Technical Field
[0001] The present invention relates to a method for stably producing a galvanized steel
sheet having low sliding resistance and excellent press formability during press molding
and also relates to a galvanized steel sheet.
Background Art
[0002] Galvanized steel sheets are widely used for various applications such as automotive
bodies. For such applications, the galvanized steel sheets are press-molded for use.
The galvanized steel sheets, however, have a disadvantage that the galvanized steel
sheets are inferior in press formability to cold-rolled steel sheets. This is because
the sliding resistance of the galvanized steel sheets to press molds is greater than
that of the cold-rolled steel sheets. That is, the galvanized steel sheets have portions
with high sliding resistance to press molds and beads and therefore are unlikely to
be provided in the press molds; hence, the galvanized steel sheets are likely to be
broken.
[0003] Galvannealed steel sheets produced through hot-dip galvanizing and then alloying
are more excellent in weldability and coatability as compared with other galvanized
steel sheets and are widely used for automotive bodies.
[0004] A galvannealed steel sheet is one obtained as follows: a steel sheet is galvanized
and is then heat-treated such that an alloying reaction occurs due to the interdiffusion
of Fe in the steel sheet and Zn in a plating layer to create an Fe-Zn alloy phase.
The Fe-Zn alloy phase is usually a coating consisting of a Γ phase, a δ
1 phase, and a ζ phase. Hardness and melting point tend to decrease with a reduction
in Fe concentration, that is, in the order of the Γ phase, the δ
1 phase, and the ζ phase. Therefore, high-Fe concentration coatings are useful in view
of slidability because the coatings have high hardness and a high melting point and
are unlikely to be adhesive. Since press formability is one of important properties
of the galvannealed steel sheet, the galvannealed steel sheet is produced so as to
include a coating with a slightly increased Fe concentration.
[0005] However, the high-Fe concentration coatings have a problem that Γ phases which are
hard and brittle are likely to be formed at plating-steel sheet interfaces to cause
a phenomenon in which peeling occurs at the interfaces, that is, so called powdering,
during machining.
[0006] Patent Documents 1 and 2 disclose techniques for solving the problem. In the techniques,
a galvanized steel sheet is improved in weldability and workability in such a manner
that an oxide film made of ZnO is formed on the galvanized steel sheet by electrolysis,
dipping, coating oxidation, or heating.
[0007] However, the application of the techniques disclosed in the Patent Documents 1 and
2 to the galvannealed steel sheet is not effective in achieving an improvement in
press formability because the galvannealed steel sheet has low surface reactivity
and large surface irregularities because of the presence of Al oxides. Since the galvannealed
steel sheet has low surface reactivity, it is difficult to form a desired coating
on the galvannealed steel sheet by electrolysis, dipping, coating oxidation, or heating
and a portion with low reactivity, that is, a portion containing a large amount of
the Al oxides, is reduced in thickness.
[0008] Since the surface irregularities are large, surface protrusions are brought into
direct contact with a press mold during press molding and contacts between the press
mold and thin portions of the surface protrusions have high sliding resistance; hence,
a sufficient improvement in press formability cannot be achieved.
[0009] Patent Document 3 discloses a technique in which a steel sheet is galvanized by hot
dipping, alloyed by heating, temper-tolled, contacted with an acidic solution with
pH buffering action, held for one to 30 seconds, and then washed with water, whereby
an oxide layer is formed on a plating surface layer.
[0010] Patent Document 4 discloses a method for forming an oxide layer on a flat surface
portion of an unalloyed hot-dip galvanized steel sheet. In the method, the hot-dip
galvanized steel sheet is temper-rolled, contacted with an acidic solution with pH
buffering action, held for a predetermined time in such a state that a film of the
acidic solution is disposed on the steel sheet, washed with water, and then dried.
[0011] A method disclosed in Patent Document 5 is effective in uniformly forming an oxide
layer on an electrogalvanized steel sheet. In this method, the electrogalvanized steel
sheet is contacted with an acidic solution with pH buffering action or an acidic electrogalvanizing
bath, held for a predetermined time, washed with water, and then dried.
Patent Document 1: Japanese Unexamined Patent Application Publication No. 53-60332
Patent Document 2: Japanese Unexamined Patent Application Publication No. 2-190483
Patent Document 3: Japanese Unexamined Patent Application Publication No. 2003-306781
Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-3004
Patent Document 5: Japanese Unexamined Patent Application Publication No. 2005-248262
[0012] In the case of using the techniques disclosed in Patent Documents 3 to 5, good press
formability can be achieved under conventional production conditions. However, it
has become clear that good press formability cannot be achieved in some cases because
the holding time of steel sheets contacted with acidic solutions cannot be sufficiently
secured under recent high-speed conditions and therefore formed oxide layers are thin.
[0013] In order to solve such a problem, it is effective to increase the distance from the
contact with an acidic solution to water washing. However, this needs to secure a
space therebetween, leading to spatial restriction.
[0014] In view of the foregoing circumstances, the present invention has an object to provide
a method capable of stably producing a galvanized steel sheet having excellent press
formability in a reduced space under high-speed conditions and an object to provide
a galvanized steel sheet having excellent press formability.
Disclosure of Invention
[0015] The inventors have made intensive investigations to solve the above problems. As
a result, the inventors have obtained findings below.
[0016] It has turned out from that in the techniques disclosed in Patent Documents 3 to
5, zinc ions dissolved from zinc plating are used to produce zinc oxide on surfaces
and therefore the time taken to dissolve the zinc ions therefrom elongates the time
taken to form the oxide films. Thus, the inventors have considered that if a solution
used to form an oxide film contains zinc ions, the time taken to dissolve the zinc
ions is not needed and therefore the time taken to form the oxide film can be reduced.
However, no oxide film has been sufficiently formed from a solution containing zinc
ions. This is probably because although environments suitable for producing zinc oxides
are created in the techniques disclosed in Patent Documents 3 to 5 since hydrogen
ions are reduced simultaneously with the dissolution of zinc and therefore the pH
in the vicinity of a surface increases, the use of the zinc ion-containing solution
is not enough to increase the pH in the vicinity of a surface and therefore any environment
suitable for producing zinc oxides is not created. Therefore, the inventors have conceived
that a galvanized steel sheet is contacted with an aqueous solution containing zinc
and is further contacted with a weak alkali solution, whereby the pH in the vicinity
of a surface therefore is increased.
[0017] The present invention is based on the above finding. The scope of the present invention
is as described below.
- (1) A method for producing a galvanized steel sheet obtained by forming an oxide layer
on a steel sheet includes contacting the steel sheet with a zinc-containing aqueous
solution having a zinc ion concentration of 1 to 100 g/l, contacting the steel sheet
with an aqueous solution with a pH of 6 to 14, washing the steel sheet with water,
and then drying the steel sheet.
- (2) In the galvanized steel sheet-producing method specified in Item (1), the zinc
ion concentration is within a range from 5 to 100 g/l and the aqueous solution has
a pH of 7 to 13.
- (3) In the galvanized steel sheet-producing method specified in Item (1) or (2), the
zinc-containing aqueous solution has a pH of 1 to 6.
- (4) A galvanized steel sheet produced by the galvanized steel sheet-producing method
specified in any one of Items (1) to (3) includes an oxide layer which principally
contains zinc as a metal component, which is disposed on a steel sheet, and which
has an average thickness of 10 nm or more.
[0018] The term "galvanized steel sheet" as used herein refers to a plated steel sheet having
a coating which is made of zinc and which is disposed thereon and includes a hot-dip
galvanized steel sheet (hereinafter simply referred to as a GI steel sheet); a galvannealed
steel sheet (hereinafter simply referred to as a GA steel sheet); an electrogalvanized
steel sheet (hereinafter simply referred to as an EG steel sheet); a zinc-deposited
steel sheet; a zinc alloy-plated steel sheet containing an alloy element such as Fe,
Al, Ni, Mg, or Co; and the like.
Brief Description of Drawings
[0019]
Fig. 1 is a schematic front view of a coefficient-of-friction tester.
Fig. 2 is a schematic perspective view showing the shape and size of a bead shown
in Fig. 1.
Best Modes for Carrying Out the Invention
[0020] According to the present invention, a galvanized steel sheet having excellent press
formability and low sliding resistance during press molding can be produced in a reduced
space under high-speed conditions.
[0021] In the course of producing a GA steel sheet, a steel sheet is galvanized by hot dipping
and is then alloyed by heating. The GA steel sheet has surface irregularities due
to the difference in reactivity between steel sheet-plating interfaces during alloying.
The alloyed steel sheet is usually temper-rolled for the purpose of material achievement.
A plating surface is smoothed by the contact with rollers during temper-rolling and
the irregularities are reduced. Thus, the force necessary for a mold to crush plating
surface protrusions is reduced during press molding and therefore sliding properties
can be improved.
[0022] Since a flat surface portion of the GA steel sheet is brought into direct contact
with the mold during press molding, the presence of a hard refractory substance capable
of preventing the adhesion to the mold is important in improving slidability. In this
viewpoint, the presence of an oxide layer on a surface layer is effective in improving
slidability because the oxide layer prevents the adhesion to the mold.
[0023] Since surface oxides are worn or are scraped during actual press molding, the presence
of a sufficiently thick oxide layer is necessary when the contact area between a mold
and a workpiece is large. Although a plating surface has an oxide layer formed by
heating during alloying, most of the oxide layer is broken during temper rolling because
of the contact with rollers and therefore a fresh surface is exposed. Hence, in order
to achieve good slidability, a thick oxide layer needs to be formed prior to temper
rolling. Even if such a thick oxide layer is formed prior to temper rolling in consideration
of this, the breakage of the oxide layer cannot be avoided during temper rolling and
therefore oxide layers are nonuniformly present on flat portions. Hence, good slidability
cannot be stably achieved.
[0024] Good slidability can be stably achieved by forming a uniform oxide layer on the temper-rolled
GA steel sheet, particularly on a plating surface flat portion.
[0025] The following technique is effective in uniformly forming a oxide layer on a zinc
plating: a technique in which a galvanized steel sheet is contacted with an acidic
solution with pH buffering action, held for a predetermined time in such a state that
a film of the acidic solution is disposed on the steel sheet, washed with water, and
then dried. However, the formed oxide layer is thin because the time for which the
steel sheet is held subsequently to the contact with the acidic solution is not sufficiently
secured under recent high-speed conditions as described above; hence, good press formability
cannot be achieved in some cases. It is effective in solving this problem to increase
the distance from the contact with the acidic solution to water washing. However,
this needs to secure a space therebetween, leading to spatial restriction.
[0026] In the present invention, it has been invented that a galvanized steel sheet is contacted
with an aqueous solution containing zinc ions and is further contacted with a weak
alkali aqueous solution such that an increase in pH is caused. In the present invention,
it is an important requirement and feature that the galvanized steel sheet is contacted
with the zinc ion-containing aqueous solution and is further contacted with the weak
alkali aqueous solution. This allows an oxide layer sufficient to secure good press
formability to be formed in a reduced space without suffering from spatial restriction.
[0027] A mechanism for forming the oxide layer is not clear but is probably as described
below. Since the galvanized steel sheet is contacted with the zinc ion-containing
aqueous solution and is then contacted with the weak alkali aqueous solution in such
a state that the steel sheet is covered with the zinc ion-containing aqueous solution,
the pH of the zinc ion-containing aqueous solution on the steel sheet is increased
to a pH level where oxides (hydroxides) are stable. This probably results in the formation
of the oxide layer, which is stable, on the galvanized steel sheet.
[0028] In the present invention, the oxide layer is formed on the galvanized steel sheet
in such a manner that the steel sheet is contacted with the zinc-containing aqueous
solution, contacted with the weak alkali aqueous solution, that is, an aqueous solution
with a pH of 6 to 14, washed with water, and then dried.
[0029] In the present invention, the weak alkali aqueous solution has a pH of 6 to 14. Zinc
is an amphoteric metal and therefore is soluble in extremely low and high pH solutions.
Thus, in order to form the oxide layer, the aqueous solution on the galvanized steel
sheet needs to be rendered alkaline. The pH thereof is preferably 7 to 13 and more
preferably 9 to 11.
[0030] The concentration of zinc in the aqueous solution is within a range from 1 to 100
g/l in the form of zinc ions. When the concentration of the zinc ions is less than
1 g/l, a sufficient amount of zinc is not supplied and therefore the oxide layer is
unlikely to be formed. When the concentration thereof is greater than 100 g/l, the
concentration of sulfuric acid in the oxide layer is high and therefore it is concerned
that the oxide layer is dissolved in a subsequent chemical conversion step to contaminate
a conversion solution. The concentration is preferably within a range from 5 to 100
g/l.
[0031] In order to form the oxide layer from a stable zinc compound, the zinc ions are preferably
used in the form of a sulfate. In the case of using the sulfate, there is probably
an advantage that sulfate ions are captured in the oxide layer to stabilize the oxide
layer.
[0032] The pH of the zinc-containing aqueous solution is not particularly limited and is
preferably 1 to 6. When the pH thereof is greater than 6, the zinc ions form precipitates
in the aqueous solution (the formation of a hydroxide) and are not provided on the
steel sheet in the form of an oxide. When the pH thereof is less than 1, the dissolution
of zinc is promoted; hence, the mass per unit area of plating is reduced and a plating
film has cracks and therefore is likely to be stripped off during machining. When
the pH thereof is high within the range of 1 to 6, the pH thereof quickly increases
to a level where oxides are stable upon the contact with the weak alkali aqueous solution.
This is advantageous in forming the oxides. Therefore, the pH thereof is preferably
within the range of 4 to 6.
[0033] The solution disclosed in Patent Document 3 is characterized by being acidic and
by having a pH buffering action. However, the zinc ion-containing aqueous solution
is used herein and therefore the oxide layer can be sufficiently formed even if Zn
is not sufficiently dissolved by reducing the pH of the aqueous solution. It is advantageous
in forming the oxides that the pH thereof quickly increases upon the contact with
the weak alkali aqueous solution. Therefore, any pH buffering action is not necessarily
essential.
[0034] In the present invention, the oxide layer, which has excellent slidability, can be
stably formed when an aqueous solution contacted with the steel sheet contains zinc.
Therefore, even if impurities such as other metal ions and inorganic compounds are
accidentally or deliberately contained in the aqueous solution, advantages of the
present invention are not reduced. N, P, B, Cl, Na, Mn, Ca, Mg, Ba, Sr, and Si can
be used as far as advantages of the present invention are not reduced even if these
elements are captured in the oxide layer.
[0035] The oxide layer is formed on the galvanized steel sheet as described above. The oxide
layer contains zinc, which is an essential component, and has a thickness of 10 nm
or more.
[0036] The term "oxide layer" as used herein refers to a layer made of an oxide and/or hydroxide
principally containing zinc, which is a metal component. The oxide layer, which principally
contains such a component as zinc, needs to have an average thickness of 10 nm or
more. When the thickness of the oxide layer less than 10 nm, an effect of reducing
slidability is insufficient. When the thickness of the oxide layer, which contains
such an essential component as Zn, is greater than 100 nm, a coating is broken during
pressing to cause an increase in slidability and weldability is likely to be reduced.
This is not preferred.
[0037] A process for contacting the galvanized steel sheet with the zinc-containing aqueous
solution is not particularly limited. Examples of such a process include a process
for dipping a plated steel sheet in an aqueous solution, a process for spraying an
aqueous solution onto a plated steel sheet, a process for applying an aqueous solution
to a plated steel sheet with a coating roller, and the like. The aqueous solution
is preferably finally present on the steel sheet in the form of a thin liquid film.
This is because when the amount of the aqueous solution present on the steel sheet
is large, the pH of a plating surface is unlikely to be uniformly and quickly increased
by alkali treatment in the next step. In this viewpoint, it is preferable and effective
that the amount of an acidic solution film formed on a steel sheet is adjusted to
50 g/m
2 or less. The amount of the solution film can be adjusted by roll drawing, air wiping,
or the like.
[0038] Examples of the galvanized steel sheet according to the present invention include
those produced by various methods such as a hot-dip plating method, an electroplating
method, a vapor deposition plating method, and a spraying method. Examples of a plating
composition include pure Zn, Zn-Fe, Zn-Al, Zn-Ni, and Zn-Mg. However, in an embodiment
of the present invention, the type of plating is not limited because the dissolution
of Zn occurs in the galvanized steel sheet, which principally contains Zn, and the
oxide layer can be formed.
Examples
[0039] The present invention is further described below in detail with reference to examples.
[0040] Plating films having a mass per unit area of 45 g/m
2 and an Al concentration of 0.20 mass percent were formed on cold-rolled steel sheets
with a thickness of 0.8 mm by hot dip galvanizing and the cold-rolled steel sheets
were then temper-rolled, whereby GI steel sheets were prepared. Plating films having
a mass per unit area of 45 g/m
2, an Fe concentration of ten mass percent, and an Al concentration of 0.20 mass percent
were formed on cold-rolled steel sheets with a thickness of 0.8 mm by an ordinary
galvannealing method and the cold-rolled steel sheets were then temper-rolled, whereby
GA steel sheets were prepared. EG steel sheets including plating films having a mass
per unit area of 30 g/m
2 were prepared, the plating films being formed on cold-rolled steel sheets with a
thickness of 0.8 mm by an ordinary electrogalvanizing method.
[0041] The GI steel sheets, GA steel sheets, and EG steel sheets obtained as described above
were dipped in zinc sulfate solutions with various concentrations shown in Table 1.
After being taken out of the zinc sulfate solutions, the steel sheets were dipped
in aqueous sodium hydroxide solutions adjusted in pH or the aqueous sodium hydroxide
solutions were sprayed onto the steel sheets. The time taken to dip the steel sheets
in the aqueous sodium hydroxide solutions or taken to spray the aqueous sodium hydroxide
solutions onto the steel sheets was one second. The steel sheets were washed with
water within one second after dipping or spraying was finished. Before being treated
with the aqueous sodium hydroxide solutions, the steel sheets were tested in such
a manner that the zinc sulfate solutions remaining thereon were wiped with rubber
rollers.
[0042] For comparison, some of the steel sheets were subjected to a test in which dipping
in a zinc-free solution and treatment with sodium hydroxide were performed, a test
in which treatment with the aqueous sodium hydroxide solutions was not performed,
a test in which dipping was not performed after temper rolling, or a test in which
the pH of a zinc ion-containing aqueous solution was adjusted with sulfuric acid.
[0043] The following test was performed as a conventional technique: a test in which the
steel sheets were dipped in a 50°C aqueous solution which contained 30 g/l sodium
acetate and which had a pH of 1.5 was performed, the amount of the aqueous solution
remaining thereon was adjusted to 10 g/m
2 after dipping was finished, and the steel sheets were held for one to 30 seconds.
[0044] For the steel sheets prepared as described above, oxide layers of tempered portions
and untempered portions of plating surface layers were measured for thickness and
also measured for coefficient of friction for the purpose of simply evaluating press
formability. Measurement methods were as described below.
(1) Press formability evaluation test (coefficient-of-friction measurement test)
[0045] For the evaluation of press formability, each test piece was measured for coefficient
of friction as described below.
[0046] Fig. 1 is a schematic front view of a coefficient-of-friction tester. As shown in
this figure, a coefficient-of-friction measurement specimen 1 taken from the test
piece is fixed on a stage 2 and the stage 2 is fixed on the upper surface of a sliding
table 3 which is horizontally movable. The lower surface of the sliding table 3 overlies
a sliding table support 5 which includes rollers 4 in contact with the lower surface
thereof and which is vertically movable. The sliding table support 5 is attached to
a first load cell 7 for measuring the pressing load N applied to the coefficient-of-friction
measurement specimen 1 from a bead 6 by raising the sliding table support 5. The sliding
table 3 has an end portion attached to a second load cell 8 for measuring the sliding
resistance force F required to horizontally move the sliding table 3 along a rail
9 in such a state that the pressing load is applied thereto. The specimen 1 was coated
with lubricating oil, that is, washing oil, PRETON R352L, available from Sugimura
Chemical Industrial Co., Ltd. and was then tested.
[0047] Fig. 2 is a schematic perspective view showing the shape and size of the bead used.
The bead 6 slides on the specimen 1 in such a state that the lower surface of the
bead 6 is pressed against the specimen 1. The bead 6 has a width of 10 mm and a length
of 12 mm in the sliding direction of the specimen and includes lower end portions,
spaced in the sliding direction thereof, having curved surfaces with a curvature of
4.5 mm R as shown in Fig. 2. The bead lower surface, against which the specimen is
pressed, has a flat area having a width of 10 mm and a length of 3 mm in the sliding
direction thereof. A coefficient-of-friction measurement test was performed under
two conditions below.
(Condition 1)
[0048] The bead shown in Fig. 2 was used, the pressing load N was 400 kgf, and the drawing
rate of the specimen (the horizontal movement speed of the sliding table 3) was 100
cm/min.
(Condition 2)
[0049] The bead shown in Fig. 2 was used, the pressing load N was 400 kgf, and the drawing
rate of the specimen (the horizontal movement speed of the sliding table 3) was 20
cm/min.
[0050] The coefficient of friction between the test piece and the bead was calculated from
the equation µ = F / N.
(2) Measurement of thickness of oxide layer (oxide layer thickness)
[0051] An Si wafer having an SiO
2 film, formed by thermal oxidation, having a thickness of 96 nm was used as a reference
and an O·Kα x-ray was measured with an X-ray fluorescence spectrometer, whereby the
average thickness of the oxide layer was determined in terms of SiO
2. The analysis area was 30 mm ϕ.
[0052] Test results obtained as described above are shown in Table 1.
Table 1
No. |
Plating type |
Treatment soluti ons |
Roll drawing |
Holding time after dipping (second) |
NaOH solutions |
Oxide layer thickness |
Coefficient of friction |
Remarks |
Components (concentration) |
pH |
pH |
Contact processes |
(nm) |
Condition 1 |
Condition 2 |
1 |
GA |
Not used |
- |
- |
- |
- |
8 |
0.180 |
0.223 |
Comparative Example |
2 |
|
Sodium acetate (30g/L) |
1.5 |
Performed |
1 |
- |
- |
13 |
0.173 |
0.220 |
Comparative Example |
3 |
|
|
|
Performed |
2 |
- |
- |
16 |
0.164 |
0.217 |
Comparative Example |
4 |
|
|
|
Performed |
5 |
- |
- |
20 |
0.141 |
0.186 |
Comparative Example |
5 |
|
|
|
Performed |
10 |
- |
- |
26 |
0.134 |
0.173 |
Comparative Example |
6 |
|
|
|
Performed |
30 |
- |
- |
31 |
0.129 |
0.167 |
Comparative Example |
7 |
|
Sodium sulfate (10g/L) |
5.8 |
- |
- |
- |
- |
9 |
0.182 |
0.225 |
Comparative Example |
8 |
|
|
|
- |
- |
10 |
Dipping |
9 |
0.183 |
0.224 |
Comparative Example |
9 |
|
|
|
- |
- |
|
Spraying |
9 |
0.180 |
0.222 |
Comparative Example |
10 |
|
Zinc sulfate (zinc: 1 g/L) |
5.7 |
- |
- |
|
Dipping |
17 |
0.158 |
0.197 |
Example of the invention |
11 |
|
|
|
- |
- |
|
Spraying |
18 |
0.151 |
0.201 |
Example of the invention |
12 |
|
Zinc sulfate (zinc: 5 g/L) |
5.5 |
- |
- |
|
Dipping |
21 |
0.136 |
0.168 |
Example of the invention |
13 |
|
|
|
- |
- |
|
Spraying |
22 |
0.137 |
0.173 |
Example of the invention |
14 |
|
Zinc sulfate (zinc: 50 g/L) |
5.0 |
- |
- |
|
- |
8 |
0.171 |
0.218 |
Comparative Example |
15 |
|
|
|
- |
- |
6 |
Dipping |
16 |
0.165 |
0.201 |
Example of the invention |
16 |
|
|
|
- |
- |
|
Spraying |
19 |
0.150 |
0.192 |
Example of the invention |
17 |
|
|
|
- |
- |
7 |
Dipping |
20 |
0.136 |
0.175 |
Example of the invention |
18 |
|
|
|
- |
- |
|
Spraying |
27 |
0.128 |
0.166 |
Example of the invention |
19 |
|
|
|
- |
- |
10 |
Dipping |
29 |
0.129 |
0.165 |
Example of the invention |
20 |
|
|
|
- |
- |
|
Spraying |
30 |
0.128 |
0.166 |
Example of the invention |
21 |
|
|
|
Performed |
- |
|
Dipping |
32 |
0.129 |
0.170 |
Example of the invention |
22 |
|
|
|
Performed |
- |
|
Spraying |
34 |
0.125 |
0.164 |
Example of the invention |
23 |
|
|
|
- |
- |
13 |
Dipping |
28 |
0.131 |
0.168 |
Example of the invention |
24 |
|
|
|
- |
- |
|
Spraying |
28 |
0.129 |
0.171 |
Example of the invention |
25 |
|
|
|
- |
- |
14 |
Dipping |
15 |
0.170 |
0.212 |
Example of the invention |
26 |
|
|
|
- |
- |
|
Spraying |
17 |
0.164 |
0.205 |
Example of the invention |
27 |
|
|
3.0 |
- |
- |
|
- |
8 |
0.176 |
0.216 |
Comparative Example |
28 |
|
|
|
- |
- |
10 |
Dipping |
25 |
0.133 |
0.169 |
Example of the invention |
29 |
|
|
|
- |
- |
|
Spraying |
26 |
0.130 |
0.165 |
Example of the invention |
30 |
|
|
1.5 |
- |
- |
|
- |
8 |
0.178 |
0.221 |
Comparative Example |
31 |
|
|
|
- |
- |
10 |
Dipping |
23 |
0.135 |
0.172 |
Example of the invention |
32 |
|
|
|
- |
- |
|
Spraying |
25 |
0.132 |
0.167 |
Example of the invention |
33 |
|
Zinc sulfate (zinc: 100 g/L) |
4.9 |
- |
- |
|
Dipping |
32 |
0.127 |
0.165 |
Example of the invention |
34 |
|
|
|
- |
- |
|
Spraying |
36 |
0.125 |
0.166 |
Example of the invention |
35 |
GI |
Zinc sulfate (zinc: 1 g/L) |
5.7 |
- |
- |
10 |
Dipping |
16 |
0.160 |
0.199 |
Example of the invention |
36 |
|
|
|
- |
- |
|
Spraying |
16 |
0.154 |
0.205 |
Example of the invention |
37 |
|
Zinc sulfate (zinc: 50 g/L) |
5.0 |
- |
- |
6 |
Dipping |
15 |
0.167 |
0.204 |
Example of the invention |
38 |
|
|
|
- |
- |
|
Spraying |
17 |
0.153 |
0.196 |
Example of the invention |
39 |
|
|
|
- |
- |
10 |
Dipping |
26 |
0.133 |
0.170 |
Example of the invention |
40 |
|
|
|
- |
- |
|
Spraying |
28 |
0.130 |
0.165 |
Example of the invention |
41 |
|
|
|
Performed |
- |
|
Dipping |
30 |
0.128 |
0.166 |
Example of the invention |
42 |
|
|
|
Performed |
- |
|
Spraying |
32 |
0.129 |
0.164 |
Example of the invention |
43 |
|
|
|
- |
- |
14 |
Dipping |
14 |
0.171 |
0.215 |
Example of the invention |
44 |
|
|
|
- |
- |
|
Spraying |
17 |
0.165 |
0.209 |
Example of the invention |
45 |
EG |
Zinc sulfate (zinc: 1 g/L) |
5.7 |
- |
- |
10 |
Dipping |
14 |
0.141 |
0.199 |
Example of the invention |
46 |
|
|
|
- |
- |
|
Spraying |
13 |
0.150 |
0.200 |
Example of the invention |
47 |
|
Zinc sulfate (zinc: 50 g/L) |
5.0 |
- |
- |
6 |
Dipping |
16 |
0.142 |
0.192 |
Example of the invention |
48 |
|
|
|
- |
- |
|
Spraying |
18 |
0.139 |
0.191 |
Example of the invention |
49 |
|
|
|
- |
- |
10 |
Dipping |
23 |
0.135 |
0.170 |
Example of the invention |
50 |
|
|
|
- |
- |
|
Spraying |
26 |
0.136 |
0.169 |
Example of the invention |
51 |
|
|
|
Performed |
- |
|
Dipping |
29 |
0.131 |
0.168 |
Example of the invention |
52 |
|
|
|
Performed |
- |
|
Spraying |
33 |
0.132 |
0.159 |
Example of the invention |
53 |
|
|
|
- |
- |
14 |
Dipping |
16 |
0.138 |
0.185 |
Example of the invention |
54 |
|
|
|
- |
- |
|
Spraying |
14 |
0.145 |
0.202 |
Example of the invention |
*GA: Galvannealing
GI: Hot-dip galvanizing
EG: Electrogalvanizing |
[0053] Issues below were clarified from the test results shown in Table 1.
[0054] Nos. 10 to 13, 15 to 26, 28, 29, and 31 to 54 are examples of the present invention
that use aqueous solutions having a zinc ion concentration within the scope of the
present invention. Oxide layers with a thickness of 10 nm or more are formed and low
coefficients of friction are exhibited. A reduction in coefficient of friction is
caused independently of whether a process for contacting a weak alkali aqueous solution
is dipping or spraying.
[0055] Nos. 28, 29, 31, and 32 are examples of the present invention that use sulfuric acid
to reduce the pH of aqueous solutions containing zinc ions. Sufficient oxide layers
are formed even at low pH and a reduction in coefficient of friction is verified.
[0056] Nos. 21, 22, 41, 42, 51, and 52 are examples in which aqueous solutions containing
Zn ions are wiped with rubber rollers prior to the contact with weak alkali aqueous
solutions. Oxide layers are formed by the contact with the Zn ion-containing aqueous
solutions independently of whether roller wiping is performed or not, resulting in
a reduction in coefficient of friction.
[0057] No. 1 has a high coefficient of friction because No. 1 is treated with no solution
and therefore an oxide layer sufficient to enhance slidability is not formed in a
flat portion.
[0058] Nos. 2 to 6 are results due to conventional techniques (comparative examples) in
which holding was performed for one to 30 seconds after dipping in a treatment solution
is finished. Oxide layers grow with the holding time, so that oxide layers with a
thickness of 20 nm or more are obtained at a holding time of five seconds or more
and oxide layers with a thickness of 30 nm or more are obtained at a holding time
of 30 seconds or more.
[0059] Nos. 7 to 9 are comparative examples using a Zn-free solution (a sodium acetate solution).
Oxide layers have a thickness of less than 10 nm, which is outside the scope of the
present invention, and have a high coefficient of friction.
[0060] Nos. 14, 27, and 30 are comparative examples performing no treatment with a weak
alkali aqueous solution. Sufficient oxide layers are not formed only by the contact
with aqueous solutions containing zinc ions and therefore no advantage is obtained.
[0061] As is clear from the results of the examples, in Nos. 2 to 6 which are conventional
techniques, oxide layers with a thickness of 20 nm or more are not obtained unless
holding is performed five seconds or more and oxide layers with a thickness of 30
nm or more are not obtained unless holding is performed 30 seconds or more. In contrast,
in the examples of the present invention, the alkali solution-dipping or -spraying
time, which corresponds to the holding time taken in each conventional technique,
can be significantly reduced to one second. In consideration of production equipment,
the present invention is applied to a facility for continuously producing a steel
strip at high speed and the rate of producing the steel strip is about 180 m per minute
in terms of the movement speed of the steel strip. Therefore, in a conventional technique,
the length of a holding facility used subsequently to dipping in a treatment solution
needs to be 15 to 90 m; however, in the present invention, only an alkali solution-dipping
or - spraying facility with a size of about 3 m at minimum is necessary. This allows
a compact facility to be used.
[0062] In the techniques disclosed in Patent Documents 3 to 5, in order to secure a sufficient
holding time after the contact with an acidic solution under high-speed production
conditions, the distance from the contact with an acidic solution to water washing
needs to be secured. The test results suggest that good slidability can be achieved
by placing a sprayer only subsequently to the contact with an acidic solution containing
zinc ions and also suggest that the present invention enables stable production in
a reduced space under high-speed conditions.
Industrial Applicability
[0063] A galvanized steel sheet according to the present invention has excellent press formability
and therefore can be used for various applications such as automotive bodies. A method
for producing a galvanized steel sheet according to the present invention is capable
of forming an oxide layer with a desired thickness in a short treatment time. This
allows a compact production facility to be used.