Specification
1
[Name of Document] DESCRIPTION
[Title of the Invention] HOT-DIP GALVANIZED STEEL SHEET AND
MANUFACTURING METHOD OF THE SAME
[Technical Field]
5 [0001] The present invention relates to a hot-dip galvanized steel sheet
and a manufacturing method of the same, and in more detail, relates to a
hot-dip galvanized steel sheet excellent in plating wettability and plating
adhesiveness and applicable as a member of products in an automotive field, a
household appliance field, or a building material field and a manufacturing
10 method of the same.
[Background Ait]
[0002] As a member of products in an automotive field, a household
appliance field, or a building material field, surface-treated steel sheets to
which rust prevention property is given are used. Among them, a hot-dip
15 galvanized steel sheet is excellent in rust prevention property and is
inexpensive, to thus be used heavily.
[0003] Generally, the hot-dip galvanized steel sheet is manufactured by
the following method in general.
[0004] First, a thin steel sheet obtained by performing a hot-working hot
20 rolling treatment, a cold-working hot rolling treatment, and a heat treatment
on a slab is prepared as a base steel sheet (a base metal). Second, in a
pretreatment step aiming at washing of the surface of the base steel sheet,
degreasing and/or pickling are/is performed, or the base steel sheet is
introduced into a preheating furnace without performing the pretreatment step,
25 and thereby oil on the surface of the base steel sheet is burned to be removed.
Third, the base steel sheet is heated to high temperature in a heating furnace
2
(an annealing furnace), to thereby be subjected to recrystallization annealing.
Fourth, the obtained base steel sheet is immersed in a hot-dip galvanizing bath,
to thereby be subjected to a hot-dip galvanizing treatment. Incidentally, the
base steel sheet is cooled down to a temperature suitable for plating prior to
5 the immersion in a molten zinc bath.
[0005] Here, there will be explained a heat treatment atmosphere. The
treatment atmosphere where the above-described recrystallization annealing is
performed is set to an Fe reducing atmosphere. This makes it possible to
suppress generation of oxides of Fe and to prevent or inhibit oxides of Fe
10 from worsening plating wettability and plating adhesiveness in the subsequent
hot-dip galvanizing treatment. Further, the treatment atmosphere of the
above-described hot-dip galvanizing treatment is also set to an Fe reducing
atmosphere similarly to the recrystallization annealing. Thereby, the hot-dip
galvanized steel sheet can be manufactured continuously without being
15 exposed to an oxidizing atmosphere such as the air.
[0006] Incidentally, the heating furnace used for performing
recrystallization annealing in a continuous hot-dip galvanizing facility
enabling the above-described continuous manufacture includes types such as
a DFF (a direct firing type), a NOF (a non-oxidizing type), an all radiant tube
20 type enabling the entire treatment atmosphere in the furnace to be changed
into an Fe reducing atmosphere (a total reducing type), and combinations of
them. At present, due to the point of easy operation, the point that roll
pickup does not occur easily in the heating furnace, and the point that a high
quality plated steel sheet can be manufactured at lower cost, a continuous
25 hot-dip galvanizing facility using an all radiant tube type heating furnace has
become widely used.
3
[0007] By the way, in recent years, in an automotive field in particular,
among the hot-dip galvanized steel sheets, a hot-dip galvanized steel sheet in
which elements such as Si and Mn are contained in a material of a base steel
sheet and thereby the base steel sheet is increased in strength has been used
5 increasingly. This is to satisfy a demand for achieving both an increase in
strength of. a member aiming at protection of passengers at the time of
collision and a decrease in weight of a member aiming at improvement of fuel
efficiency in the automotive filed.
[0008] However, Si and Mn are easily oxidizable elements as compared
10 to Fe, so that there is caused a problem that Si and Mn contained in the base
steel sheet are oxidized by heating for recrystallization annealing in the all
radiant type heating furnace in spite of the treatment atmosphere being an Fe
reducing atmosphere. Concretely, in the process of recrystallization
annealing, Si and Mn existing on the surface of the base steel sheet are
15 oxidized with a high probability, and in addition to this, thermally diffused Si
and Mn are also oxidized in the vicinity of the surface of the base steel sheet,
resulting in that oxides of Si and Mn are gradually concentrated in a surface
layer of the steel sheet. Then, in the case when oxides of Si and Mn are
concentrated in the surface layer of the base steel sheet, when the base steel
20 sheet is immersed in a molten zinc bath in the subsequent hot-dip galvanizing
treatment, the oxides of Si and the oxides of Mn exposed to the surface of the
base steel sheet prevent the molten zinc and the base steel sheet from coming
into contact with each other, to thus become a cause of worsening of plating
wettability and become a cause of inhibition of plating adhesion to the base
25 steel sheet.
[0009] As documents disclosing a technique for suppressing the
4
concentration of oxides of Si and Mn described above, ones to be described
below can be cited.
[0010] Patent Document 1 discloses that prior to a hot-dip galvanizing
treatment, an oxidation treatment is performed on a base steel sheet in such a
5 manner that a thickness of an oxide film to be formed on the surface becomes
400 to 10000 A, and subsequently Fe is reduced in an in-furnace atmosphere
containing hydrogen. Further, Patent Document 2 discloses that prior to a
hot-dip galvanizing treatment, a surface portion of a base steel sheet is first
oxidized, and subsequently an oxygen potential that determines a treatment
10 atmosphere in a reducing furnace is adjusted, and thereby reduction of Fe and
oxidation of Si inside the steel sheet (internal oxidation) are both controlled.
[0011] The techniques disclosed in these two documents are made by
focusing on the recrystallization annealing process. Here, when a time
period for reduction of Fe (reduction time period) is too long, removal of an
15 oxide film of Fe can be performed, but concentration of oxides of Si in the
surface layer of the base steel sheet is caused, and further when the reduction
time period is too short, the oxide film of Fe remains on the surface portion of
the base steel sheet. Then, realistically, when it is considered that the
thickness of the oxide film formed on the surface of the base steel sheet by the
20 oxidation treatment is non-uniform, there is caused a problem that the
technique of adjusting the reduction time period described above alone is not
sufficient for improving the plating adhesiveness. Further, when the
thickness of the oxide film of Fe formed by the oxidation treatment is too
thick, a matter in which the oxides are peeled off from the base steel sheet to
25 attach to surfaces of rolls disposed in the furnace (roll pickup) is caused. In
this case, there is also caused a problem that outlines of the oxides attached to
5
the roll surfaces are transferred onto the surface of the following steel sheet
and thereby quality is impaired (appearance flaws).
[0012] Further, Patent Documents 3, 4, and 5 each disclose a technique in
which for the puipose of solving the above-described problems caused by
5 oxidation of Fe and suppressing the aforementioned concentration of oxides
of Si and Mn, prior to a hot-dip galvanizing treatment, during recrystallization
annealing in an all radiant tube type heating furnace, an oxygen potential that
determines a treatment atmosphere is increased up to the extent that Si and
Mn are internally oxidized.
10 [0013] Similarly, Patent Documents 6, 7, 8, and 9 each disclose a
technique of adjusting a treatment atmosphere used for a heating furnace.
[0014] However, in the techniques disclosed in Patent Documents 3 to 9,
when the oxygen potential is increased too much, Si and Mn can be internally
oxidized, but Fe is also oxidized, resulting in that the same problems as those
15 described above are caused. On the other hand, even when the oxygen
potential is increased up to the extent that Fe is not oxidized, internal
oxidation of Si and Mn becomes insufficient, resulting in that oxides of Si and
Mn are concentrated in the surface layer of the base steel sheet. Thus, either
case causes a problem that the oxygen potential that determines a treatment
20 atmosphere cannot be adjusted accurately. Therefore, by these techniques, a
hot-dip galvanized steel sheet having uniform quality cannot be manufactured
securely.
[0015] Further, as another example of the technique for suppressing
concentration of oxides of Si and Mn, there can be cited a technique of
25 employing a means of further increasing steps necessary for a general
manufacturing method of hot-dip galvanizing described above. For example,
6
Patent Document 10 discloses a technique in which annealing is performed
two times prior to a hot-dip galvanizing treatment. Such a technique is
regarded that when oxides of Si formed on the surface of a base steel sheet
(surface concentrated substances) are pickled and removed after the first
5 annealing is performed, formation of surface concentrated substances can be
suppressed at the time of the second annealing. However, when the
concentration of Si in the base steel sheet is high, the surface concentrated
substances cannot be removed sufficiently by pickling, resulting in that there
is caused a problem that plating wettability and plating adhesiveness cannot
10 be improved sufficiently. Further, in order to remove the surface
concentrated substances of Si, a facility for performing annealing two times
and a facility for performing pickling are newly required, so that there is also
caused a problem that facility cost is increased, and further production cost is
also increased.
15 [0016] Further, as still another example of the technique for suppressing
concentration of oxides of Si and Mn described above, there can be cited a
technique in which prior to a plating step, Si and Mn are internally oxidized in
a hot rolling step. For example, Patent Document 11 discloses a technique in
which when manufacturing a hot-dip galvanized steel sheet in a continuous
20 hot-dip galvanizing facility, an oxygen potential is adjusted in a hot rolling
step, to thereby internally oxidize Si in a thin steel sheet (a base steel sheet).
However, in such a technique, when rolling of the base steel sheet is
performed in a cold rolling step following the hot rolling step, an internal
oxide layer is also rolled simultaneously and a thickness dimension of the
25 internal oxide layer is decreased, resulting in that in the subsequent
recrystallization annealing process, oxides of Si are concentrated in a surface
7
layer of the base steel sheet. Therefore, there is caused a problem that even
by the technique, plating wettability and plating adhesiveness cannot be
improved sufficiently. Further, in the technique, oxides of Fe are formed at
the same time as Si is internally oxidized in the hot rolling step, but as
5 described previously, there is also caused a problem that the quality of a steel
sheet to be manufactured is impaired due to peeling of oxides of Fe.
[0017] Incidentally, the hot-dip galvanized steel sheet containing Si and
Mn is not limited to the above-described problems (problems explained by
using Patent Documents 1 to 11 as examples), and has a fundamental problem
10 that workability (for example, ductility) of the base steel sheet is inferior to
that of a hot-dip galvanized steel sheet not containing Si and Mn because the
strength (hardness) of the base steel sheet is increased. Here, when the
ductility of the base steel sheet is low, even if a contact between the hot-dip
galvanizing layer and the base steel sheet is made well, for example, in the
15 case when working (for example, press forming) is performed on the hot-dip
galvanized steel sheet, a crack is caused in the base steel sheet itself or in an
interface between the base steel sheet and the hot-dip galvanizing layer and
thereby the hot-dip galvanizing layer becomes likely to be peeled off from the
base steel sheet. That is, the hot-dip galvanized steel sheet containing Si and
20 Mn is required to improve the plating adhesiveness more than the hot-dip
galvanized steel sheet not containing Si and Mn is required.
[Prior Art Document]
[Patent Document]
[0018] Patent Document 1: Japanese Laid-open Patent Publication No.
25 55-122865
Patent Document 2: Japanese Laid-open Patent Publication No.
2001-323355
Patent Document 3: Japanese Laid-open Patent Publication No.
2008-007842
Patent Document 4: Japanese Laid-open Patent Publication No.
5 2001-279412
Patent Document 5: Japanese Laid-open Patent Publication No.
2009-209397
Patent Document 6: Japanese Laid-open Patent Publication No.
2011-111670
10 Patent Document 7: Japanese Laid-open Patent Publication No.
2005-060743
Patent Document 8: Japanese Laid-open Patent Publication No.
2006-233333
Patent Document 9: International Publication Pamphlet No. WO
15 2013/047804
Patent Document 10: Japanese Laid-open Patent Publication No.
2010-196083
Patent Document 11: Japanese Laid-open Patent Publication No.
2000-309847
20 [Disclosure of the Invention]
[Problems to Be Solved by the Invention]
[0019] A principal object of the present invention is to provide a hot-dip
galvanized steel sheet that is excellent in plating wettability and plating
adhesiveness even when a base steel sheet contains Si and Mn, and a
25 manufacturing method of the same.
[0020] Here, the term of "hot-dip galvanized steel sheet" is a
9
surface-treated steel sheet provided with a plating layer (to be referred to as a
"hot-dip galvanizing layer" hereinafter) formed by undergoing a plating
treatment using a melt containing zinc as its main component (to be referred
to as a "hot-dip galvanizing treatment" hereinafter).
5 [0021] Further, the term of "plating wettability" means a property in
which plating in a molten state (molten zinc) tries to spread over a surface of
a base steel sheet (a base metal) without being repelled thereon. In more
detail, this plating wettability can be evaluated by observing a state of a
solid-liquid interface (a contact angle), but in the present invention, it is
10 evaluated depending on whether peeling of plating has occurred to the extent
that the hot-dip galvanized steel sheet is press-formed, and then an obtained
steel sheet is evaluated as an unplating defect (appearance failure, rust
prevention property failure, or the like). When appearance failure is caused
in the press-formed hot-dip galvanized steel sheet, for example, it is evaluated
15 to be "poor in plating wettability."
[0022] The term of "plating adhesiveness" means a property in which
plating in a solidified state (a hot-dip galvanizing layer) and a base steel sheet
(a base metal) are in a state of adhering to each other while being in a surface
contact with each other, or they try to maintain the state. In more detail, this
20 plating adhesiveness can be evaluated by observing a state of a solid-solid
interface, but in the present invention, it is evaluated depending on whether
when a hot-dip galvanized steel sheet is press-formed by using a metal mold,
the thing in which part of a hot-dip galvanizing layer peeled off from the steel
sheet is turned into powder to adhere to a surface of the metal mold (what is
25 called powdering) is recognized. When powdering is recognized, for
example, appearance failure is caused in the following steel sheet to be
10
obtained by press forming, or worsening of slidability of the metal mold is
caused, so that it is evaluated to be "poor in plating adhesiveness."
Incidentally, the plating adhesiveness may also be evaluated in accordance
with "Test methods for hot dip galvanized coatings" of Japanese Industrial
5 Standard JIS H 0401: 2007 (corresponding to International Standard ISO
1460: 1992).
[0023] Incidentally, those skilled in the art can understand other objects
of the present invention by referring the description of the present description
with their own common general technical knowledge. Objects of providing
10 a method for manufacturing a hot-dip galvanized steel sheet excellent in
plating wettability and plating adhesiveness and providing a hot-dip
galvanized steel sheet having excellent workability and containing Si and Mn,
for example, are also included in the object of the present invention.
[Means for Solving the Problems]
15 [0024] The present inventors, in order to solve the above-described
problems, focused on an effect of, in the vicinity of an interface between a
hot-dip galvanizing layer and a base steel sheet constituting a hot-dip
galvanized steel sheet, hardness of the base steel sheet on plating wettability
and plating adhesiveness and performed earnest examinations, and as a result,
20 found out that even when the base steel sheet contains Si and Mn, defining the
hardness of the base steel sheet by using predetermined parameters makes it
possible to provide a hot-dip galvanized steel sheet excellent in workability.
Further, the present inventors focused on manufacturing conditions for
manufacturing such a hot-dip galvanized steel sheet and performed earnest
25 examinations, and as a result, found out that conditions that treatment
atmospheres of a radiant tube type heating furnace and a soaking furnace
11
provided in a facility for manufacturing the hot-dip galvanized steel sheet
(particularly, partial pressure ratios of carbon dioxide and carbon monoxide to
be supplied into these furnaces) should satisfy are defined, thereby making it
possible to provide a method for continuously manufacturing the hot-dip
5 galvanized steel sheet excellent in plating wettability and plating adhesiveness
with uniform quality.
[0025] That is, the gist of the present invention is as follows.
[0026] (Al) A hot-dip galvanized steel sheet including a base steel sheet
and a hot-dip galvanizing layer formed on at least one surface of the base steel
10 sheet, in which
the base steel sheet contains, in mass%,
C: not less than 0.05% nor more than 0.50%,
Si: not less than 0.1% nor more than 3.0%,
Mn: not less than 0.5% nor more than 5.0%,
15 P: not less than 0.001% nor more than 0.5%,
S: not less than 0.001% nor more than 0.03%,
Al: not less than 0.005% nor more than 1.0%, and
one or two or more of elements selected from Ti, Nb, Cr, Mo,
Ni, Cu, Zr, V, W, B, Ca, and a rare-earth element REM: not less than 0% nor
20 more than 1% each, and
a balance being composed of Fe and inevitable impurities, and
in the base steel sheet, a value of HA representing average hardness in
a surface layer ranging from an interface between the base steel sheet and the
hot-dip galvanizing layer to 50 um in depth and a value of HR representing
25 average hardness in a deep portion ranging from the interface to greater than
50 um in depth satisfy all the following relational expressions (1) to (3).
12
50 ^ HA ^ 500 -(1)
50 ^ HB ^ 500 -(2)
0.5 ^ HA/HB ^ 0.9-(3)
[0027] (A2) The hot-dip galvanized steel sheet according to (Al), in
5 which
WC(A), WSi(A), and WM.i(A) representing content percentages of C, Si,
and Mn in mass% in the surface layer of the base steel sheet respectively and
WC(B> Wsj(B)> and WM„(B) representing content percentages of C, Si, and Mn
in mass% in the deep portion of the base steel sheet respectively satisfy all the
10 following relational expressions (4) to (6).
0.1 < WC(A/WC{B) ^ 0.5 -(4)
0.1 ^ WSKA/WSHB) ^ 0.5 -(5)
0-1 £ WM„(A/WMn(B) ^ 0.5-(6)
[0028] (A3) The hot-dip galvanized steel sheet according to (Al) or (A2),
15 in which
the base steel sheet contains one or two or more of elements selected
from Ti, Nb, Cr, Mo, Ni, Cu, Zr, V, W, B, Ca, and a rare-earth element REM
in not less than 0.0001% nor more than 1% each.
[0029] (A4) The hot-dip galvanized steel sheet according to any one of
20 (Al) to (A3), in which
the hot-dip galvanizing layer has a thickness in the range of not less
than 1 jim nor more than 30 |iim, and contains not less than 4 mass% nor more
than 14 mass% of Fe, not less than 0.1 mass% nor more than 1 mass% of Al,
and a balance being composed of Zn and inevitable impurities.
25 [0030] (Bl) A method for manufacturing a hot-dip galvanized steel sheet
by performing a hot-dip galvanizing treatment on a base steel sheet, in which
13
the base steel sheet is obtained after undergoing a casting step, a hot
rolling step, a pickling step, a cold rolling step, an annealing step, and a
soaking and holding step, and contains, in mass%,
C: not less than 0.05% nor more than 0.50%,
5 Si: not less than 0.1% nor more than 3.0%,
Mn: not less than 0.5% nor more than 5.0%,
P: not less than 0.001% nor more than 0.5%,
S: not less than 0.001% nor more than 0.03%,
Al: not less than 0.005% nor more than 1.0%, and
10 one or two or more of elements selected from Ti, Nb, Cr, Mo,
Ni, Cu, Zr, V, W, B, Ca, and a rare-earth element REM: not less than 0% nor
more than 1% each, and
a balance being composed of Fe and inevitable impurities,
the annealing step and the soaking and holding step are performed in a
15 continuous hot-dip galvanizing facility equipped with an all radiant tube type
heating furnace as a heating furnace and a soaking furnace,
the annealing step is performed so as to satisfy the following heating
furnace conditions:
heating temperature: a sheet temperature T0 [°C] representing
20 the maximum temperature that, when a cold-rolled steel sheet obtained after
undergoing the cold rolling step is heated in the heating furnace, the
cold-rolled steel sheet reaches is in the range of not lower than a temperature
T{ [°C] nor higher than a temperature T2 [°C];
heating time period: a heating time period So [second] in the
25 heating furnace is in the range of not shorter than a time period Si [second]
nor longer than a time period S2 [second]; and
14
atmosphere gas: a nitrogen atmosphere containing carbon
dioxide and carbon monoxide in which log(PC02/PCO) being a logarithmic
value of a value of, in the heating furnace, a partial pressure value of carbon
dioxide divided by a partial pressure value of carbon monoxide exhibits a
5 value in the range of not less than -2 nor more than 1,
here, the temperatures Ti and T2 and the time periods Sj and S2 are
defined as follows:
Ti: a temperature [°C] satisfying the following relational expression
(7) using Wsi (B> and WM„ (B> representing content percentages of Si and Mn in
10 mass% in a deep portion ranging from a surface of the cold-rolled steel sheet
to greater than 50 jim in depth respectively;
T, = 500 - 50 x Wsi(B) - 20 x WM„(B)-(7)
T2: a- temperature [°C] satisfying the following relational
expression (8) using a temperature TAc3 [°C] corresponding to a
15 transformation point Ac3 of the cold-rolled steel sheet;
T2 = TAc3 + 40-(8)
Si: a time period [second] satisfying the following relational
expression (9) using Wsi(B) [mass%] representing the content percentage of Si
and WMn (B) [mass%] representing the content percentage of Mn in the deep
20 portion of the cold-rolled steel sheet; and
S! - 50 + 20 x Wsi(B) + 10 x WM„(B)-(9)
S2: a time period [second] satisfying the following relational
expression (10) using Wc(B) [mass%] representing content percentage of C in
the deep portion of the cold-rolled steel sheet,
25 S2 = 200 + 1000 x WC(B)-(10)
the soaking and holding step is performed so as to satisfy the
15
following soaking furnace conditions:
soaking and holding time period: a time period during which the
cold-rolled steel sheet is held in the soaking furnace is in the range of not
shorter than 100 seconds nor longer than 600 seconds; and
5 atmosphere gas: a nitrogen atmosphere containing carbon dioxide and
carbon monoxide in which a value of log(PC02/PCO) in the soaking furnace
is in the range of-5 or more to less than -2, and
in the plating step, a hot-dip galvanizing layer containing not less than
4 mass% nor more than 14 mass% of Fe, not less than 0.1 mass% nor more
10 than 1 mass% of Al, and a balance being composed of Zn and inevitable
impurities is formed on the surface of the base steel sheet so as to have a
thickness of not less than 1 urn nor more than 30 urn.
[0031] (B2) The method according to (B1), in which
on the occasion of performing the hot-dip galvanizing treatment, the
15 base steel sheet obtained after undergoing the soaking and holding step is
immersed in a hot-dip galvanizing bath containing not less than 0.05 mass%
nor more than 0.20 mass% of Al, and then is subjected to an alloying
treatment in which heating is performed to a heating temperature in the range
of not lower than 450°C nor higher than 560°C.
20 [Effect of the Invention]
[0032] According to the present invention, it is possible to provide a
hot-dip galvanized steel sheet that is excellent in plating wettability and
plating adhesiveness even when a base steel sheet contains Si and Mn, and a
manufacturing method of the same.
25 [Brief Description of the Drawings]
[0032] [FIG. 1] FIG. 1 is a graph showing the relationship between, of a
16
base steel sheet, Vickers hardness HA in a surface portion and Vickers
hardness HB in a deep portion of hot-dip galvanized steel sheets manufactured
by a manufacturing method of a hot-dip galvanized steel sheet according to
the present invention (Examples Al to A72 and Bl to B36) and hot-dip
5 galvanized steel sheets manufactured by another manufacturing method
(Comparative examples CI to C7, Cll, C29 to C35, C38, C40 to C50, C52,
C53, andC56);
[FIG2] FIG. 2 is a graph showing the relationship between the Vickers
hardness HA in the surface portion of the base steel sheet and a ratio of the
10 Vickers hardness HA in the surface portion to the Vickers hardness HB in the
deep portion (HA/HB) of the hot-dip galvanized steel sheets manufactured by
the manufacturing method of the hot-dip galvanized steel sheet according to
the present invention (Examples Al to A72 and Bl to B36) and hot-dip
galvanized steel sheets manufactured by another manufacturing method
15 (Comparative examples CI to C56);
[FIG. 3] FIG. 3 is a graph showing the relationship between a value of
a ratio of, of the base steel sheet, content percentage of C in the surface
portion to content percentage of C in the deep portion (Wc (A/WC (B)) and a
value of a ratio, of the base steel sheet, content percentage of Si in the surface
20 portion to content percentage of Si in the deep portion (WSj (A/WSi (B)) of the
the hot-dip galvanized steel sheets manufactured by the manufacturing
method of the hot-dip galvanized steel sheet according to the present
invention (Examples Al to A72 and Bl to B36);
[FIG. 4] FIG 4 is a graph showing the relationship between the value
25 of the ratio of, of the base steel sheet, the content percentage of C in the
surface portion to the content percentage of C in the deep portion (Wc (A/WC
17
(B)) and a value of a ratio, of the base steel sheet, content percentage of Mn in
the surface portion to content percentage of Mn in the deep portion (WMn
(A/WMII (BJ) of the the hot-dip galvanized steel sheets manufactured by the
manufacturing method of the hot-dip galvanized steel sheet according to the
5 present invention (Examples Al to A72 and B1 to B36);
[FIG. 5] FIG. 5 is a graph showing the relationship between a
thickness of a hot-dip galvanizing layer [jam] and content percentage of Fe in
the hot-dip galvanizing layer [mass%] of the the hot-dip galvanized steel
sheets manufactured by the manufacturing method of the hot-dip galvanized
10 steel sheet according to the present invention (Examples Al to A72 and Bl to
B36);
[FIG. 6] FIG. 6 is a graph showing the relationship between the
thickness of the hot-dip galvanizing layer [\im] and content percentage of Al
in the hot-dip galvanizing layer [mass%] of the the hot-dip galvanized steel
15 sheets manufactured by the manufacturing method of the hot-dip galvanized
steel sheet according to the present invention (Examples Al to A72 and Bl to
B36);
[FIG. 7] FIG. 7 is a graph showing the relationship between a value of
difference between a sheet temperature T0 [°C] representing the maximum
20 temperature that, when a base steel sheet for a hot-dip galvanized steel sheet
is heated in a heating furnace in accordance with the manufacturing method of
the hot-dip galvanized steel sheet according to the present invention
(Examples Al to A72 and Bl to B36) and another manufacturing method
(Comparative examples CI to C8 and C17 to C24), the base steel sheet
25 reaches and a temperature Ti [°C] associated with WS; (B) [mass%]
representing the content percentage of Si and WMn (B> [mass%] representing
18
the content percentage of Mn contained in the base steel sheet (T0 to Tj) and a
value of difference between a temperature T2 [°C] associated with a
temperature TAc3 [°C] corresponding to a transformation point Ac3 of the base
steel sheet and the aforementioned sheet temperature T0 [°C] (T2 - T0);
5 [FIG. 8] FIG. 8 is a graph showing the relationship between a value of
difference between a heating time period So [second] when the base steel
sheet for a hot-dip galvanized steel sheet is heated in the heating furnace in
accordance with the manufacturing method of the hot-dip galvanized steel
sheet according to the present invention (Examples Al to A72 and Bl to B36)
10 and another manufacturing method (Comparative examples Cll to C24) and a
time period Si [second] associated with WSi (B) [mass%] representing the
content percentage of Si and WMn (B) [mass%] representing the content
percentage of Mn in the base steel sheet (S0 - Si) and a value of difference
between a time period S2 [second] associated with Wc (B) [mass%]
15 representing the content percentage of C in the base steel sheet and the
aforementioned heating time period So [second] (S2 - So);
[FIG. 9] FIG. 9 is a graph showing the relationship between a
logarithmic value of a partial pressure ratio of C02 to CO in an atmosphere
gas when the base steel sheet for a hot-dip galvanized steel sheet is heated in
20 the heating furnace and a logarithmic value of a partial pressure ratio of C02
to CO in an atmosphere gas when it is soaked and held in a soaking furnace in
accordance with the manufacturing method of the hot-dip galvanized steel
sheet according to the present invention (Examples Al to A72 and Bl to B36)
and another manufacturing method (Comparative examples C9, CIO, and C41
25 to C56);
[FIG. 10] FIG. 10 is a graph showing the relationship between a
19
heating time period [second] when the base steel sheet for a hot-dip
galvanized steel sheet is heated in the heating furnace and a soaking and
holding time period [second] when it is soaked and held in the soaking
furnace in accordance with the manufacturing method of the hot-dip
5 galvanized steel sheet according to the present invention (Examples Al to
A72 and Bl to B36) and another manufacturing method (Comparative
examples CI7 to C40); and
[FIG. 11] FIG. 11 is a graph showing the relationship between content
percentage of Al [mass%] in a hot-dip galvanizing bath when a hot-dip
10 galvanizing treatment is performed on the base steel sheet for a hot-dip
galvanized steel sheet and a heating temperature [°C] when heating is
performed for performing an alloying treatment after the hot-dip galvanizing
treatment in accordance with the manufacturing method of the hot-dip
galvanized steel sheet according to the present invention (Examples Al to
15 A72andBltoB36).
[Mode for Carrying out the Invention]
[0034] Hereinafter, there will be explained embodiments for
implementation of the present invention in detail.
[0035] A hot-dip galvanized steel sheet according to a first embodiment
20 of the present invention includes a base steel sheet and a hot-dip galvanizing
layer provided on at least one surface of the base steel sheet. In this
embodiment, the base steel sheet contains Si and Mn. Further, the hot-dip
galvanizing layer is formed on the surface of the base steel sheet by a
later-described hot-dip galvanizing treatment.
25 [0036] Subsequently, there will be explained components composing the
above-described base steel sheet and their contents. Incidentally, in the
20
present description, the percentage [%] used for the content is mass% unless
otherwise explained.
[0037] C: 0.05 to 0.50%
Carbon (C) is a useful element for increasing strength of the base steel
5 sheet by stabilizing an austenite phase of the base steel sheet, and therefore is
an essential component of the base steel sheet. Here, when the content
percentage of C is set to less than 0.05%, strength of the base steel sheet
becomes insufficient, and when it is set to greater than 0.50%, on the other
hand, workability of the base steel sheet becomes worse. Thus, the content
10 percentage of C is in the range of not less than 0.05% nor more than 0.50%,
and is preferably in the range of not less than 0.10% nor more than 0.40%.
Incidentally, even if the base steel sheet is exposed under a decarburizing
atmosphere condition defined in the present invention, the content percentage
of C hardly changes.
15 [0038] Si: 0.1 to 3.0%
Silicon (Si) is a useful element for improving strength of the base steel
sheet by concentrating the component of C solid-dissolved in a ferrite phase
of the base steel sheet in an austenite phase to increase resistance to temper
softening of steel, and therefore is one of essential components for the base
20 steel sheet. Here, when the content percentage of Si is set to less than 0.1%,
strength of the base steel sheet becomes insufficient, and when it is set to
greater than 3.0%, on the other hand, workability of the base steel sheet
becomes worse and it is not possible to sufficiently improve plating
wettability and plating adhesiveness of the hot-dip galvanized steel sheet.
25 Thus, the content percentage of Si is in the range of not less than 0.1% nor
more than 3.0%, and is preferably in the range of not less than 0.5% nor more
21
than 2.0%.
[0039] Mn: 0.5 to 5.0%
Manganese (Mn) is a useful element for increasing strength of the
base steel sheet by increasing hardenability of the base steel sheet, and
5 therefore is one of essential components for the base steel sheet. Here, when
the content percentage of Mn is set to less than 0.5%, strength of the base
steel sheet becomes insufficient, and when it is set to greater than 5.0%), on
the other hand, workability of the base steel sheet becomes worse and it is not
possible to sufficiently improve plating wettability and plating adhesiveness
10 of the hot-dip galvanized steel sheet. Thus, the content percentage of Mn is
in the range of not less than 0.5% nor more than 5.0%, and is preferably in the
range of 1.0% or more to less than 3.0%.
[0040] P: 0.001 to 0.5%
Phosphorus (P) is an element to contribute to improvement in strength
15 of the base steel sheet, and therefore is a component to be added to a raw
material of the base steel sheet according to the magnitude of strength
required for the base steel sheet. Here, when the content percentage of P
exceeds 0.5%, the material of the base steel sheet deteriorates due to grain
boundary segregation. Thus, the upper limit of the content percentage of P is
20 0.5%>. On the other hand, considerable cost is necessary for setting the
content percentage of P to less than 0.001% at the stage of steelmaking, so
that the lower limit of the content percentage of P is 0.001%.
[0041] S: 0.001 to 0.03%
Sulfur (S) is an impurity inevitably contained in the raw material of
25 the base steel sheet. The component of S forms plate-shaped inclusions of
MnS in the cold-rolled base steel sheet to impair workability of the base steel
22
sheet, so that the content percentage of S is desirably low. However,
decreasing the content percentage of S excessively (desulfurization) causes a
cost increase in a steelmaking step. Thus, the content percentage of S is in
the range of not less than 0.001% nor more than 0.03%.
5 [0042] Al: 0.005 to 1.0%
Aluminum (Al) is an element capable of fixing N solid-dissolved in
the base steel sheet as a precipitate because of having a high affinity for
nitrogen (N) in the base steel sheet, and therefore is useful as a component
improving workability of the base steel sheet. On the other hand, when an
10 excessive amount of Al is added to the raw material of the base steel sheet, it
deteriorates workability of the base steel sheet on the contrary. Thus, the
content percentage of Al is in the range of not less than 0.005% nor more than
1.0%.
[0043] The component except for the above-described components (a
15 balance) of the base steel sheet is composed of Fe and inevitable impurities.
As an example of the inevitable impurities, Ti, Nb, Cr, Mo, Ni, Cu, Zr, V, W,
B, Ca, and a rare-earth element (REM) can be cited. The content percentage
of each of the inevitable impurities is in the range of not less than 0% nor
more than 1%. Incidentally, at the stage of steelmaking, adjustment may
20 also be performed so that the content percentage of each of the inevitable
impurities contained in the base steel sheet may fall within the range of not
less than 0.0001% nor more than 1%. Thereby, an effect that plating
wettability and plating adhesiveness of the hot-dip galvanized steel sheet to be
manufactured are further improved is exhibited. Incidentally, the reason
25 why the plating adhesiveness is improved is thought that on the occasion of a
hot-dip galvanizing treatment, these elements improve reactivity of the
23
molten zinc and the base steel sheet. However, a mechanism for
improvement in reactivity is not revealed. The above-described effect
cannot be exhibited sufficiently when the content percentage of each of the
elements is less than 0.0001%, but the above-described effect is saturated
5 when the content percentage of each of the elements is greater than 1%.
[0044] Incidentally, in a modified example of this embodiment, one or
. two or more of elements selected from Ti, Nb, Cr, Mo, Ni, Cu, Zr, V, W, B, Ca,
and a rare-earth element (REM) cited as the inevitable impurities in the
above-described embodiment may also be added to the raw material of the
10 base steel sheet intensionally so that each content percentage may fall within
the range of not less than 0.0001% nor more than 1%. Thereby, the effect
equal to that described above can be exhibited. Incidentally, it is
uneconomical to add each of the elements to the raw material of the base steel
sheet so that each content percentage may become greater than 1%.
15 [0045] A manufacturing method of the base steel sheet is not limited in
particular, and may be a well-known manufacturing method. As one
example of the well-known manufacturing method, starting from preparation
of the raw material of the base steel sheet, casting, hot rolling, pickling, and
cold rolling are performed in this order, and thereby a cold-rolled steel sheet
20 (a thin steel sheet) can be manufactured. The cold-rolled steel sheet
obtained in this manner has a predetermined sheet thickness in the range of
0.1 mm or more to 3.5 mm, and preferably in the range of not less than 0.4
mm nor more than 3 mm. However, in the first embodiment of the present
invention and the modified example, hardness of the manufactured base steel
25 " sheet needs to be defined by predetermined parameters as will be described in
detail below. Therefore, on the occasion of manufacturing such a base steel
24
sheet having hardness defined by predetermined parameters, at least part of a
manufacturing method to be described later as a second embodiment of the
present invention is preferably employed.
[0046] Subsequently, the hardness of the base steel sheet that should be
5 manufactured in the first embodiment of the present invention and the
modified example will be explained in detail.
[0047] In this embodiment, roughly, hardness of a surface layer of the
above-described base steel sheet is lower than that of an arbitrary place of a
portion different from the surface layer (a deep portion). That is, on the base
10 steel sheet, a treatment is performed so that the hardness of the surface layer
may become lower than that of the deep portion. Incidentally, one example
of the treatment will be explained in the later-described second embodiment
of the present invention.
[0048] Concretely, in this embodiment, when first hardness representing
15 average hardness of the surface layer ranging from an interface between the
base steel sheet and the hot-dip galvanizing layer to 50 u,m in depth and
second hardness representing average hardness of the deep portion ranging
from the interface to greater than 50 u.m in depth are represented by average
Vickers hardnesses HA and HB respectively, all the following relational
20 expressions (1) to (3) are satisfied.
50 ^ HA ^ 500 -(1)
50 ^ HB ^ 500 -(2)
0.5 ^ HA/Hn ^ 0.9-(3)
[0049] Here, the average Vickers hardness (HA) is calculated by
25 averaging Vickers hardnesses measured at plural measurement points on a
side cross section of the exposed base steel sheet obtained by removing the
25
hot-dip galvanizing layer from the hot-dip galvanized steel sheet. Here, the
Vickers hardness is measured based on "Vickers hardness test-Test method"
of Japanese Industrial Standard JIS Z 2244: 2009 (corresponding to
International Standard ISO 6507-4: 2005). For the measurement of the
5 Vickers hardness, plural measurement points are set on the side surface (cross
section) side of the exposed base steel sheet. Therefore, the base steel sheet
is placed on a support table so that the side surface (cross section) of the base
steel sheet may be positioned vertically to the direction of movement of an
indenter of a Vickers hardness testing machine. However, in this
10 embodiment, a load used for the measurement of the Vickers hardness is set to
10 gf (0.00102N), as the depth of the measurement point (the depth from the
surface of the base steel sheet), 10 um,-20 urn, 30 jam, 40 um, and 50 um are
employed, and at each of the depths, 3-point measurement (N3 measurement)
is performed, and thereby the average Vickers hardness HA is calculated.
15 Further, the measurement points are set on the side surface (cross section) of
the base steel sheet, and each interval between the plural measurement points
is set in the range of not less than 40 um nor more than 100 um so that a
measurement trace formed at one measurement point may not affect the
measurements at the other measurement points. Incidentally, the
20 measurement of the Vickers hardness may also be performed before the
hot-dip galvanizing layer is provided on the surface of the base steel sheet.
The average Vickers hardness (HB) is also calculated in the same manner as
that of the average Vickers hardness (HA), and in this embodiment, as the
depths of the measurement points, the range from 60 urn to the position of a
25 quarter of a sheet thickness of the base steel sheet is employed at 10-um pitch
and at each of the depths, 3-point measurement (N3 measurement) is
26
performed, and thereby the average Vickers hardness HB is calculated.
Incidentally, in the portion other than the surface layer of the base steel sheet
(the deep portion), the hardnesses can be said to be substantially fixed, so that
an average value of values of the hardnesses measured at the plural
5 measurement points does not have to be calculated, and in this case, hardness
measured at an arbitrary measurement point in the deep portion is referred to
as the above-described average Vickers hardness (HB).
[0050] As described above, the values of HA and HB are each not less
than 50 nor more than 500 (see the above-described relational expressions (1)
10 and (2)). This is reflected also in the graph shown in FIG. 1. Here, from
results of examples and comparative examples whose results are described in
the graph in FIG. 1 (see also Table 1, Tables 2-1 to 2-4, Tables 3-1 to 3-2, and
Table 4-1 to Table 4-2 provided in the section of Example to be described
later), the following is clarified. When the values of HA and HB are each less
15 than 50, the base steel sheet is locally deformed easily due to a contact with a
metal mold at the time of presswork and the hot-dip galvanizing layer cannot
follow the deformation to peel off from the base steel sheet, resulting in that
such a hot-dip galvanized steel sheet is evaluated to be poor in both plating
wettability and plating adhesiveness. Further, when the values of HA and HB
20 are each greater than 500, a crack is caused in the base steel sheet when
presswork, due to this, a crack is caused also in the hot-dip galvanizing layer,
and the base steel sheet is exposed, resulting in that such a hot-dip galvanized
steel sheet is evaluated to be poor in both plating wettability and plating
adhesiveness. Incidentally, more preferable values of the values of HA and
25 HB are each in the range of not less than 100 nor more than 500 (see FIG. 1).
[0051] The value of HA/HB is not less than 0.5 nor more than 0.9 in this
27
embodiment (see the above-described relational expression (3)). This is
reflected also in the graph shown in FIG, 2. Further, from results of
corresponding examples (examples and comparative examples), the following
is clarified. When the value of HA/HB is less than 0.5, the surface layer (with
5 the the depth of 50 um or less) of the base steel sheet is locally deformed
easily at the time of presswork and the hot-dip galvanizing layer cannot
follow the deformation to peel off from the base steel sheet, resulting in that
such a hot-dip galvanized steel sheet is evaluated to be poor in both plating
wettability and plating adhesiveness. Further, when the value of HA/HB is
10 greater than 0.9, deformation force and shear stress when presswork
concentrate in the hot-dip galvanizing layer, resulting in that such a hot-dip
galvanized steel sheet is evaluated to be poor in both plating wettability and
plating adhesiveness. Incidentally, a more preferable value of HA/HB is in
the range of not less than 0.6 nor more than 0.8 (see FIG. 2).
15 [0052] From the above, the above-described relational expressions (1) to
(3) of the base steel sheet are all satisfied, and thereby the hot-dip galvanized
steel sheet can be made excellent also in workability. In this embodiment in
particular, although the base steel sheet contains Si and Mn to thus be
increased in strength (hardness), the hot-dip galvanized steel sheet can exhibit
20 the above-described effects.
[0053] Further, the difference in hardness between the deep portion and the
surface layer of the above-described base steel sheet can also be expressed by
difference in content percentage of the components contained in the base steel
sheet. In the case when the formation of the surface layer of the base steel
25 sheet is performed by using a heating furnace and a soaking furnace, for
example, when attention is focused on Si and Mn and it is considered that a
28
treatment atmosphere in the furnaces is a decarburizing atmosphere, this
embodiment is also expressed as follows. Incidentally, it goes without
saying that the base steel sheet is defined by both the difference in hardness
and the difference in content percentage of components, thereby making it
5 possible to provide a hot-dip galvanized steel sheet having uniform quality.
[0054] Wc (A), WSi (A), and WMn (A) representing the content percentages of C,
Si, and Mn in mass% in the surface layer of the base steel sheet respectively
and Wc(B), WSi(B), and WMn(B) representing the content percentages of C, Si,
and Mn in mass% in the deep portion of the base steel sheet respectively
10 satisfy all the following relational expressions (4) to (6).
0.1 ^ WC(A/WC(B) ^ 0.5 -.(4)
0.1 ^ WSKA/WSKB) ^ 0.5 .-(5)
0.1 ^ WMII(A/WMII(B) ^ 0.5-(6)
[0055] Here, measurements ofWC(A), WSJ(A), and WMn(A) are performed
15 by performing analysis in the depth direction with the surface of the base steel
sheet being a starting point roughly. Concretely, the surface of the hot-dip
galvanized steel sheet is analyzed by XPS (X-ray photoelectron spectroscopy)
while being sputtered at intervals of 10 um. In this embodiment, WC(A> WSI
(A), and WM.i (A) mean average values of analysis values of the respective
20 components (the content percentage of C, the content percentage of single
element Si, and the content percentage of single element Mn) in the range of
the position where Zn is not detected substantially to 50 urn in depth.
Similarly, Wc (B> Wsi (B)> and WMn (B) mean average values of analysis values,
being analysis values at the position deeper than where Zn is not detected
25 substantially, of the respective components (the content percentage of C, the
content percentage of single element Si, and the content percentage of single
29
element Mn) in the range of 100 urn to 200 um in depth.
[0056] The above-described relational expressions (4) to (6) are reflected
also in the graphs shown in FIG 3 and FIG. 4. Further, from results of
corresponding examples (examples and comparative examples), the following
5 is clarified. When the values of Wc (A/WC (B), WS; (A/WSI (B> and WMn
(A/WMH (B> are each not less than 0.1 nor more than 0.5, such a hot-dip
galvanized steel sheet is evaluated to be excellent in both plating wettability
and plating adhesiveness. On the other hand, when the values of these ratios
are each less than 0.1, C, Si, and Mn solid-dissolved in the base steel sheet are
10 segregated in the depth direction inside the base steel sheet and concentration
distribution is generated, hardness and workability (ductility) of the base steel
sheet vaiy largely, and due to the variations, the base steel sheet is deformed
locally at the time of presswork and plating is easily peeled off from the base
steel sheet, resulting in that such a hot-dip galvanized steel sheet is evaluated
15 to be poor in plating wettability and plating adhesiveness. When the values
of these ratios are each greater than 0.5, C, Si, and Mn solid-dissolved in the
base steel sheet inhibit reaction at the interface between the base steel sheet
and the hot-dip galvanizing layer, and further due to the hardness of the base
steel sheet being uniform, deformation force and shear stress when presswork
20 concentrate in the hot-dip galvanizing layer, resulting in that such a hot-dip
galvanized steel sheet is evaluated to be poor in plating wettability and plating
adhesiveness. Moi*e preferable values of Wc (A/WC (B> WSI (A/WSI (B> and
WMn (A/WMH (B) are each in the range of not less than 0.15 nor more than 0.4
(see FIG 3 and FIG 4).
25 [0057] Further, in a more preferable aspect of this embodiment, the
hot-dip galvanizing layer of the hot-dip galvanized steel sheet has a thickness
30
in the range of not less than 1 (am nor more than 30 urn. Additionally, the
hot-dip galvanizing layer contains not less than 4 mass% nor more than 14
mass% of Fe and not less than 0.1 mass% nor more than 1 mass% of Al, and
contains a balance being composed of Zn and inevitable impurities. By
5 satisfying these conditions, such a hot-dip galvanized steel sheet is evaluated
to be more excellent in plating wettability and plating adhesiveness. This is
reflected in the graphs shown in FIG. 5 and FIG. 6. Further, from results of
corresponding examples (examples and comparative examples), the following
is clarified.
10 [0058] When the thickness of the hot-dip galvanizing layer is less than 1
um, a rust prevention property of the hot-dip galvanized steel sheet becomes
insufficient, and further uniform plating adhesion to the surface of the base
steel sheet becomes difficult and thereby unplating defects of the hot-dip
galvanized steel sheet are caused. That is, there is caused a problem of
15 worsening of plating wettability. When the thickness of the hot-dip
galvanizing layer is greater than 30 um, an effect of improvement in corrosion
resistance is saturated and it is uneconomical, and further inside the hot-dip
galvanizing layer, residual stress increases, resulting in that plating
adhesiveness becomes worse on the contrary. Incidentally, in this
20 embodiment, the thickness of the hot-dip galvanizing layer is calculated in a
manner that a region having a size of 100 um x 100 um of a cross section of
the hot-dip galvanizing layer is observed by a SEM (scanning electron
microscope), the thickness of the hot-dip galvanizing layer is measured by N
= 5, and values of obtained measurement results are averaged.
25 [0059] Further, when the content percentage of Fe in the hot-dip
galvanizing layer is less than 4%, reactivity of the hot-dip galvanizing layer
31
and the base steel sheet is poor, resulting in that such a hot-dip galvanized
steel sheet is evaluated to be poor in plating wettability and plating
adhesiveness. On the other hand, when the content percentage of Fe is
greater than 14%, in the interface between the hot-dip galvanizing layer and
5 the base steel sheet, a T phase or Ti phase of hard Fe-Zn alloy is formed in
large amounts, resulting in that such a hot-dip galvanized steel sheet is
evaluated to be poor in plating wettability and plating adhesiveness.
[0060] Further, when the content percentage of Al of the hot-dip
galvanizing layer is less than 0.1, it becomes impossible to sufficiently exhibit
10 an effect that slidabiiity of plating can be improved by containing Al in
plating, resulting in that such a hot-dip galvanized steel sheet is evaluated to
be poor in plating wettability and plating adhesiveness. On the other hand,
when the content percentage of Al is greater than 1%, the hot-dip galvanizing
layer becomes hard, resulting in that such a hot-dip galvanized steel sheet is
15 evaluated to be poor in plating wettability and plating adhesiveness.
[0061] Incidentally, the content percentage of Fe and the content
percentage of Al in the hot-dip galvanizing layer are calculated in the
following manner, for example. A sample having a size of 30 mm x 30 mm
cut out from the hot-dip galvanized steel sheet is immersed in a 5%
20 hydrochloric acid aqueous solution to which 0.02 vol% of an inhibitor
(IBIT700A manufactured by ASAHI Chemical Co., Ltd.) is added, and
thereby only the plating layer is dissolved. Subsequently, the obtained
solution is analyzed by an ICP (an emission spectrochemical analyzer), and
from its analysis result, the mass of Fe, the mass of Zn, and the mass of Al are
25 found. Then, the mass of Fe is divided by (the mass of Fe + the mass of Zn
+ the mass of Al) and is multiplied by 100, and thereby the content percentage
32
of Fe is calculated. Further, the mass of Al is divided by (the mass of Fe +
the mass of Zn + the mass of Al) and is multiplied by 100, and thereby the
content percentage of Al is calculated.
[0062] Next, there will be explained a manufacturing method of a hot-dip
5 galvanized steel sheet according to the second embodiment of the present
invention.
[0063] In this second embodiment, the hot-dip galvanized steel sheet is
manufactured by performing a hot-dip galvanizing treatment on a base steel
sheet containing Si and Mn basically. More concretely, the manufacturing
10 method according to this embodiment includes at least the following steps.
Annealing step: an annealing step of performing an annealing
treatment by heating on the aforementioned base steel sheet in the presence of
a first gas mixture containing carbon monoxide and carbon dioxide in a
heating furnace;
15 Soaking and holding step: a soaking and holding step of holding the
base steel sheet having had the aforementioned annealing treatment
performed thereon at a fixed temperature in the presence of a second gas
mixture containing carbon monoxide and carbon dioxide in a soaking furnace
connected to the aforementioned heating furnace; and
20 Plating step: a plating step of performing a hot-dip galvanizing
treatment on the base steel sheet obtained after undergoing the
aforementioned soaking and holding step
[0064] Additionally, in the manufacturing method according to this
embodiment, a manufacturing method of the base steel sheet, components of
25 the base steel sheet and their content percentages, a facility for manufacture,
heating furnace conditions in the annealing step, soaking furnace conditions
33
in the soaking and holding step, treatment conditions in the plating step, and
the like are set as follows.
[0065] • Manufacturing method of the base steel sheet and components of
the base steel sheet and their content percentages
5 The base steel sheet contains the components explained in the first
embodiment and the modified example basically. Concretely, the base steel
sheet is obtained after undergoing a casting step, a hot rolling step, a pickling
step, a cold rolling step, the above-described annealing step, and the
above-described soaking and holding step, and contains, in mass%,
10 C: not less than 0.05% nor more than 0.50%,
Si: not less than 0.1% nor more than 3.0%,
Mn: nor more than 0.5% nor more than 5.0%,
P: not less than 0.001% nor more than 0.5%,
S: not less than 0.001% nor more than 0.03%
15 Al: not less than 0.005% nor more than 1.0%, and
one or two or more of elements selected from Ti, Nb, Cr, Mo, Ni, Cu,
Zr, V, W, B, Ca, and a rare-earth element REM: not less than 0% nor more
than 1% each, and
a balance being composed of Fe and inevitable impurities.
20 [0066] • Facility for manufacture
As a facility for manufacture, a continuous hot-dip galvanizing facility
explained in the column of background art is used. That is, the annealing
step and the soaking and holding step are.performed in a continuous hot-dip
galvanizing facility equipped with an all radiant tube type heating furnace as a
25 heating furnace and a soaking furnace. Thereby, the base steel sheet (a
cold-rolled steel sheet) can be passed through in the heating furnace and in the
34
soaking furnace without being exposed to an oxidizing atmosphere such as
the air.
[0067] • Heating furnace conditions in the annealing step
The annealing step is performed so as to satisfy the following heating
5 furnace conditions.
Heating temperature: a sheet temperature T0 [°C] representing
the maximum temperature that, when a cold-rolled steel sheet obtained after
undergoing the cold rolling step is heated in the heating furnace, the
cold-rolled steel sheet reaches is in the range of not lower than a temperature
10 Ti [°C] nor higher than a temperature T2 [°C];
Heating time period: a heating time period So [second] in the
heating furnace is in the range of not shorter than a time period S\ [second]
nor longer than a time period S2 [second]; and
Atmosphere gas: a nitrogen atmosphere containing carbon
15 dioxide and carbon monoxide in which log(PC02/PCO) being a logarithmic
value of a value of, in the heating furnace, a partial pressure value of carbon
dioxide divided by a partial pressure value of carbon monoxide exhibits a
value in the range of not less than -2 nor more than 1.
[0068] Here, the temperatures Ti and T2 and the time periods Si and S2
20 described above are defined as follows.
Ti: a temperature [°C] satisfying the following relational expression
(7) using Wsi (B) and WM„ (BJ representing content percentages of Si and Mn in
mass% in a deep portion ranging from a surface of the cold-rolled steel sheet
to greater than 50 jam in depth respectively;
25 Ti = 500 - 50 x WSi(B) - 20 x WMn(B)-(7)
T2: a temperature [°C] satisfying the following relational expression
35
(8) using a temperature TAc3 [°C] corresponding to a transformation point AC3
of the cold-rolled steel sheet;
T2-TAc3 + 40..-(8)
Si: a time period [second] satisfying the following relational
5 expression (9) using WSi (B> [mass%] representing the content percentage of Si
and WMn 2/PCO) in the soaking furnace becomes -2 or more,
an internal oxidation reaction of Si and Mn progresses excessively to cause
10 that intercrystalline cracking caused by internal oxides occurs in grain
boundaries of the surface layer of the base steel sheet, and further carbon in
the surface layer of the base steel sheet oxidizes excessively to be released
from the base steel sheet and hardness of the base steel sheet decreases
significantly, resulting in that such a hot-dip galvanized steel sheet is
15 evaluated to be poor in plating wettability and plating adhesiveness.
[0086] Incidentally, after performing the annealing step in the heating
furnace and the soaking and holding step in the soaking furnace, and before
performing the plating step, other treatment steps may also be performed.
As such a treatment step, at least one step selected.from a slow cooling step, a
20 quenching step, an overaging step, a second cooling step, a water quenching
step, and a reheating step is performed. Similarly, after performing the
plating step, other treatment steps may also be performed.
[0087] • Plating step
Further, a bath temperature of a hot-dip galvanizing bath is preferably
25 440°C or higher and lower than 550°C. When the bath temperature is lower
than 440°C, there is a possibility that solidification of molten zinc is caused in
45
the bath, so that it is inappropriate, and when it exceeds 550°C, evaporation of
molten zinc is hard on the surface of the bath, and thus in terms of operation
cost and further in terms of attachment of vaporized zinc to the inside of the
furnace, operational problems are caused.
5 [0088] • Treatment conditions in the plating step
The treatment conditions in the plating step will be explained.
Schematically, the components of the hot-dip galvanizing layer and
the content percentages of them are defined, and the thickness of the hot-dip
galvanizing layer is defined. In this embodiment, as explained previously,
10 the hot-dip galvanizing layer is defined to contain not less than 4 mass% nor
more than 14 mass% of Fe and not less than 0.1 mass% nor more than 1
mass% of Al and contain a balance being composed of Zn and inevitable
impurities, and the thickness of the hot-dip galvanizing layer formed on the
surface of the base steel sheet is defined to fall within the range of not less
15 than 1 jam nor more than 30 jam.
[0089] In a preferable aspect of this embodiment, the concentration of Al
in a melt in the hot-dip galvanizing bath to be used in the plating step is set to
be in the range of not less than 0.05% nor more than 0.20%. Thereby, it is
possible to manufacture a hot-dip galvanized steel sheet excellent in plating
20 wettability and plating adhesiveness. This is reflected also in FIG. 11.
Further, from results of corresponding examples (examples and comparative
examples), the following is clarified. When the concentration of Al becomes
less than 0.05%, a £ phase is formed in large amounts, resulting in that such a
hot-dip galvanized steel sheet is evaluated to be poor in plating adhesiveness.
25 On the other hand, when the concentration of Al becomes greater than 0.2%o,
the amount of Al oxidized in the hot-dip galvanizing bath or on the hot-dip
46
galvanizing bath increases and the reactivity of the hot-dip galvanizing and
the base steel sheet becomes worse, resulting in that such a hot-dip galvanized
steel sheet is evaluated to be poor in plating wettability and plating
adhesiveness.
5 [0090] Further, in another preferable aspect of this embodiment, after
performing the annealing step in the heating furnace and the soaking and
holding step in the soaking furnace, and before performing the hot-dip
galvanizing treatment, cooling of the base steel sheet is performed, and
temperature keeping is performed according to need. Further, in this aspect,
10 after performing the hot-dip galvanizing treatment, an alloying treatment is
performed.
[0091] On the occasion of the above-described alloying treatment, a
heating temperature when heating is in the range of not lower than 450°C nor
higher than 560°C. Thereby, an obtainable hot-dip galvanized steel sheet
15 can be made excellent in plating wettability and plating adhesiveness. The
range of this heating temperature is shown also in FIG. 11. Further, from
results of corresponding examples (examples and comparative examples), the
following is clarified. When the heating temperature of the alloying
treatment is lower than 440°C, an alloying reaction does not progress
20 sufficiently, so that an obtainable hot-dip galvanized steel sheet is evaluated to
be poor in plating wettability and plating adhesiveness. On the other hand,
when the heating temperature of the alloying treatment is higher than 560°C,
due to overalloying, a T phase or T\ phase of hard and brittle Zn-Fe alloy is
formed in large amounts on an interface of a base iron, plating adhesiveness
25 becomes worse or deteriorates, and further carbide of Fe is formed, and thus
the balance between strength and ductility of the base steel sheet also
47
becomes worse. Incidentally, this is caused even if the base steel sheet is a
DP steel or a TRIP steel. Thus, also in the case of the heating temperature
being too high, an obtainable hot-dip galvanized steel sheet is evaluated to be
poor in plating wettability and plating adhesiveness.
5 Example
[0092] Hereinafter, examples according to the present invention (the
examples and the comparative examples) will be explained concretely.
[0093] Cold-rolled steel sheets obtained after undergoing normal casting,
hot rolling, pickling, and cold rolling and having a thickness of 1 mm were
10 prepared as sample materials 1 to 72 (see Table 1). On these sample
materials, an annealing treatment and a hot-dip galvanizing treatment were
performed in a continuous hot-dip galvanizing facility equipped with an all
radiant tube type heating furnace. The all radiant tube type heating furnace
was used, so that roll pickup was not easily caused and further productivity
15 was also good. The temperature TAc3 corresponding to an Ac3 point being a
transformation point in Table 1 was calculated by using a calculation
expression of a transformation temperature provided on a web site of Welding
Technology Information Center of The Japan Welding Engineering Society
(http://www-it.jwes.or.jp/weld_simulator/call.jsp).
20 [0094] [Table 1]
49
[0095] In Tables 2-1 to 4-2 below, treatment conditions in the heating
furnace and a soaking furnace and a logarithmic value log(PC02/PCO) of a
value of a carbon dioxide partial pressure divided by a carbon monoxide
partial pressure are shown. The comparative examples are shown in Table
4-1 and Table 4-2. Incidentally, the treatment atmosphere in the furnaces
was set to a nitrogen gas containing carbon dioxide and carbon monoxide.
Carbon dioxide and carbon monoxide were supplied into the furnaces as a
mixed gas.
[0096] [Table 2-1]
58
[0104] After the treatment in the soaking furnace, the sample materials
underwent a general slow cooling step, quenching step, overaging step, and
second cooling step and were immersed in a hot-dip galvanizing bath.
Conditions of the hot-dip galvanizing bath and an alloying furnace are also
5 shown in Tables 2-1 to 4-2. Each thickness of hot-dip galvanizing layers
was adjusted by nitrogen gas wiping. Plating wettability and plating
adhesiveness of obtained hot-dip galvanized steel sheets were evaluated.
Results of the evaluation are also shown in Tables 2-1 to 4-2.
[0105] Of the obtained hot-dip galvanized steel sheets, Vickers
10 hardnesses HA and HB and WC(A), WSi(A), WMn(A), WC(B), Wsi(B), and WMn(B)
were found by the previously described methods. Further, of the hot-dip
galvanizing layers, thicknesses, content percentages of Fe, and content
percentages of Al were also found by the previously described methods.
Respective results are shown in Tables 2 to 4.
15 [0106] The plating adhesiveness was measured by a powdering test, and
the case of a peeled width of the hot-dip galvanizing layer being greater than
2 mm was evaluated as rejection (x) because of adhesiveness being bad, the
case of the peeled width being 2 mm or less and greater than 0.5 mm was
evaluated as pass (O) because of adhesiveness being good, and the case of
20 the peeled width being 0.5 mm or less was evaluated as pass (©) because of
adhesiveness being extremely good. The powdering test is an adhesiveness
inspection method, in which to an alloyed hot-dip galvanized steel sheet, a
Sellotape (registered trademark) is applied, a tape surface is bent at 90° and is
bent back, and then the tape is peeled off, and a peeled width made at that
25 time is measured.
[0107] With regard to the plating wettability, after the plating
59
adhesiveness was measured by the powdering test, a plating surface having a
size of 200 (im x 200 urn in the adhesiveness measured portion was subjected
to EPMA mapping of Zn and Fe, and the case of an area ratio of a place where
there is no Zn and Fe is exposed being not less than 20% nor more than 100%
5 was evaluated as rejection (x) because of wettability being bad, the case of the
area ratio being 5% or more and less than 20% was evaluated as pass (O)
because of wettability being good, and the case of the area ratio being less
than 5% was evaluated as pass (©) because of wettability being extremely
good.
10 [0108] Examination results of the plating wettability and the plating
adhesiveness of the examples of the present invention and the comparative
examples were rated with points, in which © was regarded as 2 points, O
was regarded as 1 point, and x was regarded as 0 point. Then, the sum of
points of the plating wettability and points of the plating adhesiveness was set
15 to a total point. With regard to overall evaluation, the evaluation of plating
wettability was O or ©, the evaluation of plating adhesiveness was O or
©, and the total point was 2 points or more (2 points to 4 points), which was
regarded as pass. It was found that Levels Al to A72, Bl to B72, and CI to
C72 in Tables 2-1 to 3-2 that are the examples of the present invention are
20 excellent in plating wettability and plating adhesiveness as compared to
Levels Dl to D56 in Tables 4-1 to 4-2 that are the comparative examples.
[Industrial Applicability]
[0109] The hot-dip galvanized steel sheet according to the present
invention is excellent in plating wettability and plating adhesiveness, to thus
25 be usable as a member of products in an automotive field, a household
appliance filed, or a building material filed, for example.
60
[Name of Document] Claim
[Claim 1] A hot-dip galvanized steel sheet including a base steel sheet
and a hot-dip galvanizing layer formed on at least one surface of the base steel
sheet, wherein
the base steel sheet contains, in mass%,
C: not less than 0.05% nor more than 0.50%,
Si: not less than 0.1% nor more than 3.0%,
Mn: not less than 0.5% nor more than 5.0%,
P: not less than 0.001% nor more than 0.5%,
S: not less than 0.001% nor more than 0.03%,
Al: not less than 0.005% nor more than 1.0%, and
one or two or more of elements selected from Ti, Nb, Cr, Mo,
Ni, Cu, Zr, V, W, B, Ca, and a rare-earth element REM: not less than 0% nor
more than 1% each, and
a balance being composed of Fe and inevitable impurities, and
in the base steel sheet, a value of HA representing average hardness in
a surface layer ranging from an interface between the base steel sheet and the
hot-dip galvanizing layer to 50 um in depth and a value of HB representing
average hardness in a deep portion ranging from the interface to greater than
50 um in depth satisfy all the following relational expressions (1) to (3).
50 ^ HA ^ 500 -(1)
50 ^ HB ^ 500 -(2)
0.5 ^ HA/HB ^ 0.9-(3)
[Claim 2] The hot-dip galvanized steel sheet according to claim 1,
wherein
Wc(A> Wsi(A> a nd WMH(A) representing content percentages of C, Si,
61
and Mn in mass% in the surface layer of the base steel sheet respectively and
Wc (B> Wsi (B), and WM,i (B) representing content percentages of C, Si, and Mn
in mass% in the deep portion of the base steel sheet respectively satisfy all the
following relational expressions (4) to (6).
0.1 £ WC(A/WC(B) ^ 0.5 -(4)
0.1 ^ WSKA/Wsi(B) ^ 0.5-.(5)
0.1 ^ WMn(A/WMaai) ^ 0.5 ..<6)
[Claim 3] The hot-dip galvanized steel sheet according to claim 1 or 2,
wherein
the base steel sheet contains one or two or more of elements selected
from Ti, Nb, Cr, Mo, Ni, Cu, Zr, V, W, B, Ca, and a rare-earth element REM
in not less than 0.0001% nor more than 1% each.
[Claim 4] The hot-dip galvanized steel sheet according to any one of
claims 1 to 3, wherein
the hot-dip galvanizing layer has a thickness in the range of not less
than 1 fim nor more than 30 urn, and contains not less than 4 mass% nor more
than 14 mass% of Fe, not less than 0.1 mass% nor more than 1 mass% of Al,
and a balance being composed of Zn and inevitable impurities.
[Claim 5] A method for manufacturing a hot-dip galvanized steel sheet
by performing a hot-dip galvanizing treatment on a base steel sheet, wherein
the base steel sheet is obtained after undergoing a casting step, a hot
rolling step, a pickling step, a cold rolling step, an annealing step, and a
soaking and holding step, and contains, in mass%,
C: not less than 0.05% nor more than 0.50%,
Si: not less than 0.1% nor more than 3.0%,
Mn: not less than 0.5%) nor more than 5.0%,
62
P: not less than 0.001% nor more than 0.5%,
S: not less than 0.001% nor more than 0.03%,
Al: not less than 0.005% nor more than 1.0%, and
one or two or more of elements selected from Ti, Nb, Cr, Mo,
Ni, Cu, Zr, V, W, B, Ca, and a rare-earth element REM: not less than 0% nor
more than 1% each, and
a balance being composed of Fe and inevitable impurities,
the annealing step and the soaking and holding step are performed in a
continuous hot-dip galvanizing facility equipped with an all radiant tube type
heating furnace as a heating furnace and a soaking furnace,
the annealing step is performed so as to satisfy the following heating
furnace conditions:
heating temperature: a sheet temperature T0 [°C] representing
the maximum temperature that, when a cold-rolled steel sheet obtained after
undergoing the cold rolling step is heated in the heating furnace, the
cold-rolled steel sheet reaches is in the range of not lower than a temperature
Ti [°C] nor higher than a temperature T2 [°C];
heating time period: a heating time period S0 [second] in the
heating furnace is in the range of not shorter than a time period Sf [second]
nor longer than a time period S2 [second]; and
atmosphere gas: a nitrogen atmosphere containing carbon
dioxide and carbon monoxide in which log(PC02/PCO) being a logarithmic
value of a value of, in the heating furnace, a partial pressure value of carbon
dioxide divided by a partial pressure value of carbon monoxide exhibits a
value in the range of not less than -2 nor more than 1,
here, the temperatures T{ and T2 and the time periods Si and S2 are
63
defined as follows:
Ti: a temperature [°C] satisfying the following relational expression
(7) using WSi (B) and WMP (B) representing content percentages of Si and Mn in
mass% in a deep portion ranging from a surface of the cold-rolled steel sheet
to greater than 50 iim in depth respectively;
T, = 500 - 50 x WSUB) - 20 x WMn(B)-(T)
T2: a temperature [°C] satisfying the following relational expression
(8) using a temperature TAc3 [°C] corresponding to a transformation point AC3
of the cold-rolled steel sheet;
T2 = TAc3 + 40-(8)
Si: a time period [second] satisfying the following relational
expression (9) using Wsi (B) [mass%] representing the content percentage of Si
and WMH (B) [mass%] representing the content percentage of Mn in the deep
portion of the cold-rolled steel sheet; and
S, = 50 + 20 x Wsi
Documents
Application Documents
#
Name
Date
1
POWER OF AUTHORITY.pdf ONLINE
2015-03-03
2
PCT-IB-304.pdf ONLINE
2015-03-03
3
OTHER RELEVANT DOCUMENT.pdf ONLINE
2015-03-03
4
FORM 5.pdf ONLINE
2015-03-03
5
FORM 3.pdf ONLINE
2015-03-03
6
FORM 2 + SPECIFICATION.pdf ONLINE
2015-03-03
7
DRAWING.pdf ONLINE
2015-03-03
8
1525-DELNP-2015.pdf
2015-03-03
9
POWER OF AUTHORITY.pdf
2015-03-13
10
PCT-IB-304.pdf
2015-03-13
11
OTHER RELEVANT DOCUMENT.pdf
2015-03-13
12
FORM 5.pdf
2015-03-13
13
FORM 3.pdf
2015-03-13
14
FORM 2 + SPECIFICATION.pdf
2015-03-13
15
DRAWING.pdf
2015-03-13
16
1525-delnp-2015-Form-1-(17-03-2015).pdf
2015-03-17
17
1525-delnp-2015-Correspondence Others-(17-03-2015).pdf
2015-03-17
18
1525-delnp-2015-Form-3-(19-06-2015).pdf
2015-06-19
19
1525-delnp-2015-Correspondence Other-(19-06-2015).pdf
2015-06-19
20
1525-delnp-2015-Form-3-(17-09-2015).pdf
2015-09-17
21
1525-delnp-2015-Correspondence Others-(17-09-2015).pdf
2015-09-17
22
Form 3 [24-05-2016(online)].pdf
2016-05-24
23
Form 3 [15-11-2016(online)].pdf
2016-11-15
24
Form 3 [04-05-2017(online)].pdf
2017-05-04
25
1525-DELNP-2015-FORM 3 [04-12-2017(online)].pdf
2017-12-04
26
1525-DELNP-2015-FORM 3 [08-08-2018(online)].pdf
2018-08-08
27
1525-DELNP-2015-FER.pdf
2019-03-18
28
1525-DELNP-2015-FORM 3 [17-05-2019(online)].pdf
2019-05-17
29
1525-DELNP-2015-RELEVANT DOCUMENTS [10-06-2019(online)].pdf
2019-06-10
30
1525-DELNP-2015-FORM 13 [10-06-2019(online)].pdf
2019-06-10
31
1525-DELNP-2015-Power of Attorney-120619.pdf
2019-06-20
32
1525-DELNP-2015-OTHERS-120619.pdf
2019-06-20
33
1525-DELNP-2015-Correspondence-120619.pdf
2019-06-20
34
1525-DELNP-2015-OTHERS [30-07-2019(online)].pdf
2019-07-30
35
1525-DELNP-2015-FER_SER_REPLY [30-07-2019(online)].pdf
2019-07-30
36
1525-DELNP-2015-DRAWING [30-07-2019(online)].pdf
2019-07-30
37
1525-DELNP-2015-CORRESPONDENCE [30-07-2019(online)].pdf
2019-07-30
38
1525-DELNP-2015-COMPLETE SPECIFICATION [30-07-2019(online)].pdf
2019-07-30
39
1525-DELNP-2015-CLAIMS [30-07-2019(online)].pdf
2019-07-30
40
1525-DELNP-2015-US(14)-HearingNotice-(HearingDate-12-11-2021).pdf
2021-10-17
41
1525-DELNP-2015-FORM-26 [09-11-2021(online)].pdf
2021-11-09
42
1525-DELNP-2015-Correspondence to notify the Controller [09-11-2021(online)].pdf
2021-11-09
43
1525-DELNP-2015-Written submissions and relevant documents [23-11-2021(online)].pdf
2021-11-23
44
1525-DELNP-2015-PatentCertificate12-04-2022.pdf
2022-04-12
45
1525-DELNP-2015-IntimationOfGrant12-04-2022.pdf
2022-04-12
46
1525-DELNP-2015-Response to office action [15-06-2022(online)].pdf
2022-06-15
47
1525-DELNP-2015-Annexure [15-06-2022(online)].pdf
2022-06-15
48
1525-DELNP-2015-Response to office action [11-07-2022(online)].pdf
2022-07-11
Search Strategy
1
1525delnp2015_15-03-2019.pdf
ERegister / Renewals
Inforce
3rd: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹4,000
Certificate #46802
From 02/08/2015 - To 02/08/2016
4th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹4,000
Certificate #46803
From 02/08/2016 - To 02/08/2017
5th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹4,000
Certificate #46804
From 02/08/2017 - To 02/08/2018
6th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹4,000
Certificate #46805
From 02/08/2018 - To 02/08/2019
7th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹12,000
Certificate #46806
From 02/08/2019 - To 02/08/2020
8th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹12,000
Certificate #46807
From 02/08/2020 - To 02/08/2021
9th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹12,000
Certificate #46808
From 02/08/2021 - To 02/08/2022
10th: 25 Jun 2022
CBR 24145
Renewal 25/06/2022
Renewal Amount ₹12,000
Certificate #46809
From 02/08/2022 - To 02/08/2023
11th: 07 Jul 2023
CBR 30457
Renewal 07/07/2023
Renewal Amount ₹24,000
Certificate #67251
From 02/08/2023 - To 02/08/2024
12th: 04 Jul 2024
CBR 44608
Renewal 04/07/2024
Renewal Amount ₹24,000
Certificate #161079
From 02/08/2024 - To 02/08/2025
13th: 02 Jul 2025
CBR 34569
Renewal 02/07/2025
Renewal Amount ₹24,000
Certificate #54332
From 02/08/2025 - To 02/08/2026