.2, combustion gas, etc. may be used. The concentration of oxygen on the bath surface may also be controlled.

(46) If the amount of plating deposition increases, in general the corrosion resistance is improved. Conversely, the workability and weldability fall. The present invention enables this effect to be obtained even with a little amount of deposition since the plating composition is excellent in corrosion resistance. The amount of plating deposition (total amount of deposition of plating layer and alloy layer of intermetallic compound) preferably is a thickness of 9 to 35 μm (25 to 100 g/m.sup.2 per side). If the amount of plating deposition is less than 9 μm per side (25 g/m.sup.2), the corrosion resistance becomes insufficient. If the amount of plating deposition exceeds 35 μm (100 g/m.sup.2), the corrosion resistance becomes saturated and further the press formability, plating adhesion, and resistance weldability become poor. From the viewpoint of the corrosion resistance, the lower limit of the amount of deposition is more preferably 10.5 μm (30 g/m.sup.2), still more preferably 12.3 μm (35 g/m.sup.2).

(47) The composition of the plated sheet which is used in the present invention is not particularly limited. For applications where a high degree of workability is demanded, use of IF steel excellent in workability is desired. Further, to secure air-tightness after the welding and secondary workability, steel sheet to which several ppm of B is added is preferable. Conversely, for applications where strength is demanded, low carbon steel, high tension steel, etc. naturally may be used.

(48) In the present invention, the post-treatment of the plated steel sheet is not particularly limited. Of course, the sheet may also have a post-treatment film aimed at improvement of the workability. For example, chromate-free chemical conversion using Zr, V, Cr.sup.3+, etc. and resin coating are also possible. For the chemical conversion, phosphoric acid, silica, etc. may be used.

(49) Further, an Mg-based compound may be added. As the type of resin, for example, there are an acrylic acid or methacrylic acid ester, vinyl carboxylic acid ester, vinylether, styrene, acrylamide, acrylonitrile, halogenated vinyl, or other ethylenic unsaturated compound and epoxy, urethane, polyester, etc.

(50) Furthermore, in addition to chemical conversion and resin coating, treatment for making the appearance uniform after hot dip coating such as zero spangle treatment, treatment for modifying the plating such as annealing, temper rolling for adjusting the surface conditions and properties, etc. may be applied.

(51) To make the steel sheet and plating bath uniformly react and obtain a stable appearance, pretreatment such as preplating, washing, etc. may be applied before hot dip coating. For example, preplating by Ni, Co, Sn, and Zn may be considered. Next, a fuel tank which uses the plated steel sheet according to the present invention will be explained.

(52) The fuel tank of the present invention is not particularly limited in application. It may be used in automobiles, motorcycles, buses, trucks, etc. Furthermore, the method of working the plated steel sheet according to the present invention is also not particularly limited. This is because the sheet has workability equivalent to conventional plated steel sheet. As a result, the fuel tank according to the present invention is also not particularly limited in shape.

(53) Summarizing the above, the fuel tank according to the present invention can be produced by an existing design technique while using an existing production process. However, only naturally, in the case of plated steel sheet which is plated on only one surface, the plated surface has to be made the surface which contacts the flex fuels.

(54) The plated steel sheet according to the present invention itself has excellent corrosion resistance to flex fuels, so fuel tanks which use the same also have excellent corrosion resistance.

EXAMPLES

(55) Below, examples of the present invention will be explained. Cold rolled steel sheet (sheet thickness 0.8 mm) was used as the base material for hot dip aluminum coating. The composition of the plating bath was based on Al and was changed in the amounts of Si, Mg, Ca, and Ti in various ways. In addition to these, as an impurity element, the Fe which enters from the steel sheet etc. was contained in an amount of 1 to 2% or so (mass %).

(56) The sheet temperature of the steel sheet when entering the plating bath and the bath temperature were both made 670° C. The time of dipping in the bath was changed to control the thickness of the alloy layer. The amount of plating deposition was adjusted after plating by N.sub.2 gas wiping. The cooling was controlled from 670° C. to 620° C. (first stage cooling) and from 620° C. to 570° C. (second stage cooling). The thus produced samples were checked for plating composition, long axis (μm) and aspect ratio of Mg.sub.2Si, thickness of alloy layer, and plating thickness.

(57) The plating layer was evaluated by peeling off only the plating layer and evaluating it in accordance with the test methods of properties of plating layers which are described with reference to JIS H 8672. That is, the aluminum coating layer was electrolytically peeled off in a 241 g/l solution of AlCl.sub.2.6H.sub.2O. The peeled off area at this time was 25 cm.sup.2, and the current density was 20 mA/cm.sup.2. When reaching the potential which shows the alloy layer, the current was immediately stopped, the alloy layer was exposed, and the solution of the dissolved plating layer was quantitatively analyzed by ICP (inductively coupled plasma). The thickness of the alloy layer was measured by a 400× cross-section micrograph.

(58) Further, the hot dip coated steel sheet was evaluated for appearance, corrosion resistance, and overall condition by the methods explained below. The results are shown in Tables 1 to 4. (Note that, Table 1-1 and Table 1-2 will together be called Table 1.)

(59) Evaluation of Appearance

(60) E (Excellent): Visibly beautiful with no wrinkles

(61) F (Fair): Visible slight wrinkles

(62) P (Poor): Visible wrinkles

(63) Corrosion Resistance

(64) Using an Erichsen testing machine, diameter 50 mm, depth 40 mm, flat bottom cupped samples were used to seal in the following three types (Degraded E10, Degraded E25, and Degraded E100) of ethanol-mixed gasoline 40 ml at 45° C. for 1500 hours and examined for appearance.

(65) A sample with corrosion products was washed by ultrasonically waves while sealing in fuel. The corrosion products deposited on the sample and the corrosion products floating free in the fuel were filtered using a 0.8 μm mesh membrane filter.

(66) A membrane filter on which corrosion products were trapped was used to further filter normal heptane 100 ml, then the membrane filter was dried at 80° C. for 1 hour and the dry weight of the corrosion products was measured.

(67) Degraded E10 is a mixed solution of 99.5 vol % of a mixed gasoline containing 10 vol % of ethanol and 0.5 vol % of corrosive water (to which acetic acid 100 ppm and chlorine 100 ppm are added)

(68) Degraded E25 is a mixed solution of 98 vol % of a mixed gasoline containing 25 vol % of ethanol and 2 vol % of corrosive water (to which acetic acid 100 ppm and chlorine 100 ppm are added)

(69) Degraded E100 is a mixed solution of 93 vol % of ethanol and 7 vol % of corrosive water (to which acetic acid 100 ppm and chlorine 100 ppm are added)

(70) Evaluation of Corrosion Resistance

(71) E (Excellent): No change in appearance and less than 12 mg/liter of corrosion products

(72) G (Good): No change in appearance and less than 24 mg/liter of corrosion products

(73) F (Fair): White rust present and 24 mg/liter or more of corrosion products

(74) P (Poor): Red rust and white rust confirmed

(75) Overall Evaluation

(76) E (Excellent): No problem in appearance and corrosion resistance

(77) G (Good): Usable level

(78) F (Fair): Usable level, some problem in corrosion resistance or appearance

(79) P (Poor): Problem in appearance or corrosion resistance—unusable level

(80) Table 1 shows the results of study of the chemical composition of the plating layer. Comparative Example No. 1 had a low amount of Mg outside of the present invention, so red rust and white rust were confirmed and the corrosion resistance was inferior.

(81) Comparative Example No. 9 had a high amount of Mg outside of the present invention, so the appearance was inferior.

(82) Comparative Example No. 10 had a low amount of Si outside of the present invention, so the amount of formation of Mg.sub.2Si was insufficient and the corrosion resistance was inferior. Conversely, Comparative Example No. 20 had a high amount of Si outside of the present invention, so the plating bath was too high in melting point and the plating bath could not be prepared.

(83) Comparative Example No. 21 had a low amount of Ca outside of the present invention, so wrinkles occurred and the appearance was inferior. As the amount of Ca became greater as in Nos. 22 and 23, wrinkling was suppressed. With the amount of Ca of No. 24, a beautiful appearance was obtained. However, if the amount of Ca became further greater as in No. 31 to No. 34, the plating bath became viscous and operation became difficult. Comparative Example No. 35 had a high amount of Ca outside of the present invention, so the makeup of the bath became difficult and a sample which could be evaluated could not be prepared.

(84) No. 36 to No. 46 changed the amount of Ti. The tendency was recognized that as the amount of Ti increases, the Mg.sub.2Si becomes smaller in long axis and the Mg.sub.2Si becomes smaller in aspect ratio (that is, becomes close to spherical).

(85) Comparative Example No. 36 had no Ti added, while Comparative Example No. 37 had an insufficient amount of Ti. The corrosion resistance was inferior. On the other hand, when the amount of Ti is over 0.02%, the liquidus temperature of the Al—Si—Mg—Ca alloy is raised, so this is not preferable. Further, the reduction of dross by oxidation of Ti and other aspects of operational stability are also impaired. Comparative Example No. 46 had too great a Ti. The makeup of the bath became difficult and a sample which could be evaluated could not be prepared.

(86) As opposed to this, the invention examples were all excellent in appearance and corrosion resistance. The overall evaluations were also excellent.

(87) Next, the inventors took the plating composition of Invention Example No. 5 and changed the first and second cooling rates after hot dip coating. The results are shown in Table 2. In No. 47 to No. 53, the first stage cooling rate was changed. If the first stage cooling rate increases, a tendency is observed of the Mg.sub.2Si becoming smaller in aspect ratio (that is, becoming closer to a sphere).

(88) In Comparative Example No. 47 and Comparative Example No. 48, the first stage cooling rate was insufficient, the rate was insufficient for fine dispersion and precipitation of Mg.sub.2Si, and the aspect ratio could not be controlled to 3 or less. Note that like in No. 53, if making the cooling rate over 30° C./sec, a pattern is formed due to the increase in flow rate of the jet cooler. This is also inefficient economically.

(89) In No. 54 to No. 62, the second stage cooling rate was changed. If the second stage cooling rate increases, a tendency is observed of the Mg.sub.2Si becoming smaller in long axis.

(90) In Comparative Example No. 54, the second stage cooling rate is insufficient, so the Mg.sub.2Si becomes larger in long axis and the corrosion resistance becomes insufficient. On the other hand, if making the cooling rate excessive such as in No. 61 and No. 62, the Mg.sub.2Si becomes smaller in long axis and the amount of precipitation becomes insufficient, so a sufficient corrosion resistance becomes hard to obtain.

(91) Next, the test results on the effects of the thickness of the alloy layer are shown in Table 3. The inventors took the plating composition of Invention Example No. 5 and changed the time for dipping in the hot dip coating bath and the thickness of the alloy layer for evaluation. The results are shown in Table 3.

(92) Invention Example No. 62 to No. 66 were obtained by a 670° C.×2 second bath dipping time and gave a 2 to 5 μm alloy layer thickness. The appearance and corrosion resistance were excellent and the overall evaluation was excellent.

(93) Invention Example No. 67 was obtained by a 620° C.×4 second bath dipping time and gave a 6.0 μm alloy layer thickness. It had visible slight wrinkles in appearance, white rust in the corrosion resistance test with Degraded E100, corrosion products of 24 mg/l or more, and somewhat poor E100 corrosion resistance, but was evaluated overall as being usable.

(94) No. 68 was obtained by a 620° C.×6 second bath dipping time and gave a 7.0 μm alloy layer thickness. It had visible slight wrinkles in appearance, white rust in the corrosion resistance test with Degraded E25 and Degraded E100, corrosion products of 24 mg/l or more, and poor E100 corrosion resistance.

(95) It is believed that as the alloy layer thickness becomes greater, the uneven thickness of the alloy layer caused fine wrinkles in the surfacemost plating layer. Further, a thick alloy layer is poor in workability. Cracks occurred which propagated to the plating layer in the process of cupping.

(96) From the above test results, it was confirmed that when the thickness of the alloy layer is over 5 μm, use is possible, but the appearance becomes poor and the workability falls.

(97) Next, the effects of the plating thickness will be evaluated. The inventors took the plating composition of Invention Example No. 5 and changed the wiping after hot dip coating to run a test on the effects of the plating thickness. The results are shown in Table 4.

(98) As shown in Invention Example Nos. 69 to 71 of Table 4, when the plating thickness is less than 12.3 (amount of plating deposition per side of 35 g/m.sup.2), the corrosion resistance becomes poorer. Conversely, as shown in Comparative Example No. 82 to No. 84, when plating thickness is more than 35 μm (amount of plating deposition per side of 100 g/m.sup.2), not only is the result uneconomical, but also the separately evaluated press formability, plating adhesion (plating internal breakage), and resistance weldability fall.

(99) From the above test results, the plating thickness does not have much an effect on the corrosion resistance or appearance. If in the above-mentioned range, it was confirmed that hot dip coated steel sheet which has excellent appearance and corrosion resistance can be obtained.

(100) Above, the present invention will be explained by examples. Note that, the embodiments of the present invention are not limited to these examples.

(101) TABLE-US-00001 Alloy Plating 1.sup.st 2nd Mg.sub.2Si layer Plating composition cool- cool- long Mg.sub.2Si thick- thick- Corrosion resistance Overall mass % ing ing axis aspect ness ness Appear- Degraded Degraded Degraded evalu- No Mg Si Ca Ti ° C./s ° C./s μm ratio μm μm ance E10 E25 E100 ation Remarks Table 1-1 1 2 8 0.2 0.015 28 26 6 1.2 3 15 E F F P P Comparative example 2 3 8 0.2 0.015 28 26 6 1.2 3 15 E E G F E 3 4 8 0.2 0.015 28 26 6 1.2 3 15 E E E F E 4 5 8 0.2 0.015 28 26 6 1.2 3 15 E E E E E 5 6 8 0.2 0.015 28 26 6 1.2 3 15 E E E E E 6 7 8 0.2 0.015 28 26 6 1.2 3 15 E E E E E 7 8 8 0.2 0.015 28 26 6 1.2 3 15 F E E E E 8 9 8 0.2 0.015 28 26 6 1.2 3 15 F E E E F 9 10 8 0.2 0.015 28 26 6 1.2 3 15 P E E E P Comparative example 10 6 1 0.2 0.015 28 26 6 1.2 3 15 E F F P P Comparative example 11 6 2 0.2 0.015 28 26 6 1.2 3 15 E E E E F 12 6 3 0.2 0.015 28 26 6 1.2 3 15 E G G F F 13 6 4 0.2 0.015 28 26 6 1.2 3 15 E E G G G 14 6 5 0.2 0.015 28 26 6 1.2 3 15 E E E G G 15 6 6 0.2 0.015 28 26 6 1.2 3 15 E E E E E 16 6 7 0.2 0.015 28 26 6 1.2 3 15 E E E E E 17 6 9 0.2 0.015 28 26 6 1.2 3 15 E E E E E 18 6 10 0.2 0.015 28 26 6 1.2 3 15 E E E E E 19 6 11 0.2 0.015 28 26 6 1.2 3 15 E E E E E 20 6 12 0.2 0.015 — — — — — — — — — — — Comp. ex., bath makeup difficult 21 6 8 0.08 0.015 28 26 6 1.2 3 15 P E E E P Comparative example 22 6 8 0.1 0.015 28 26 6 1.2 3 15 F E E E F 23 6 8 0.12 0.015 28 26 6 1.2 3 15 F E E E F 24 6 8 0.15 0.015 28 26 6 1.2 3 15 E E E E E 25 6 8 0.3 0.015 28 26 6 1.2 3 15 E E E E E Table 1-2 29 6 8 3 0.015 28 26 6 1.2 3 15 E E E E E 30 6 8 4 0.015 28 26 6 1.2 3 15 E E E E E 31 6 8 4.2 0.015 28 26 6 1.2 3 15 E E E E E Operation difficult 32 6 8 4.5 0.015 28 26 6 1.2 3 15 E E E E E Operation difficult 33 6 8 4.8 0.015 28 26 6 1.2 3 15 E E E E E Operation difficult 34 6 8 5 0.015 28 26 6 1.2 3 15 E E E E E Operation difficult 35 6 8 5.5 0.015 — — — — — — — — — — — Comp. ex., bath makeup difficult 36 6 8 0.2 0 28 26 10 6.3 3 15 E E F P P 37 6 8 0.2 0.003 28 26 8 3.2 3 15 E E F P P Comparative example 38 6 8 0.2 0.005 28 26 8 2.8 3 15 E E E F G 39 6 8 0.2 0.008 28 26 6 2.5 3 15 E E E E E 40 6 8 0.2 0.01 28 26 6 2.1 3 15 E E E E E 41 6 8 0.2 0.018 28 26 5 1.2 3 15 E E E E E 42 6 8 0.2 0.02 28 26 4 1.1 3 15 E E E E E Operation difficult 43 6 8 0.2 0.03 28 26 4 1.1 3 15 E E E E E Operation difficult 44 6 8 0.2 0.04 28 26 4 1.1 3 15 E E E E E Operation difficult 45 6 8 0.2 0.048 28 26 4 1.1 3 15 E E E E E Operation difficult 46 6 8 0.2 0.052 — — — — — — — — — — — Comp. ex., bath makeup difficult

(102) TABLE-US-00002 TABLE 2 Alloy Plating 1.sup.st 2nd Mg.sub.2Si layer Plating composition cool- cool- long Mg.sub.2Si thick- thick- Corrosion resistance Overall mass % ing ing axis aspect ness ness Appear- Degraded Degraded Degraded evalu- No Mg Si Ca Ti ° C./s ° C./s μm ratio μm μm ance E10 E25 E100 ation Remarks 47 6 8 0.2 0.015 15 26 6 3.8 3 15 E E P P P Comparative example 48 6 8 0.2 0.015 16 26 6 3.2 3 15 E G F P P Comparative example 49 6 8 0.2 0.015 19 26 6 2.7 3 15 E E G F F 50 6 8 0.2 0.015 22 26 6 2.4 3 15 E E E G G 51 6 8 0.2 0.015 25 26 6 1.9 3 15 E E E E E 52 6 8 0.2 0.015 28 26 6 1.2 3 15 E E E E E 53 6 8 0.2 0.015 31 26 6 1.1 3 15 F E E E G 54 6 8 0.2 0.015 28 14 12 2.3 3 15 E G F P P Comparative example 55 6 8 0.2 0.015 28 16 10 2.1 3 15 E G G F F 56 6 8 0.2 0.015 28 18 8 1.8 3 15 E E G G G 57 6 8 0.2 0.015 28 20 7 1.6 3 15 E E E G G 58 6 8 0.2 0.015 28 22 6 1.3 3 15 E E E E E 59 6 8 0.2 0.015 28 24 5 1.2 3 15 E E E E E 60 6 8 0.2 0.015 28 26 4 1.2 3 15 E E E E E 61 6 8 0.2 0.015 28 28 2 1.2 3 15 E E E G G 62 6 8 0.2 0.015 28 30 1.5 1.1 3 15 E E E G G

(103) TABLE-US-00003 TABLE 3 Alloy Plating 1.sup.st 2nd Mg.sub.2Si layer Plating composition cool- cool- long Mg.sub.2Si thick- thick- Corrosion resistance Overall mass % ing ing axis aspect ness ness Appear- Degraded Degraded Degraded evalu- No Mg Si Ca Ti ° C./s ° C./s μm ratio μm μm ance E10 E25 E100 ation Remarks 63 6 8 0.2 0.015 28 26 6 1.2 2 15 E E E E E 64 6 8 0.2 0.015 28 26 6 1.2 3 15 E E E E E 65 6 8 0.2 0.015 28 26 6 1.2 4 15 E E E E E 66 6 8 0.2 0.015 28 26 6 1.2 5 15 E E E E E 67 6 8 0.2 0.015 28 26 6 1.2 6 15 F E E G G 68 6 8 0.2 0.015 28 26 6 1.2 7 15 F E G G G

(104) TABLE-US-00004 TABLE 4 Alloy Plating 1.sup.st 2nd Mg.sub.2Si layer Plating composition cool- cool- long Mg.sub.2Si thick- thick- Corrosion resistance Overall mass % ing ing axis aspect ness ness Appear- Degraded Degraded Degraded evalu- No Mg Si Ca Ti ° C./s ° C./s μm ratio μm μm ance E10 E25 E100 ation Remarks 69 6 8 0.2 0.015 28 26 6 1.2 3 8 E G G F F 70 6 8 0.2 0.015 28 26 6 1.2 3 10 E E G G G 71 6 8 0.2 0.015 28 26 6 1.2 3 12 E E E G G 72 6 8 0.2 0.015 28 26 6 1.2 3 13 E E E E E 73 6 8 0.2 0.015 28 26 6 1.2 3 15 E E E E E 74 6 8 0.2 0.015 28 26 6 1.2 3 18 E E E E E 75 6 8 0.2 0.015 28 26 6 1.2 3 20 E E E E E 76 6 8 0.2 0.015 28 26 6 1.2 3 23 E E E E E 77 6 8 0.2 0.015 28 26 6 1.2 3 25 E E E E E 78 6 8 0.2 0.015 28 26 6 1.2 3 28 E E E E E 79 6 8 0.2 0.015 28 26 6 1.2 3 31 E E E E E 80 6 8 0.2 0.015 28 26 6 1.2 3 32 E E E E E 81 6 8 0.2 0.015 28 26 6 1.2 3 35 E E E E E 82 6 8 0.2 0.015 28 26 6 1.2 3 37 E E E E E Press formability, plating adhesion, and resistance weldability fall 83 6 8 0.2 0.015 28 26 6 1.2 3 40 E E E E E Press formability, plating adhesion, and resistance weldability fall 84 6 8 0.2 0.015 28 26 6 1.2 3 45 E E E E E Press formability, plating adhesion, and resistance weldability fall

INDUSTRIAL APPLICABILITY

(105) The plated steel sheet according to the present invention can not only be utilized in automobiles, motorcycles, buses, trucks, etc., in particular as fuel tanks of flex fuels, but can also be utilized as members in which resistance to corrosion by flex fuels etc. is demanded.