US 20080206592A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2008/0206592 A1
Kim et al. (43) Pub. Date: Aug. 28, 2008
(54) GALVANIZED STELL-SHEET WITHOUT Publication Classification
SPANGLE, MANUFACTURING METHOD (51) Int. Cl.
THEREOF AND DEVICE USED THEREFOR
B32B I5/0 (2006.01)
BSD L/18 (2006.01)
(75) Inventors: Sang-Heon Kim, BOSC3/02 (2006.01)
Kyungsangbook-do (KR); Noi-Ha
Cho, Kyungsangbook-do (KR); (52) U.S. Cl. .......... 428/653; 428/684; 427/457; 118/620
Yeong-Sool Jin, (57) ABSTRACT
Kyungsangbook-do (KR)
A Spangle-free, hot-dip galvanized steel sheet, and a method
Correspondence Address: and device for manufacturing the same. The hot-dip galva
THE WEBB LAW FIRM, P.C. nized steel sheet is characterized in that a solidified zinc
700 KOPPERS BUILDING, 436 SEVENTH crystal of hot-dip galvanized layer has an average crystalline
AVENUE texture particle diameter of 10 to 88 um and there is no
PITTSBURGH, PA 15219 (US) Solidification traces of dendrites upon observing under a
microscope at a magnification of 100x. The method com
(73) Assignee: POSCO, Pohang (KR) prises dipping a steel sheet in a bath of a zinc-coating Solution
containing 0.13 to 0.3% by weight of aluminum; air-wiping
(21) Appl. No.: 11/722,759 the steel sheet to remove an excess of the coating solution;
spraying water or an aqueous solution on the air-wiped steel
(22) PCT Filed: Oct. 31, 2005 sheet, using a steel sheet temperature in the range of a hot-dip
galvanization temperature to 419' C. as a spray initiation
(86). PCT No.: PCT/KROS/O3637 temperature and using a steel sheet temperature in the range
of 417° C. to 415° C. as a spray completion temperature:
S371 (c)(1), passing sprayed liquid droplets of water or aqueous Solution
(2), (4) Date: Nov. 13, 2007 through a mesh-like high-voltage charged electrode which is
electrically charged with a high voltage of -1 to -50 kV; and
(30) Foreign Application Priority Data allowing the electrode-passed liquid droplets to be bound to
the surface of the steel sheet and hereby being served as
Dec. 28, 2004 (KR) ........................ 10-2004-O114090 Solidification nuclei of molten zinc.

Number
Of
Spangle

s 88 5

KB)
Patent Application Publication Aug. 28, 2008 Sheet 1 of 6 US 2008/0206592 A1

Fig. 1)
Patent Application Publication Aug. 28, 2008 Sheet 2 of 6 US 2008/0206592 A1

Fig.2)

1.0 pum

0.00 0.50 1.00 1.50 2.50

Patent Application Publication Aug. 28, 2008 Sheet 3 of 6 US 2008/0206592 A1

Fig. 3)
(a)
CA) CB)

Skin-pass 0% Skin-pass 1.5%

KA)

Skin-pass 0% Skin-pass 1.5%

Patent Application Publication Aug. 28, 2008 Sheet 4 of 6 US 2008/0206592 A1

Fig. 4
Patent Application Publication Aug. 28, 2008 Sheet 5 of 6 US 2008/0206592 A1

Fig. 5)

O 0.5 1 15 2 2.5
Skin-pass drawing ratio (%)
Patent Application Publication Aug. 28, 2008 Sheet 6 of 6 US 2008/0206592 A1

- -

2.111111121-111111-1-1-121
US 2008/0206592 A1 Aug. 28, 2008

GALVANIZED STELL-SHEET WITHOUT can be said that the size of Spangles is dependent on the size
SPANGLE, MANUFACTURING METHOD of skeleton of the coating texture which was determined at the
THEREOF AND DEVICE USED THEREFOR early stage of Solidification.
0006 Further, when dendrites grow, since they solidify
TECHNICAL FIELD while consuming molten Zinc present therearound, a region of
dendrites convexly protrudes and a region of the pool con
0001. The present invention relates to a spangle-free, hot cavely depresses, thereby resulting in a non-uniform thick
dip galvanized steel sheet, and a method and device for manu ness of the coating layer, i.e., occurrence of hills and Valleys
facturing the same. More specifically, the present invention on the coating Surface.
relates to a spangle-free, hot-dip galvanized Steel sheet having 0007 Further, upon solidification of molten zinc, features
Superior corrosion resistance, oil stain resistance and black and forms of Spangles vary depending upon what manner
ening resistance and exhibiting favorable Surface appearance, hexagonal crystal structures of Zinc are crystallographically
and a method and device for manufacturing the same. arranged on the Surface of the steel sheet. In other words, one
BACKGROUND ART
hot-dip galvanized layer is composed of various forms of zinc
crystals (spangles), thus representing that hexagonal crystal
0002 Hot-dip galvanized (HDG) steel sheets have advan structures of Zinc are placed at different angles according to
tages Such as manufacturing compared to electrocoating and respective regions of the coating layer. Generally, crystal
low costs of products and therefore their uses are recently orientation in which a basal plane of Zinc is placed parallel to
extending to broad areas Such as household electric appli the surface of the steel sheet is known to exert the most
ances and motor vehicles. However, in spite of their low costs, Superior corrosion resistance, blackening resistance and
the hot-dip galvanized steel sheets have surface qualities infe chemical stability, but it is very difficult to make all of the
rior to those of electro-galvanized (EG) steel sheets and there spangles to have desired basal planes.
fore are not widely used for applications in which distinctness 0008 Consequently, each and every spangle in one hot
of image (DOI) or favorableness of external appearance after dip galvanized steel sheet has different crystal planes of Zinc
painting is a very important factor. Such as outer plates of exposed to the surface and there are differences in chemical
motor vehicles or household electric appliances. Further, hot reactivity according to respective regions due to non-unifor
dip galvanized steel sheets suffer from problems and disad mity of crystal orientation, which are believed to result in
Vantages such as inferior corrosion resistance, blackening inferior corrosion resistance, oil stain resistance and black
resistance and oil stain resistance, as compared to electro ening resistance of the hot-dip galvanized steel sheet as com
galvanized steel sheets. pared to electro-galvanized (EG) steel sheets having uniform
0003. As such, in compliance with their extended uses, the Surface texture.
hot-dip galvanized steel sheets are required to have Superior 0009 Meanwhile, generally in corrosion, the exterior of
quality characteristics in conjunction with favorable Surface grains, grain boundary, has a high electrochemical potential
appearance comparable to that of electro-galvanized steel and thereby serves as an anode where corrosion proceeds,
sheets, and in particular, there are required improvements in whereas the interior of grains serves as a cathode. Where the
Surface appearance, oil stain resistance and blackening resis area of the anode is relatively small as compared to that of the
tance, which are inferior to those of electro-galvanized steel cathode, corrosion locally and rapidly progresses.
sheets. 0010. In a hot-dip galvanization process, when skin-pass
0004 Disadvantageous properties of the hot-dip galva rolling for improving Surface appearance via securing of
nized steel sheets Such as inferior Surface appearance, corro mechanical properties and inhibition of Spangle exposure is
sion resistance, oil stain resistance and blackening resistance, carried out, adverse effects such as non-uniformity of crystal
as compared to those of electro-galvanized steel sheets, result structures and occurrence of coarse coating texture are more
from coating layer-formation reactions and manufacturing pronounced. That is, each spangle exhibits a different degree
processes of the hot-dip galvanized steel sheets. In electro of deformation caused by rolling, and as a result, adverse
galvanization, the coating layer is composed of fine crystal effects due to non-uniformity of crystal structures become
line grain. Whereas, the coating layer obtained by hot-dip even worse. Further, as the coarse coating texture exhibits
galvanization is composed of large crystalline grains. As a more conspicuous shapes of dendrites, there are significant
result, there is a difference in grain boundary therebetween. unevenness of Surface profile according to respective regions
That is, the coating layer obtained by electro-galvanization is of the coating layer. As a result, regions protruded upon
made up of fine crystalline S having a size of several to skin-pass rolling are mechanically further deformed, result
several tens of Ll whereas the coating layer of the hot-dip ing in serious problems associated with heterogeneous quali
galvanized steel sheet is susceptible to occurrence of a unique ties according to respective regions.
coating texture aspect, called a spangle or flower pattern, and 0011. In order to solve the above-mentioned shortcomings
the coating texture of commercially available hot-dip galva due to Spangles and in order to obtain qualities comparable to
nized steel sheets generally has a texture region size of more those of electro-galvanized steel sheets, it is necessary to
than 500 micronize Spangles to the maximum extent possible. For Such
0005. Occurrence of such coarse spangles is due to char reasons, a variety of methods for decreasing the Spangle size
acteristics of solidification reaction of zinc. That is, when Zinc have been proposed.
is solidified, dendrites in the form of the branches of a tree 0012 For example, mention may be made of the following
rapidly grow from a solidification nucleus as a starting point methods: (1) Method using a coating bath to which antimony
at an early stage of solidification, forming a skeletal structure (Sb) or lead (Pb) is not added, (2) Method involving perform
of the coating texture, and thereafter a non-solidified molten ing skin-pass rolling after coating is complete, and (3)
Zinc pool, which remained between dendrites, solidifies, thus Method involving spraying water or an aqueous solution
resulting in completion of Solidification reaction. That is, it immediately before solidification of the zinc-coating layer.
US 2008/0206592 A1 Aug. 28, 2008

0013 However, the coating methods (1) and (3) may DISCLOSURE OF INVENTION
reduce the size of spangles, but suffer from difficulty to Technical Problem
achieve a decrease of the Spangle size equal to the level of
electrocoating, due to a high solidification rate of zinc. Here 0019. Therefore, the present invention has been made in
inafter, the reasons for that will be specifically described. view of the above problems, and it is an object of the present
0014. The first reason is based on solidification properties invention to provide a hot-dip galvanized steel sheet having
of molten zinc. That is, the steel sheet has a thickness of about Superior corrosion resistance, oil stain resistance and black
0.4 to 2.3 mm, whereas the hot-dip galvanized layer typically ening resistance and exhibiting favorable Surface appearance.
has a thickness of about 7 to 10 and does not exceed a 0020. It is another object of the present invention to pro
maximum of 50 which is verythin as compared to the steel vide a spangle-free hot-dip galvanized steel sheet that can be
sheet. used as a material for use in inner and outer plates of carbody,
household electric appliances and building materials and
0015. As such, when the coating layer is solidified while steel sheet for painting.
being cooled, Solidification of the coating layer takes some 0021. It is a further object of the present invention to
period of time because the steel sheet has a large amount of provide a method of manufacturing a hot-dip galvanized Steel
latent heat stored therein. At this time, dendrites grow in the sheet having Superior corrosion resistance, oil stain resistance
surface direction of the steel sheet. Therefore, spangles hav and blackening resistance and exhibiting favorable Surface
ing a size of about 0.5 to 1 mm occur even with combined use appearance.
of Method 1 and Method 3, and it has been regarded by 0022. It is yet another object of the present invention to
consumers of the steel sheet that such a size is almost free of provide a hot-dip galvanization hot-dip galvanized device for
spangles and is sufficient to be used in desired applications. use in manufacturing a hot-dip galvanization steel sheet hav
0016 For consumers requiring favorable surface appear ing Superior corrosion resistance, oil stain resistance and
ance, it is necessary to completely remove traces of Span blackening resistance and exhibiting favorable Surface
gling. For this purpose, the steel sheet is prepared by increas appearance.
ing an amount of skin-pass rolling in Method (2). Here, the
coating layer is crushed by skin-pass rolling, resulting in Technical Solution
elimination of Surface heterogeneity Such as Spangling, and
thereby it is possible to achieve surface qualities similar to the 0023. In accordance with an aspect of the present inven
level of the electroplated material to some extent. However, tion, the above and other objects can be accomplished by the
since the coating layer is deformed by mechanical force, more provision of a hot-dip galvanized Steel sheet wherein a solidi
skin-pass rolling leads to poor blackening resistance, oil stain fied Zinc crystal of hot-dip galvanized layer has an average
resistance and corrosion resistance, thus presenting a prob crystalline texture particle diameter of 10 to 88 and there is
lem of short-term storage of the steel sheet. no solidification traces of dendrites upon observing under a
0017. As a method of reducing the spangle size by con microscope at a magnification of 100x.
trolling the Solidification reaction of the coating layer, there is 0024. In accordance with another aspect of the present
a method of solidifying the coating layer by vigorously spray invention, there is provided a hot-dip galvanized steel sheet
ing an aqueous solution at relatively high-pressure or by wherein a solidified zinc crystal of hot-dip galvanized layer
spraying a finely divided Zinc powder upon Solidification of has an average crystalline texture particle diameter of 10 to 88
the coating layer. However, high-pressure spray is likely to D and not less than 50% of aluminum (Al) on a surface layer
result in damaged appearance due to marks pitted by portion of a coating layer is present around the grain bound
impingement of sprayed liquid droplets of the aqueous solu ary.
tion on the zinc-coating layer in a molten state. In addition, 0025. In accordance with a further aspect of the present
spraying of Zinc powder Suffers from problems such as envi invention, there is provided a hot-dip galvanized steel sheet
ronmental contamination due to scattering of Zinc dust inside wherein a solidified zinc crystal of hot-dip galvanized layer
plants and dent defects on the steel sheet caused by Sticking of has an average crystalline texture particle diameter of 10 to 88
Zinc powder, which was not completely fixed thereon, to D, and a height difference betweenhills and valleys formed on
various rolls. the coating layer in an arbitrarily selected circular area having
0.018 AS techniques relating to Spangle-free hot-dip gal a radius of 5 mm on the surface of the steel sheet is less than
Vanized steel sheets and manufacturing methods thereof, ref 25% of a coating thickness.
erence may be made to Japanese Patent Laid-Open Publica 0026. In accordance with yet another aspect of the present
tion Nos. 1999-100653, 1985-181260 and 1982-108254, invention, there is provided a method of manufacturing a
Korean Patent Laid-Open Publication No. 2001-57547 and hot-dip galvanized steel sheet, comprising:
EP 1348773 A1, which disclose a galvanized steel sheet hav 0027 preparing a steel sheet for hot-dip galvanization;
ing a spangle size of 10 to 100 l. However, there is no 0028 dipping the steel sheet in a bath of a zinc-coating
disclosure on hot-dip galvanized steel sheets having no traces solution containing 0.13 to 0.3% by weight of aluminum;
of dendrite solidification, control of aluminum content in the 0029 air-wiping the steel sheet having the coating solu
coating layer and control of height differences between hills tion bound thereto, thereby removing an excess of the coating
and Valleys in the coating layer. In addition, Korean Patent Solution;
Laid-Open Publication No. 61451 and U.S. Pat. No. 4,500, 0030 spraying water or an aqueous solution onto the sur
561 disclose a method for minimization of Spangling on hot face of the air-wiped steel sheet, using a steel sheet tempera
dip galvanized Steel strip by forming an electric field and ture in the range of a hot-dip galvanization temperature to
passing liquid droplets through the electric field, but do not 419' C. as a spray initiation temperature and using a steel
mention about fabricating a charged electrode into a mesh sheet temperature in the range of 417°C. to 415° C. as a spray
shape. completion temperature;
US 2008/0206592 A1 Aug. 28, 2008

0031 passing sprayed liquid droplets of water or aqueous 0048 FIG. 6 is a schematic view of a hot-dip galvanization
Solution through a mesh-like high-voltage charged electrode device in accordance with the present invention.
which is electrically charged with a high voltage of -1 to -50
kV; and BEST MODE FOR CARRYING OUT THE
0032 allowing the electrode-passed liquid droplets to be INVENTION
bound to the surface of the steel sheet and thereby being 0049. From examination of relationship between an aver
served as Solidification nuclei of molten zinc. age crystalline texture particle diameter of a hot-dip galva
0033. In accordance with a still further aspect of the nized layer and qualities and Surface appearance of a steel
present invention, there is provided a device for manufactur sheet, it was found that the steel sheet has the appearance of a
ing a hot-dip galvanized Steel sheet, comprising: favorable surface when the average crystalline texture
0034) a pair of air knives positioned over a zinc-coating (Spangle) particle diameter of a solidified Zinc crystal of a Zinc
galvanized layer becomes Small in a range of not more than 88
bath to control a coating amount of a plated Steel sheet; (which is a resolution limit of object recognition by naked
0035 one or more water or aqueous solution-spray eyes. The reason why Such characteristics appear is because
nozzles positioned toward the steel sheet in a spray bath over differences in scattering and reflection phenomena of light
air knives; and due to differences between grains in coating layer are not
0036 a mesh-like charged electrode positioned between recognized by naked eyes, when the Solidified Zinc crystal of
the spray nozzle and steel sheet. coating layer has an average crystalline texture grain size of
not more than 88 D.
BRIEF DESCRIPTION OF THE DRAWINGS 0050. Therefore, electro-galvanized (EG) steel sheets
made up of microcrystalline Zinc grains presents difficulty to
distinguish differences between grains in coating layers via
0037. The above and other objects, features and other naked eyes, whereas it is possible to distinguish Such differ
advantages of the present invention will be more clearly ences in conventional hot-dip galvanized steel sheets made up
understood from the following detailed description taken in of microcrystalline Zinc grains and as a result, the Surface of
conjunction with the accompanying drawings, in which: the coating layer has the feeling of non-uniformity due to
0038 FIG. 1a (A) is a surface micrograph of a galvanized differences in light reflection between grains in the hot-dip
steel sheet in Example 5 (top) and (B) is a graph showing size galvanized layer. However, the inventors of the present inven
distribution of spangles of galvanized steel sheet in Example tion have discovered that when a Spangle size in the zinc
5 (bottom), respectively; galvanized layer is decreased to a range of not more than 88
0039 FIG.1b is a surface micrograph of a zinc-galvanized i.e., Spangles disappear, there is a critical grain size at which
steel sheet in Comparative Example 3: characteristics Such as corrosion resistance, blackening resis
tance and oil stain resistance are sharply improved.
0040 FIG.1c is a surface micrograph of a zinc-galvanized 0051. That is, the hot-dip galvanized steel sheet, in which
steel sheet in Comparative Example 9: the average crystalline texture particle diameter (hereinafter,
0041 FIG.2a is a graph showing results of determination also referred to as “average texture size or spangle size of a
on a degree of Surface unevenness of a coating layer in Solidified Zinc crystal of hot-dip galvanized layer is in a range
Example 5: of 10 to 88 land solidification traces of dendrites are not
0042 FIG.2b is a graph showing results of determination observed under a microscope at a magnification of 100x.
on a degree of surface unevenness of a coating layer in Com exhibits Superior blackening resistance, oil stain resistance,
parative Example 3: corrosion resistance and Surface appearance.
0043 FIG. 3a is a graph showing a (0002) preferred ori 0.052 Although it is preferred to reduce a size of the coat
entation plane of a coating layer in Example 5: ing texture to the maximum extent possible since a smaller
size of the coating texture leads to tendency of improvements
0044 FIG. 3b is a graph showing a (0002) preferred ori in Surface appearance, corrosion resistance, blackening resis
entation plane of a coating layer in Comparative example 7: tance and oil stain resistance evenina range of coating texture
0045 FIG. 4a is an EM showing a segregation degree of limited by the present invention, there is substantially no
aluminum in a coating layer of Example 5 (left), an EM further improvement in Such characteristics at a spangle size
showing results of analysis of a coating layer of Example 5 of less than 10 D. In addition, micronization of the zinc grain
using an electron probe micro-analyzer(EPMA) (middle) and involves increased numbers of spray nozzles, an increased
a view showing solidification behavior of a grainboundary in concentration of an aqueous phosphate solution and intensi
coating layer of Example 5 (right), respectively; fication of applied high-voltage, thus imposing heavy bur
0046 FIG. 4b is an EM showing a segregation degree of dens on manufacturing processes. Therefore, where the
aluminum in a coating layer of Comparative Example 7 (left), spangle size is less than 10 l an efficiency of a coating
an EM showing results of analysis of a coating layer of layer-formation process is deteriorated. In contrast, where the
spangle size exceeds 88 differences in scattering and reflec
Comparative Example 7 using EPMA (middle) and a view tion phenomena of light due to differences between zinc
showing Solidification behavior of a grain boundary in coat grains are recognized by naked eyes, as discussed above.
ing layer of Comparative Example 7 (right), respectively; Thus, it is impossible to obtain improved effects of corrosion
0047 FIG. 5 is a graph showing changes in blackening resistance, blackening resistance, oil stain resistance and Sur
resistance of steel sheets of Example 5 and Comparative face appearance.
Example 7 with respect to variation of a skin pass drawing 0053 Hereinafter, the construction and effects of the
ratio; and present invention will be described in more detail via physi
US 2008/0206592 A1 Aug. 28, 2008

cochemical phenomena of a coating layer appearing when a fact that Galfan or Galvalume, which is a zincfaluminum
coating texture becomes Smaller. alloy, is used in applications requiring high corrosion resis
0054 As discussed hereinbefore, a grain boundary has a tance. In addition, in conventional zinc-galvanized Steel
high electrochemical potential in corrosion, and thereby sheets, an improvement of corrosion resistance by aluminum
serves as an anode. As a crystal size becomes Smaller, an area can be confirmed from the fact that aluminum-added hot-dip
of the grain boundary is increased, thus representing that the galvanized steel sheets exhibit corrosion resistance Superior
area of anode in corrosion is increased. to electro-galvanized steel sheets. Upon considering Such
0055 As such, although the small area of anode results in improved corrosion resistance of Zinc by aluminum, it can be
local corrosion, it is possible to prevent such local corrosion seen that aluminum stabilizes unstable electrochemical prop
by increasing the area of anode. Therefore, when the coating erties of the grain boundaries, thereby improving corrosion
texture is micronized, Zinc is uniformly consumed and it is resistance.
thereby possible to prevent the steel sheet from being locally 0061 Accordingly, where aluminum (Al) in a surface
exposed to the atmosphere, thus improving corrosion resis layer portion of the coating layer, except for an iron/alumi
tance. That is, as the area of anode to be corroded is increased, num alloy phase, is present in an amount of 50% or more,
the coating layer can be uniformly corroded. preferably 95% or more at the grain boundaries, superior
0056 Meanwhile, the dendrite refers to a coating texture corrosion resistance is exerted. Herein, % content of alumi
skeleton which is formed in the form of the branches of a tree num present at the grain boundaries among the Surface layer
from Solidification nucleus as a starting point when Zinc portion of the coating layer refers to % distribution of alumi
solidifies. Generally, a pool of non-solidified molten zinc, num present at the grain boundaries among total aluminum
which remained between dendrites, is finally solidified, distribution observed in the surface layer portion of the coat
thereby resulting in completion of solidification of the coat ing layer. Where the content of aluminum at the grainbound
ing layer. Further, upon growing, since dendrites Solidify aries is less than 50%, it is undesirable in that there is no
while consuming molten Zinc present therearound, the den electrochemically stabilizing effect of aluminum on the grain
drite region convexly protrudes and the molten Zinc pool boundaries. As higher 96 of aluminum at the grainboundaries
region concavely depresses, thereby resulting information of leads to an increase in corrosion resistance, an upper limit of
a non-uniform coating layer. Then, Such non-uniformity leads aluminum components present at the grain boundaries is not
to differences in chemical reactivity according to respective particularly limited. According to experiments, a smaller size
regions and failure to obtain the hot-dip galvanized steel sheet of crystalline texture leads to an increase in the aluminum
having uniform corrosion resistance, oil stain resistance and content present at the grain boundaries, and where a size of
blackening resistance and favorable appearance of Surface the coating texture exceeds 88, the aluminum content at the
texture. However, since the hot-dip galvanized steel sheet in grain boundaries becomes less than 50%.
accordance with the present invention is controlled to a state 0062. Without wishing to be bound to any particular
where no solidification traces of dendrites are present upon theory, it is believed that the reason why large quantities of
observing under a microscope at a magnification of 100x, the aluminum are present at the grain boundaries is due to the
coating layer is uniformly formed, which results in uniform solidification reaction which will be described below.
chemical reactivity throughout the coating layer, and as a 0063. Since zinc and aluminum contained in the coating
result, the steel sheet displays improved corrosion resistance, layer, upon solidification, results in eutectic reaction, a higher
oil stain resistance and blackening resistance, and favorable content of aluminum lowers a solidification point of the coat
Surface appearance. ing layer. That is, a Zinc alloy, in which aluminum is partially
0057. In addition, if solidification proceeds in a manner contained, results in lowering of the solidification point
that dendrites grow, it is difficult to obtain the coating texture thereof as compared to pure Zinc and upon solidification,
having a size of not more than 88 due to a very high growth proceeds with Solidification in a manner that pure Zinc is
rate of the dendrites, but less solidification traces of dendrites firstly crystallized and then a homogeneous atom, aluminum,
increases the possibility of obtaining finer Zinc grain. is continuously pushed into a liquid phase. As a result, large
0058. In another embodiment of the present invention, amounts of aluminum are segregated at the grain boundaries
there is provided a hot-dip galvanized steel sheet in which the where the latest solidification takes place. Here, as described
average crystalline texture particle diameter of a solidified above, aluminum present at the grain boundaries improves
Zinc crystal of hot-dip galvanized layer exhibiting Superior corrosion resistance of the unstable grain boundaries, thus
corrosion resistance, oil stain resistance and blackening resis resulting in uniform and improved corrosion resistance
tance and favorable Surface appearance is in a range of 10 to throughout the coating layer. By the way, upon development
88 and not less than 50% of aluminum (Al) in a surface layer of dendrites, they are formed first and as a result, aluminum
portion of a coating layer is in the vicinity of the grainbound does not migrate from the initial nucleation sites to the grain
ary. boundaries but aluminum is trapped between arms of den
0059. That is, in the hot-dip galvanized steel sheet in drites. Consequently aluminum cannot be present at the grain
accordance with the present invention, the average texture boundaries and is present in the pool of molten Zinc formed
size of the coating layer is in a range of 10 to 88 and a certain between dendrites. In this case, stabilization effects of the
portion of aluminum (Al) present in a Surface layer portion of grain boundaries by aluminum cannot be obtained as
the coating layer should be segregated in the vicinity of grain described above, and corrosion resistance is then deterio
boundaries. Aluminum having high corrosion resistance is rated. However, since the hot-dip galvanized steel sheet in
largely distributed around grain boundaries, leading to stabi accordance with the present invention refers to a steel sheet
lization of grain boundaries, and thus serves to inhibit corro that contains a small amount of molten Zinc pool due to a
sion of grain boundaries. Small Spangle size and no growth traces of dendrites, alumi
0060 An increase in corrosion resistance exerted by alu num is enriched at the grain boundaries upon Solidification
minum in the hot-dip galvanized layer can be seen from the and the grainboundaries are finally solidified. Hence, in order
US 2008/0206592 A1 Aug. 28, 2008

to ensure that aluminum is distributed at the grainboundaries, ness and whiteness according to respective regions through
it is advantageous when dendrites are not observed in the out the surface of the steel sheet provides the feeling of overall
coating texture and the size of the coating texture is Smaller. non-uniformity, thereby deteriorating the grade of external
0064. In a further embodiment of the present invention, appearance.
there is provided a hot-dip galvanized steel sheet wherein an 0071. However, in the hot-dip galvanized steel sheet in
average texture size of a hot-dip galvanized layer having accordance with the present invention wherein an average
Superior corrosion resistance, oil stain resistance and black texture size of hot-dip galvanized layer is in a range of 10 to
ening resistance and favorable Surface appearance is in a 88 and a height difference betweenhills and valleys formed
range of 10 to 88 land a height difference between hills and on the coating layer in an arbitrarily selected circular area
Valleys formed on the coating layer in an arbitrarily selected having a radius of 5 mm on the surface of the steel sheet is less
circular area having a radius of 5 mm on the Surface of the than 25% of a coating thickness, occurrence of flow marks or
steel sheet is less than 25% of a coating thickness. Surface defects after skin-pass rolling is significantly reduced.
0065 Solidification traces of dendrites, when they are 0072 That is, where the unevenness degree of coating
Solidified, occur due to particular crystal planes and crystal layer is not less than 25% of the coating thickness, skin-pass
directions at which solidification nuclei preferentially grow. rolling leads to locally non-uniform roughness of the coating
When dendrites grow, since solidification of dendrites layer, thereby resulting in poor Surface appearance. In con
progresses in the thickness direction of the coating layer and trast, as the unevenness degree of coating layer becomes
the direction parallel to the surface of the steel sheet while Smaller, the coating layer exhibits Superior physical proper
consuming molten Zinc present therearound, the point where ties such as favorable Surface appearance, and high corrosion
solidification of dendrites is first initiated takes a convex resistance, oil stain resistance and blackening resistance.
shape (/), whereas the grain boundary, which corre Where the unevenness degree of coating layer is less than
sponds to a pool of molten zinc which is finally solidified, 25% of the coating thickness, it is difficult to recognize non
takes a concave shape (), which may result in unevenness of uniformity of roughness by naked eyes even when non-uni
Surface profile. Increases in unevenness on the Surface of the form roughness after skin-pass rolling occurs due to differ
coating layer may cause the problems which will be illus ences in thicknesses of the coating layer, and thereby the
trated hereinafter. coating layer is recognized to have uniform appearance.
0066. In the hot-dip galvanized steel sheets, skin-pass roll 0073. Additionally, in many cases of hot-dip galvanized
ing is usually carried out after Solidification of the coating steel sheets, crystal lattice planes usually exhibit preferred
layer. Skin-pass rolling is performed in order to improve orientation of (0002) plane. As the (0002) plane exhibits
Surface mechanical properties, remove Surface defects, Superior corrosion resistance and blackening resistance, it is
impart uniform Surface roughness and improve steel sheet advantageous to have preferred orientation of (0002) plane in
flatness. terms of quality. Meanwhile, when it is skin-pass rolled, the
0067. Usually, where skin-pass rolling is performed, Zinc-galvanized texture is deformed by mechanical force and
minute spot-like Surface defects Such as dross are not discern thereby preferred orientation of (0002) plane is broken as an
ible by naked eyes, due to Surface roughness-conferring amount of skin-pass rolling is increased. However, where the
effects by skin-pass rolling. However, where minute uneven spangle size is not more than 88 and the unevenness degree
ness is present on the coating layer, Such surface unevenness of coating layer is less than 25% of the coating layer thick
is further revealed by skin-pass rolling and thus Surface ness, preferred orientation of (0002) plane is not impaired
appearancehaving the feeling of inferiority may beformed on even with skin-pass rolling and preferred orientation prior to
the coating layer. skin-pass rolling is maintained.
0068 Occurrence of non-uniform appearance following 0074 These results represent that deformation of the coat
skin-pass rolling may be due to non-flatness of the Steel sheet, ing texture occurs less by skin-pass rolling as the coating
but surface defects, called flow marks and check marks, result texture becomes smaller. Such phenomena is believed to be
from minute differences in degrees of skin-pass rolling due to the fact that deformation in the coating texture was
according to respective regions because there is the presence Small due to a small amount of unevenness in the coating layer
of unevenness on the Surface of the coating layer. and deformation upon skin-pass rolling took place along the
0069. That is, if skin-pass rolling is not carried out, it is grain boundaries.
difficult to observe differences in scattering and reflection of 0075. It is preferred that less amounts of zinc grains having
light due to minute unevenness by naked eyes. Whereas, if a spangle size exceeding 88 are present in the coating layer
skin-pass rolling is carried out, this may lead to non-unifor of the hot-dip galvanized steel sheet in accordance with the
mity in Surface roughness and therefore the respective regions present invention, but an amount of spangles exceeding 88 in
may be viewed differently and may have the feeling of non a particle diameter may be permitted within a range of 10%
uniform appearance. and preferably 5%. However, if the amount of spangles is
0070. In other words, if local unevenness occur in the greater than the above range, this may result in problems
depth direction of the Surface of the coating layer, roughness associated with degradation of corrosion resistance, oil stain
imparted by skin-pass rolling is different according to respec resistance and blackening resistance, and deterioration of
tive regions. Hence, differences occur in reflection properties Surface appearance.
of light and Such differences appear as Superficial defects. 0076 Further, the surface layer portion of the coating layer
That is, the convex (-) region protruded from the surface preferably contains phosphorus in an amount of 0.1 to 500
of the coating layer is Subject to a large amount of skin-pass mg/m. Where the content of phosphorus is less than 0.1
rolling, which results in a rough Surface, thereby lowering mg/m, a binding amount of phosphorus which plays an
gloss and increasing whiteness. Whereas, the concave (III) important role in creation of solidification nuclei is too small,
region, which is Subject to less skin-pass rolling, exhibits high thereby leading to failure in micronization of the coating
gloss and low whiteness. Occurrence of differences in glossi texture. In contrast, where the content of phosphorus exceeds
US 2008/0206592 A1 Aug. 28, 2008

500 mg/m, the binding amount of phosphorus is too large, 419° C., and most preferably 420° C. to 419° C. As used
thereby resulting in a high risk of adverse effects on phos hereinbefore, the term hot-dip galvanization temperature
phate treatment performance in a painting process of motor refers to a temperature of the steel sheet which was air-wiped
vehicles. in a coating process. By spraying water or aqueous solution
0077. The hot-dip galvanized steel sheet in accordance on the steel sheet from the point of hot-dip galvanization
with the present invention having the coating texture as temperature, the steel sheet is cooled and molten Zinc is
described above can be manufactured as follows. Solidified. However, according to experiments, only the liq
0078. In general, when a zinc-galvanized layer in a molten uid droplets, which were bound at the steel sheet temperature
state is cooled, the coating layer is solidified through a pro of about 419°C., can serve as solidification nuclei, whereas
cess in which solidification nuclei are produced and the nuclei water or aqueous solution, which was sprayed on the Steel
grow. Therefore, in order to hot-dip galvanize a steel sheet sheet before or after the molten zinc began to solidify, merely
Such that the Spangle-free hot-dip galvanized steel sheet in plays a role to take heat capacity from the steel sheet. There
accordance with the present invention is obtained, it is nec fore, in order to form a multitude of solidification nuclei, it is
essary to accelerate formation of the Solidification nuclei and essential to spray water or aqueous solution on the steel sheet
inhibit growth thereof in the solidification reaction. That is, at near 419°C. That is, if the temperature of the steel sheet at
solidification should be completed under conditions that a the initiation point of solution spraying is lower than 419°C.,
density of the solidification nuclei is increased in a solidifi the coating texture becomes large and there is a risk traces of
cation reaction step of the coating layer and dendrites are not dendrites will occur. However, since it is difficult to precisely
developed and grown. According to the present invention, in
order to secure large amounts of Solidification nuclei and determine a temperature of the steel sheet under production,
prevent development and growth of dendrites, the density of although it is safe to spray the solution at a temperature of
the Solidification nuclei is increased by spraying water or an 419 C. or higher at which point the zinc is in a completely
aqueous solution on the surface of the steel sheet. Further, molten state because coarsening of the coating texture can be
liquid droplets of the aqueous solution are passed through a prevented, it is preferred to render the spray temperature as
mesh-like high-voltage charged electrode which is electri close to 419°C. to the maximum extent possible. Further, if
cally charged with a high voltage of -1 to -50 kV, thereby spraying of the solution is stopped when the temperature of
increasing the density of the Solidification nuclei. That is, due the steel sheet is higher than 417° C., there is a risk of re
to application of high-voltage, the aqueous Solution is melting of solidification nuclei which were already produced.
sprayed in the form of a multitude of Small liquid droplets Therefore, upon cooling to a maximum of 415°C., sufficient
which are then bound to the steel sheet, and the small liquid Solidification and cooling are effected and spraying of water
droplets serve as Solidification nuclei, thereby resulting in an or aqueous Solution is completed. Most preferably, spraying
increased density of Solidification nuclei. Consequently, a is finished at the temperature of the steel sheet of about 417
Solidification rate increases and dendrites do not develop, C
thereby resulting in formation of particulate fine texture. I0081. It is important to bind large numbers of liquid drop
0079. In a manufacturing method of a hot-dip galvanized lets to the steel sheet per unit area of the steel sheet in the
steel sheet in accordance with one embodiment of the present above spray initiation and completion temperature ranges.
invention, a steel sheet for hot-dip galvanization is first pre Upon considering this point, it is advantageous to spray
pared and is dipped in a bath of a zinc-coating Solution con Small-sized liquid droplets rather than large-sized liquid
taining 0.13 to 0.3% by weight of conventional aluminum. droplets at the same spraying amount of the solution because
Kinds of the steel sheets are not particularly limited and larger numbers of liquid droplets can be secured.
therefore any steel sheets which are known to be commonly
used in hot-dip galvanization can be used in the present inven I0082. Therefore, in the present invention, sprayed liquid
tion. After dipping the steel sheet in the zinc-coating Solution droplets of water or aqueous Solution are passed through a
bath, the coating solution excessively bound to the steel sheet mesh-like high-voltage charged electrode which is electri
is removed and the steel sheet is air-wiped to control a coating cally charged with a high voltage of -1 to -50 kV, thereby
amount. The coating amount may be generally controlled by charging liquid droplets of the water or aqueous solution with
consumers of the steel sheet, if necessary. Although the coat static electricity, which results in binding of liquid droplets to
ing amount is not particularly limited, it is adjusted to a range the steel sheet via electrical attraction therebetween. Since
of about 40 to 300 g/m in terms of zinclm of one side of the use of the mesh-like charged electrode results in a uniform
steel sheet. electrical field formed by the charged electrode, effects by a
0080. Thereafter, spraying of water or aqueous solution is high voltage are more effective. When the liquid droplets of
initiated at the temperature of the air-wiped steel sheet and is water or aqueous solution pass through the mesh-like high
continued until the steel sheet is cooled to at least 417°C. That Voltage charged electrode, electrostatic atomization occurs
is, water or aqueous Solution is sprayed onto the Surface of the and large-sized liquid droplets are finely divided into Small
air-wiped steel sheet, using a steel sheet temperature in the sized liquid droplets, thus resulting in a decreased average
range of a hot-dip galvanization temperature to 419' C. as a size of liquid droplets and increased numbers thereof. In
spray initiation temperature and using a steel sheet tempera addition, Small liquid droplets as well as large liquid droplets
ture in the range of 417°C. to 415° C. as a spray completion are bound to the steel sheet via electrical attraction therebe
temperature. This is because, in order to facilitate formation tween, thereby improving binding efficiency and therefore it
of solidification nuclei, it is effective to impart solidification is possible to diminish a size of the coating texture.
nuclei from an external source. Spraying of water or aqueous I0083. Further, since water or aqueous solution liquid drop
solution is preferably initiated at a steel sheet temperature in lets are bound to the steel sheet via electrostatic attraction
a range of a hot-dip galvanization temperature to 417° C. therebetween, occurrence of pitting caused by impingement
preferably 460° C. to 419°C., more preferably 430° C. to of large liquid droplets having large momentum against the
US 2008/0206592 A1 Aug. 28, 2008

Zinc-galvanized layer in a molten state is prevented and as a phorus bound to the surface layer portion of the steel sheet.
result, damage to Surface appearance of the steel sheet is Where the content of phosphate is less than 0.1 mg/m, the
prevented. binding amount of phosphorus which plays an important role
0084 As the applied voltage is higher, such effects are in creation of solidification nuclei is too small, thereby lead
pronounced. However, where the voltage is less than -1 kV. ing to failure in micronization of the coating texture. In con
coarse Zinc grains are formed. An excessive increase in Volt trast, where the content of phosphate exceeds 500 mg/m, the
age may cause occurrence of electrical sparks between the binding amount of phosphorus is too large, thereby resulting
charged electrode and steel sheet and therefore it is preferred in high risk of adverse effects on phosphate treatment perfor
to use a voltage of not more than -50 kV. At this time, high mance in a painting process of motor vehicles. The amount of
voltage may be applied by DC, pulse, or DC with addition of phosphorus bound to the surface layer portion of the steel
a high Voltage pulse. Preferably, the high Voltage pulse has a sheet is controllable by adjusting the content of phosphate in
frequency of not more than 1000 Hz. Where frequency is the solution and the spray amount of the aqueous solution.
higher than 1000 Hz, binding efficiency-improving effects 0090. Meanwhile, in continuous zinc-galvanization lines,
possessed by the high Voltage pulse are not exerted, thus there are flows of fluid due to numerous factors, which pre
failing to obtain effects of using an expensive pulse generator. vents binding of liquid droplets, such as air current moving
0085. Further, upon spraying the aqueous solution on the along with the steel sheet upon movement thereof, a rising
steel sheet, liquid droplets of water or aqueous Solution are current of air ascending from a high-temperature hot-dip
preferably sprayed by two-fluid spray nozzle. This is because galvanization pot, and air current resulting from a high-tem
use of the two-fluid spray nozzle is preferred in atomization of perature of the steel sheet. Smaller liquid droplets are signifi
liquid droplets. cantly affected by such air currents, leading to difficulty in
I0086. In addition, as a solute dissolved in the sprayed binding thereof to the steel sheet. Therefore, in order to over
aqueous Solution, it is effective to use the solute that can come such disadvantages, it is necessary to control spray
promote formation of Solidification nuclei on the coating pressure of water or aqueous Solution and air and a ratio
layer. As the Solute that can serve as Solidification nuclei, it is between pressure of water or aqueous solution and air pres
preferred to use phosphate. That is, an aqueous phosphate SU

solution in which phosphate is dissolved in water may be 0091 For such reasons, it is preferred to ensure that upon
used. spraying, pressure of water or aqueous solution is in a range
0087. Where phosphate is used as the solute of the aque of 0.3 to 5 kgf/cm, air pressure is in a range of 0.5 to 7
ous solution, droplets of the aqueous phosphate solution kgf/cm and a ratio of the pressure of water or aqueous solu
bound to the surface of the steel sheet take away latent heat of tion/air pressure is in a range of /10 to 9/10. Where the pressure
the steel sheet by decomposition of phosphoric acid in com of water or aqueous solution is less than 0.3 kgf/cm, there is
bination with water evaporation. POs compounds remaining no atomizing effects of a particle size of zinc crystals. Where
on the surface of the steel sheet serve as solidification nuclei, the pressure of water or the aqueous solution exceeds 5 kgf/
and the coating layer proceeds to Solidify from around those cm, it is undesirable in that surface appearance of the steel
solidification nuclei. Since about one solidification nucleus sheet is damaged due to occurrence of pitting marks caused
forms one spangle, Smaller droplets of the aqueous Solution at by collision of liquid droplets of the solution on the surface of
the same spray amount thereof lead to increased density of the steel sheet.
Solidification nuclei and are thus advantageous for production 0092. Meanwhile, where air pressure is less than 0.5 kgf/
of a spangle-free hot-dip galvanized steel sheet. Therefore, cm, this may undesirably lead to difficulty in binding of
the hot-dip galvanized steel sheet in accordance with the liquid droplets of the sprayed solution to the steel sheet due to
present invention can be advantageously produced by a excessively low spray pressure. In contrast, where air pres
method of spraying the aqueous phosphate solution having a sure exceeds 7 kgf/cm, the kinetic energy of sprayed liquid
proper concentration of phosphate in order to further accel droplets is too large and this undesirably results in occurrence
erate creation of solidification nuclei in the solidification of pitting marks wherein the Surface of the coating layer is
reaction. hollowed by liquid droplets, thereby causing damage to Sur
0088. There is no particular limit to kinds of phosphates face appearance of the coating layer.
and conventional phosphates may be used. Examples of phos 0093. Where a ratio of water or aqueous solution pressure/
phates that can be used in the present invention may include air pressure is less than /10, the solution is not sprayed,
ammonium hydrogen phosphate, ammonium calcium phos thereby failing to exert micronizing effect of the coating
phate and ammonium Sodium phosphate. In addition, a con texture. In contrast, where a ratio of water or aqueous Solution
centration of phosphate in the aqueous Solution is preferably pressure/air pressure exceeds 9/10, drop marks occur, which
in a range of 0.01 to 5% by weight interms of phosphoric acid. then results in damage to Surface appearance.
Where the concentration of phosphoric acid is less than 0094. By installing air curtains at the bottom of a solution
0.01% by weight, it is undesirable due to no effects of phos spray bath to blockair currents ascending from a molten Zinc
phate used. In contrast, where the concentration of phospho bath, it is preferred to constantly maintain flowing condition
ric acid exceeds 5% by weight, it is undesirable because of the of the solution spray bath if possible while simultaneously
possibility to cause plugging of a spray nozzle by the phos keeping the steel sheet at the constant temperature upon
phate compound which is present in a particulate state with spraying the solution. In addition, as liquid droplets falling
out being dissolved. from the solution spray bath to a coating bath are removed by
0089 Even though the amount of phosphate in the aque the air which is blown into the air curtain, the air curtain
ous Solution, necessary to obtain the coating texture proposed eliminates liquid droplets falling from the spray bath to the
by the present invention, may be varied depending on latent coating bath. Consequently, the air curtain serves to block
heat possessed by the steel sheet, the amount of phosphate is liquid droplets falling to the coating bath from the Solution
preferably in a range of 0.1 to 500 mg/m in terms of phos spray bath.
US 2008/0206592 A1 Aug. 28, 2008

0095. When liquid droplets bind to the steel sheet, water stabilization roll 4 serves to fix the steel sheet 2 so as not to be
evaporates in the form of vapor. In addition, a portion of water shaken when it is introduced into the spray bath 6.
or aqueous solution liquid droplets, which were not bound to 0100. The spray bath 6 is located at an appropriate position
the steel sheet, are removed by suction hoods installed at the over air knives 5. The appropriate position is restrained by
top of the solution spray bath and therefore it is possible to hot-dip galvanization conditions and limitations of steel sheet
ensure pleasant working conditions. temperature upon spraying, and the appropriate position of
0096. The hot-dip galvanized steel sheet prepared by the the spray bath 6 may be optimally determined by those skilled
method of the present invention has aparticle diameter of zinc in the art, taking into consideration the above-mentioned
crystals of a coating layer ranging from 10 to 88 and shows factors. For example, as a thickness of the steel sheet, line
no solidification traces of dendrites upon observing under a speed and/or coating amounts increase, the distance between
microscope at a magnification of 100x. These results are the spray bath and air knives becomes more distant. The steel
believed to be due to the fact that liquid droplets bound to the sheet 2 is air-wiped at air knives 5, thereby controlling an
steel sheet serve as Solidification nuclei, thus leading to amount of molten zinc bound to the steel sheet 2.
increased density of Solidification nuclei, and consequently a 0101 Spray nozzle 7 and charged electrode 8 are placed
particle diameter of Zinc crystals becomes Small and Solidi inside the spray bath 6. The spray nozzle 7 is placed at a
fication is completed under conditions at which dendrites did suitable distance from the steel sheet 2 such that the spray
not develop and grow. Because Solidification is completed nozzle 7 is directed toward the steel sheet 2. The spray nozzle
under conditions at which dendrites failed to develop, crystal 7 may be one or more and two-fluid spray nozzle is preferred
orientation according to respective Zinc grain is maintained at as mentioned hereinbefore. Charged electrodes 8 are placed
almost the same state, thereby providing uniform electro between the steel sheet 2 and spray nozzle 7 such that charged
chemical properties as compared to when dendrites are electrode 8 is directed toward faces of the steel sheet 2.
present.
0102. By having Such an arrangement, as liquid droplets of
0097. In addition, as a zinc crystal particle diameter of the water or aqueous solution sprayed through spray nozzle 7
coating layer becomes finer, a difference in height between pass through a mesh-like high-voltage charged electrode 8
hills (/) and valleys (III) on the surface of the coating layer which is electrically charged with a high Voltage, the liquid
is reduced and as a result, an arbitrarily selected circular area droplets are electrostatically charged and thereafter may be
having a radius of 5 mm on the surface of the steel sheet
exhibits a height difference betweenhills and valleys formed bound to the steel sheet 2. The charged electrode 8 may be one
in the coating layer, which is less than 25% of a coating or more. In addition, a distance between the steel sheet 2 and
thickness. mesh-like charged electrode 8 should be shorter than a dis
0.098 Meanwhile, under conventional solidification con tance between the spray nozzle 7 and charged electrode 8. By
ditions, aluminum is not present at the grainboundaries but is fabricating to have such arrangement, an electrical field may
present in the interior of grains. However, if creation of solidi be effectively formed between the charged electrode 8 and
fication nuclei is accelerated and growth of dendrites is inhib steel sheet 2 and binding efficiency of liquid droplets is
ited by the method of the present invention, solidification of increased.
the zinc-galvanized layer is terminated toward the Surface 0103) Further, air curtains 9 are additionally installed at
layer portion thereof and progresses in a direction parallel to the bottom of the spray bath 6 so as to block air currents
the Surface of the steel sheet, thereby resulting in segregation ascending from the hot-dip galvanizing bath 1. Such that
of aluminum near the grain boundaries. flowing condition of the spray bath 6 is constantly maintained
0099. The above hot-dip galvanized steel sheet of the if possible while simultaneously keeping the steel sheet at
present invention having properties similar to those of elec constant temperature upon spraying the Solution. Air curtains
troplated materials and the method of manufacturing the 9 also block liquid droplets falling to the zinc-coating bath 1
same provide Superior corrosion resistance, oil stain resis from the solution spray bath 6. Air curtains 9 have slit-like air
tance and blackening resistance, and favorable Surface spray orifices which are parallel to the surface of the steel
appearance. Therefore, Such a steel sheet can be used as a sheet 2.
material for use in inner and outer plates of car body, house 0104 Suctionhoods 10 are additionally installed at the top
hold electric appliances and building materials and steel sheet of the spray bath 6, in order to prevent sprayed liquid droplets
for painting. In the method of manufacturing the hot-dip
galvanized steel sheet in accordance with the present inven from being scattered into a plant along the steel sheet 2 from
tion, there may be used a device for manufacturing a hot-dip the top of the spray bath 6. That is, after liquid droplets are
galvanized steel sheet, comprising a pair of air knives posi bound to the steel sheet, water which is evaporated in the form
tioned over a zinc-coating bath to control a coating amount of of vapor, and a portion of water or aqueous solution liquid
a plated Steel sheet; one or more water or aqueous solution droplets which are evaporated without being bound to the
spray nozzles positioned toward the steel sheet in a spray bath steel sheet, are removed by suction hoods 10 located on the
over air knives; and a mesh-like charged electrodepositioned top of the spray bath 6 and therefore it is possible to ensure
between the spray nozzle and steel sheet. FIG. 6 is a sche pleasant working conditions.
matic view showing a hot-dip galvanization device in accor
dance with the present invention. As shown in FIG. 6, upon Mode for the Invention
hot-dip galvanization, a steel sheet 2 is dipped in a coating
bath 1, and the steel sheet 2 is then passed through a sink roll EXAMPLES
3 and a stabilization roll 4 in the coating bath 1 and is provided
to a spray bath 6. The sink roll 3 serves to diverta direction of 0105 Now, the present invention will be described in more
the steel sheet introduced into the coating bath 1, and the detail with reference to the following examples. These
US 2008/0206592 A1 Aug. 28, 2008

examples are provided only for illustrating the present inven observed for the coating layers formed by the above-men
tion and should not be construed as limiting the scope and tioned hot-dip galvanization. The results thus obtained are
spirit of the present invention. given in Table 1 below.
0108. The grain size of the zinc was determined by a
Example 1 method involving magnifying a Surface area of a specimen
having a size of 10 mmx10 mm to 100x and measuring the
0106 A steel sheet having a thickness of 0.8 mm was number of total crystalline Zinc grains contained in that area.
air-wiped under conditions of moving at 80 m/min in a hot Traces of dendrites were observed under a microscopy at a
dip galvanizing solution bath composed of a composition magnifying power of 100x. Upon application of a Voltage, the
containing impurities including Fe which is unavoidably Sum of a DC voltage and a high Voltage pulse are set to be a
present and 0.18% by weight of aluminum (Al), such that Zinc target Voltage. Here, Voltage strength of DC and AC was the
was bound to the steel sheet in the sum of 140 g/m for both same. The applied frequency of the high Voltage pulse was
sides of the steel sheet. Then, an aqueous solution of ammo 100 HZ.

TABLE 1.
Solution-spray Characteristics of
Conc. Content in Spray pressure steel sheet coating texture
of surface layer Applied Water or (Water or temperature Coating
phosphate portion of high- aqueous aqueous (initiation- texture Traces of
(1) coating layer voltage solution Air Solutionair) completion) size dendrites
(wt %) (mg/m) (KV) (kgf/cm) (kgf/cm) ratio (° C.) (Lm) others
Examples 1 O.S 1 -50 O3 O.S O6 420-417 80 Nonet
2 O.1 3OO -30 18 3 O6 30 Nonet
3 5 30 -1 18 3 O6 70 Nonet
4 O.S 500 -20 5 7 O.71 20 Nonet
5 O.S 1OO -20 18 3 O6 40 Nonet
6 2 O.1 -30 O6 6 O.1 80 Nonet
7 3 2OO -10 4 5 O.8 30 Nonet
Comparative 1 O.6 <0.1 (trace) O.S OS 3 O.17 423-419 150 Foun
Examples 2 O <0.1 (trace) -50 5 7 O.71 200 Found. Pitting
marks
3 O.S <0.1 (trace) O 18 3 O6 >200 Foun
4 O.S 3OO -60 18 3 O6 30 None, Arc
generated
5 O.S 600 -20 6 8 0.75 30 None/Pitting
marks
6 O.S 550 -20 18 1.7 O6 80 Slightly/Drop
marks
7 O.S <0.1 (trace) -20 18 3 O6 417-415 >200 Foun
8 6 700 -20 1.4 3.0 O.47 420-418 40 None, Nozzle
plugged
9 O.S O.OS -15 O3 0.4 O.8 420-418 100 Foun
10 0.7 <0.1 (trace) -30 O2 O.8 O.25 420-418 >200 Foun
11 0.7 <0.1 (trace) -20 O2 1 O.2 420-418 >200 Foun
12 0.7 600 -20 3 8 0.375 420-418 50 None/Pitting
marks
13 0.7 600 -30 5 6 O.83 420-418 40 None?drop
marks
14 0.7 <0.1 (trace) -30 OS 6 O.08 420-418 2OO Foun

(1) Concentration of phosphate refers to a concentration in terms of phosphoric acid in the aqueous solution.

nium hydrogen phosphate (NH. (H2PO4)) was sprayed on the 0109 Examples 1 through 7 shows the results obtained
surface of the steel sheet via a two-fluid spray nozzle to impart when steel sheets were treated in specified ranges of the
Solidification nuclei, thereby preparing a coating layer. A present invention, and it was possible to obtain coating tex
mesh-like high-voltage charged electrode is disposed tures in accordance with the present invention. As a high
between the two-fluid spray nozzle and steel sheet, such that Voltage is increased, the concentration of phosphate is
the aqueous Solution of ammonium hydrogen phosphate increased and spray pressure is increased, further micronized
passed through the spray nozzle was bound to the steel sheet Zinc grains can be obtained.
via the charged electrode. Coating was carried out by install 0110 Comparative Example 1 shows the results obtained
ing air curtains at the bottom of the spray nozzle and installing when a high-voltage is low and it can be seen that a coarse
Suction hoods at the top of the spray bath. texture was formed. In Comparative Example 2, high air
pressure was used and it can be seen that kinetic energy of
0107 Here, a deviation in binding amounts of the coating sprayed liquid droplets was too large and thereby liquid drop
layer was 10%. Solidification conditions of the coating layers lets caused occurrence of pitting marks, thus resulting in
in Examples 1 through 7 and Comparative Examples 1 hollowing of the coating layer Surface. Comparative Example
through 14 were varied as set forth in Table 1 below. Grain 3 corresponds to when a high Voltage was not applied, thus
sizes of zinc and solidification traces of dendrites were representing that coarse coating texture was formed similar to
US 2008/0206592 A1 Aug. 28, 2008

Comparative Example 1. Comparative Example 4 corre given in Table 2 below. Corrosion resistance, oil stain resis
sponds to when a high Voltage exceeds the specified range of tance and blackening resistance were evaluated according to
the present invention, and the results show that a fine coating the following methods.
layer was formed at an early stage, but there was a risk of fire
in hot-dip galvanization facilities due to occurrence of elec Corrosion Resistance
tric arc during coating operations. In Comparative Example 5.
high-spray pressure of the aqueous solution and air was used 0112 Corrosion resistance was determined by a Salt
and pitting marks were occurred similar to Comparative Spray Test. For this purpose, saltwater was sprayed on a steel
Example 2. Comparative Example 6 is the case in which sheet. The Salt Spray Test was carried out according to JIS Z
water pressure was higher than air pressure. The results show 2371 as follows: salt water was sprayed on a steel sheet under
that an average size of the coating texture was 80 l but large test conditions of a salt concentration: 5+1 wt %, pH: 6.9,
Solution drops have quenched the coating texture, thus lead temperature: 35+1° C., a spray amount: 1 cc/hr, for 72 hr.
ing to occurrence of drop marks and the coating texture hav followed by evaluating a degree of occurrence of red rust on
the surface of the steel sheet.
ing a size of more than 88 has exceeded 10%. Comparative
Example 7 is the case in which a temperature of the steel sheet Oil Stain Resistance
was low upon spraying a solution and the results show that a
size of the coating texture was large and traces of dendrites 0113 For measuring oil stain resistance, 5% by weight of
were observed. Comparative Example 8 is the case in which water was suspended in anti-corrosive oil, BW-90EG (Buh
a concentration of phosphate was high and the results show mwoo corporation, Seoul, Korea), and the resulting Suspen
that prolonged operation has resulted in clogging of a nozzle. sion was applied to a steel sheet. After one day storage of the
Comparative Examples 9 through 11 correspond to when steel sheet in a hot-air drying furnace at 85°C., a degree of
spray pressure of aqueous solutions was low and the results discoloration in appearance thereof was evaluated.
show that there were no micronizing effects of the Zinc grain.
Comparative Example 12 is the case in which airpressure was Blackening Resistance
high and the results show that occurrence of pitting marks was
observed similar to Comparative Example 2. Comparative 0114 Blackening resistance was evaluated by storing a
Example 13 is the case in which a ratio of a solution:air specimen in a humidity cabinet at 49° C. and relative humid
pressure exceeded a limited range. The results show that the ity of 95% for 120 hours and measuring a degree of discol
coating texture having a size of 40 was obtained and the oration of the steel sheet.
coating texture having a size of not less than 88 was also less 0.115. As a conventional hot-dip galvanized material
than 10%, but occurrence of drop marks was observed. Com which was used as a reference for analyzing effects of the
parative Example 14 is the case in which a ratio of a solution: present invention, a steel sheet was used which was obtained
air pressure was below a limited range, and the results show by air-wiping the Steel sheet having a thickness of 0.8 mm in
that micronizing effects of the coating texture were not a hot-dip galvanizing Solution bath of Example 1 under con
observed due to failure of Solution spraying. ditions of a moving rate of 80 m/min such that Zinc was bound
to the steel sheet in the sum of 140 g/m for both sides of the
Example 2 steel sheet and then Solidifying the hot-dip galvanized layer
viaaair-cooling manner instead of using an aqueous solution
0111 For the cases in which there were no problems asso spray manner.
ciated with Surface appearance and workability among 0116. In evaluation of corrosion resistance, blackening
Examples 1 through 7 and Comparative Examples 1 through resistance and oil stain resistance, respective symbols have
14, a coating thickness, a size of coating texture, the presence? the following meanings: Q: remarkably improved as com
absence of traces of dendrites, a ratio of difference in a height pared to conventional material; A: equivalent to conventional
between hills and Valleys in a coating layer, segregation of hot-dip galvanized material or a degree of improvement is not
aluminum, corrosion resistance, blackening resistance and oil significant; and X: level equivalent to conventional hot-dip
stain resistance were evaluated. The results thus obtained are galvanized material.

TABLE 2
Height
Size of difference
Coating coating betweenhill and Al
thickness texture Traces of valley coating segregation Corrosion Blackening Oil stain
(Lm) (Lm) dendrites thickness (%) resistance resistance resistance
Examples 1 10 80 None O.20 70 (C) (C) (C)
2 8.5 30 None O.O7 8O (C) (C) (C)
3 10 70 None O.20 70 (C) (C) (C)
4 8 20 None O.OS 8O (C) (C) (C)
5 10 40 None O.13 60 (C) (C) (C)
6 2O 80 None O.25 50 (C) (C) (C)
7 10 30 None O.10 60 (C) (C) (C)
Comparative 1 10 150 Found 30 30 X X X
Examples 3 2O >200 Found O.SO 2O X X X
7 10 >200 Found O.SO 25 X X X
9 8.5 100 Found 0.27 40 A A A
US 2008/0206592 A1 Aug. 28, 2008
11

TABLE 2-continued
Height
Size of difference
Coating coating betweenhill and Al
thickness texture Traces of valley coating segregation Corrosion Blackening Oil stain
(Lm) (Lm) dendrites thickness (%) resistance resistance resistance
10 10 >200 Found O.S 2O X X X
11 8.5 >200 Found 0.4 2O X X X
12 2OO 150 Found O.3 25 X X X
14 10 200 Found O.31 30 X X X

0117. As the coating texture becomes finer and the coating steel sheet, and the axis of ordinates (Y-axis) represents a
thickness is thinner, a ratio of height difference between hills height at a position of the horizontal axis (X-axis). FIG. 2a
and Valleys becomes Smaller and a degree of enrichment of corresponds to Example 5, and represents that a height dif
aluminum at grain boundaries tends to increase. All of ference between the highest point and the lowest point is
Examples 1 through 7 satisfied limited ranges regarding within 1 and at this time, upon considering that a thickness
height difference betweenhills and valleys/coating thickness of a coating layer is a level of 10D (coating amounts for both
ratio and aluminum segregation, and exhibited Superior cor sides: 140 g/D), a height difference between hills and valleys
rosion resistance, blackening resistance and oil stain resis is less than 25% of the coating thickness. FIG.2b is a graph
tance. showing results of determination on a height difference
0118. In Comparative Examples 1, 3, 7, 9 to 12 and 14, between hills and valleys of the coating layer obtained in
corrosion resistance, blackening resistance and oil stain resis Comparative Example 3. When it was measured as in the
tance of the zinc-galvanized steel sheet were not satisfactory, same manner as FIG. 2a, the height difference between hills
Surface unevenness of the coating layer were severe and there and Valleys was not less than 25% of the coating thickness.
was no tendency for preferred segregation of aluminum at
grain boundaries. Example 5
Example 3 0.124. This example was carried out to examine whether
preferred orientation toward (0002) plane of zinc-galvanized
0119. In this example, a size of zinc crystals and the pres layer is maintained after skin-pass rolling of hot-dip galva
ence/absence of dendrites in coating layers of Examples and nized steel sheets under the conditions in which a length of a
Comparative Examples were examined. steel sheet is 1.5% increased by skin-pass rolling, depending
0120 Micrographs (100x) of hot-dip galvanized steel on coating layer textures. FIG. 3a is a graph showing pre
sheet obtained in Example 5 and Comparative Examples 3 ferred orientation of (0002) plane of a coating layer obtained
and 9 are shown in FIGS. 1a, 1b and 1c, respectively. in Example 5. Here, preferred orientation of (0002) plane is
0121. As can be seen from FIG.1a (A), an average particle not damaged even when skin-pass rolling is carried out and
diameter of Zinc crystals in the plating layer of the steel sheet therefore preferred orientation prior to skin-pass rolling is
obtained in Example 5 was in a range of 10 to 88 and maintained. FIG.3b is a graph showing preferred orientation
formation of dendrites was not observed (top). The bottom of of (0002) plane of coating layer obtained in Comparative
FIG. 1a (B) is a graph showing size distribution of coating Example 7. Here, as an amount of skin-pass rolling is
texture in the coating layer of the steel sheet obtained in increased, preferred orientation of (0002) plane is broken.
Example 5. As can be seen therefrom, Zinc crystal particles These results indicate that skin-pass rolling dose not result in
having a diameter exceeding 88 were not more than 10%. deformation of a coating texture when the coating texture is
0122 FIG. 1b is a surface micrograph of a steel sheet small. Such phenomena are presumed to be due to the fact that
obtained in Comparative Example 3, thus representing that unevenness on the coating layer are small, which leads to less
there was development of dendrites in which a diameter of deformation in the coating texture, and also deformation upon
zinc-galvanized texture is not less than 200 FIG. 1c is a skin-pass rolling has occurred along grain boundaries.
Surface micrograph of a steel sheet obtained in Comparative
Example 9, thus representing that an average particle diam Example 6
eter of zinc crystals in a hot-dip galvanized layer was 100 D, 0.125. This example was carried out to measure a degree of
and coating texture exceeding 88 in a size was greater than segregation of aluminum in coating layers.
10%. Further, growth of the coating layer into dendrites was 0.126 FIG. 4a is an EM (200x) showing a degree of seg
also observed.
regation of aluminum in a coating layer of example 5 (left)
Example 4 and an EM (200x) showing results of analysis on a coating
layer of Example 5 using an electron probe micro-analyzer
0123. In this example, height differences between hills (EPMA) (middle). FIG. 4b is an EM (40x) showing a degree
and Valleys of coating layers of hot-dip galvanized steel of segregation of aluminum in a coating layer of Comparative
sheets prepared in a manner of Example 5 and Comparative Example 7 (left) and a photograph (40x) showing results of
Example 3 were measured. As a measuring apparatus, the analysis on a coating layer of Comparative Example 7 using
three-dimensional surface profilometer (WYCO, USA) was an EPMA (middle).
used. In FIGS. 2a and 2b, the horizontal axis (X-axis) repre I0127. The electron probe micro-analyzer (EPMA) is an
sents a distance in a direction of width on the surface of the apparatus which is used for plane analysis of certain ele
US 2008/0206592 A1 Aug. 28, 2008

ments. When the subject element to be analyzed is present on an unstable grain boundary, thus resulting in uniform
the Surface of interest, this apparatus enables confirmation of improvement of corrosion resistance through the coating
the presence of such an element by exhibition of different layer.
Surface colors between an element-free region and element I0134) From comparison between photographs (left and
containing region. middle) of FIG. 4b, corresponding to a coating layer of Com
0128. According to the analysis results of FIG. 4a(middle) parative Example 7, it can be seen that large amounts of
corresponding to Examples of the present invention and FIG. aluminum are segregated in the interior of grains, rather than
at the grain boundary.
4b(middle), obtained by the EPMA, the region in which alu 0.135 FIG. 4b(right) is a side-cross sectional view of a
minum is present is shown brightly, whereas the aluminum coating layer of Comparative Example 7 under Solidification,
free region is shown darkly. wherein a lower part, which is represented by reference
0129. As used herein, the term “grainboundary is defined numeral 11", is a steel sheet and an upper part, which is
as an area within 5 in the right and left direction from the line represented by reference numeral 12", is a coating layer under
representing boundaries of crystals, as shown in EM of FIGS. solidification. Generally, when the hot-dip galvanized layer is
4a (left) and 4b(left). solidified, solidification unclei are created on the interface
0130. A range limited in the present invention is defined as between the steel sheet and coating layer. Thereafter, growth
follows. Firstly, as area of a region exhibiting color difference of dendrites not only progresses laterally but also progresses
(brightness difference) on photographs upon performing toward the Surface. Particularly, upon growing toward the
electron probe micro-analysis is analyzed by an image ana Surface, dendrites grow while consuming molten Zinc present
lyzer and the total area of the region exhibiting color differ therearound. As a result, aluminum is trapped between arms
ence is calculated. Then, the calculated area is divided by the of dendrites, instead of migrating from the initial nucleation
sites to the grainboundary and aluminum is not present at the
total area within 5 in the right and left directions from the grainboundary but is present in a pool of molten Zinc formed
grain boundary as shown in micrographs. Based on these between dendrites. Upon observation of such solidification
calculations, the value in which the area of a region exhibiting behavior by naked eyes, it can be seen that a solidification
color difference (brightness difference) is greater than 50% is pool 14 of molten zinc is formed over a broad area between
the range limited by the present invention. two crystalline textures or within crystalline textures at the
0131 Since Zinc and aluminum contained in the coating end of solidification (see FIG. 4b, right). Via such a solidifi
layer, upon solidification, results in eutectic reaction, a higher cation process, aluminum is, instead of being enriched at the
content of aluminum lowers a solidification point of the coat grain boundary 13, is widely distributed throughout the sur
ing layer. That is, a Zinc alloy, in which a portion of aluminum face of the coating layer. Upon measuring amounts of alumi
is contained, results in lowering of the Solidification point num present at the grain boundary by the above-mentioned
thereof as compared to pure Zinc and upon solidification, method, about 25% of aluminum observed on the surface of
proceeds with Solidification in a manner that pure Zinc is the coating layer was present at the grain boundary. Conse
firstly crystallized and then a homogeneous atom, aluminum, quently, stabilizing effects of aluminum on the grain bound
is continuously pushed into a liquid phase. As a result, a ary cannot be achieved, thus resulting in low corrosion resis
concentration of aluminum is high in a region where the latest tance.
Solidification takes place, while a concentration of aluminum 0.136. As described above, a solidification manner of the
is low in a region where solidification takes place first. coating layer in the hot-dip galvanized steel sheet of Example
0.132. From comparison between photographs (left and 5 becomes different from that of Comparative Example 7, and
middle) of FIG. 4a, corresponding to a coating layer of due to Such a fact, the hot-dip galvanized steel sheet of
Example 5, it can be seen that large amounts of aluminum are Example 5 is believed to have Superior qualities as compared
segregated at the grainboundaries. In addition, when amounts to Comparative Example 7, as shown in Table 2.
of aluminum present at the grainboundary were measured by Example 7
the above-mentioned method, about 60% of aluminum
observed on the Surface of the coating layer was present at the 0.137 This example represents changes blackening resis
grain boundaries. tance of a coating layer with respect to a varying amount of
0.133 FIG. 4a(right) is a side-cross sectional view of a skin-pass rolling. FIG. 5 shows the results of measurement of
coating layer of Example 5 under Solidification, wherein a changes in blackening resistance of Steel sheets, when the
lower part, which is represented by reference numeral 11, is a amount of skin pass rolling is varied for steel sheets of
steel sheet and an upper part, which is represented by refer Example 5 and Comparative Example 7. Here, the amount of
ence numeral 12, is a coating layer under Solidification. A skin-pass rolling was expressed as a degree of how much a
solution, which was sprayed toward the surface of the steel length of the steel sheet was extended by skin-pass rolling.
sheet, forms large quantities of Solidification unclei and That is, much skin-pass rolling of the steel sheet leads to an
increases a cooling rate to accelerate Solidification and extended length thereof. Example 5 exhibits maintenance of
thereby interfaces between the steel sheet and coating layer satisfactory blackening resistance regardless of the amount of
and the Surface of the coating layer are solidified almost at the skin pass rolling (see FIG. 5, line 2). Whereas, it can be seen
same time and grow laterally. In this manner, since the coating from Comparative Example 7 that blackening resistance of
layer is solidified almost simultaneously due to a multitude of the steel sheet is deteriorated as the amount of skin pass
solidification unclei, Zinc is solidified with formation of a rolling increases (see FIG. 5, line 1). It is believed that the
narrow grainboundary 13 (see FIG. 4a, right). At this time, as reason why Such phenomena occur is because, in the coating
the grain boundary 13 undergoes the latest Solidification, texture proposed by the present invention, the preferred ori
large quantities of aluminum are segregated at the grain entation of (0002) plane is maintained even when skin pass
boundary 13, which in turn improves corrosion resistance of rolling is performed and therefore it is possible to maintain
US 2008/0206592 A1 Aug. 28, 2008

quality characteristics which were exhibited before skin pass steel sheet temperature in the range of 417°C. to 415°C.
rolling, regardless of skin pass rolling. as a spray completion temperature;
passing sprayed liquid droplets of water or aqueous solu
INDUSTRIAL APPLICABILITY tion through a mesh-like high-voltage charged electrode
0138 A hot-dip galvanized steel sheet having a coating which is electrically charged with a high Voltage of -1 to
texture in accordance with the present invention exhibits -50 kV; and
advantages such as Superior corrosion resistance, blackening allowing the electrode-passed liquid droplets to be bound
resistance, oil stain resistance, Surface friction coefficient and to the surface of the steel sheet and thereby being served
as solidification nuclei of molten zinc.
Surface appearance. Such a hot-dip galvanized steel sheet is
prepared by a manufacturing method disclosed in the present 7. The method according to claim 6, wherein the spray
invention. The hot-dip galvanized steel sheet having Such initiation temperature is a steel sheet temperature in the range
of 420° C. to 4199 C.
Superior physical properties in accordance with the present
invention can be used for a variety of materials such as inner 8. The method according to claim 6, wherein the liquid
and outer plates of car body, household electric appliances droplets of water oraqueous solution are sprayed by two-fluid
and building materials and steel sheet for painting. spray nozzle.
0.139. Although the preferred embodiments of the present 9. The method according to claim 6, wherein the aqueous
invention have been disclosed for illustrative purposes, those Solution is an aqueous phosphate Solution containing 0.01 to
skilled in the art will appreciate that various modifications, 5% by weight of phosphoric acid.
additions and Substitutions are possible, without departing 10. The method according to claim 6, wherein surface layer
from the scope and spirit of the invention as disclosed in the portion of coating layer contain 0.1 to 500 mg/m of phos
accompanying claims. phorus.
1. A hot-dip galvanized steel sheet wherein a solidified Zinc 11. The method according to claim 6, wherein the liquid
crystal of hot-dip galvanized layer has an average crystalline droplets are sprayed at a pressure of water oraqueous solution
texture particle diameter of 10 to 88 um, and there is no of 0.3 to 5 kgf/cm, an air pressure of 0.5 to 7 kgf/cm and the
Solidification traces of dendrites upon observing under a ratio between the pressure of water or aqueous solution and
microscope at a magnification of 100x. air pressure is in a range of /10 to 9/10.
2. A hot-dip galvanized steel sheet wherein a solidified zinc 12. The method according to claim 6, wherein, among
crystal of hot-dip galvanized layer has an average crystalline sprayed liquid droplets, liquid droplets falling to the coating
textureparticle diameter of 10 to 88 um, and not less than 50% bath are removed by air which is blown into the air curtain.
of aluminum (Al) on a Surface layer portion of a coating layer 13. The method according to claim 6, where, among
is present around the grain boundary. sprayed liquid droplets, liquid droplets other than those
3. A hot-dip galvanized steel sheet wherein a solidified zinc bound to the steel sheet are removed by a suction hood.
crystal of hot-dip galvanized layer has an average crystalline 14. The method according to claim 6, wherein, the high
texture particle diameter of 10 to 88 um, and a height differ voltage is applied by DC, pulse, or DC with addition of a high
ence between hills and Valleys formed on the coating layer in Voltage pulse.
an arbitrarily selected circular area having a radius of 5 mm 15. The method according to claim 14, wherein, the high
on the surface of the steel sheet is less than 25% of a coating voltage pulse has a frequency of not more than 1000 Hz.
thickness. 16. A device for manufacturing a hot-dip galvanized steel
4. The hot-dip galvanized steel sheet according to claim 1, sheet, comprising:
wherein a Zinc crystal particle having a diameter exceeding a pair of air knives positioned over a zinc-coating bath to
88 um is present in an amount of less than 10% in the coating control a coating amount of a plated Steel sheet;
layer texture. one or more water or aqueous solution-spray nozzles posi
5. The hot-dip galvanized steel sheet according to claim 1, tioned toward the steel sheet in a spray bath over air
wherein the Surface layer portion of the coating layer contains knives; and
0.1 to 500 mg/m of phosphorus. a mesh-like charged electrode positioned between the
6. A method of manufacturing a hot-dip galvanized Steel spray nozzle and steel sheet.
sheet, comprising: 17. The device according to claim 15, where, the bottom of
preparing a steel sheet for hot-dip galvanization; the spray bath further includes air curtains, in order to block
dipping the Steel sheet in a bath of zinc-coating Solution air current ascending from the zinc-coating bath.
containing 0.13 to 0.3% by weight of aluminum; 18. The device according to claim 17, wherein, the air
air-wiping the steel sheet having the coating Solution curtains have slit-like air spray orifices which are parallel to
bound thereto, thereby removing an excess of the coat the surface of the steel sheet.
ing solution; 19. The device according to claim 16, wherein, the device
spraying water or an aqueous solution onto the Surface of further includes suction hoods positioned at the top of the
the air-wiped steel sheet, using a steel sheet temperature spray bath.
in the range of a hot-dip galvanization temperature to
419' C. as a spray initiation temperature and using a