Title of Invention

COATED STEEL SHEET AND METHOD FOR MANUFACTURING THE SAME

Abstract A coated steel sheet having a coated layer on surfaces of a steel sheet of a composition containing not less than 0.1 mass% and under 3 mass% of Al, wherein a following condition A or B is met: A: An AlN precipitate layer exists on a matrix side near an interface between said steel sheet and said coated layer B: Oxide of Al exists in said matrix right under said surfaces of said steel sheet.
Full Text COATED STEEL SHEET AND
METHOD FOR MANUFACTURING THE SAME
TECHNICAL FIELD
The present invention relates to a coated steel sheet and
a method for manufacturing the coated steel sheet suitable for
technical fields, such as automobiles, construction materials,
and household appliances.
BACKGROUND ART
In recent years, in fields, such as automobiles,
construction materials, household appliances, and so on, the
use of high-tensile steel sheet has increased. Particularly
in the automotive industry, the adoption of high-tensile steel
sheet is increasing rapidly with a view to reducing car weight
for better fuel economy and improved crashworthiness.
In addition to high tensile strength, to provide
ductility to withstand a complicated press-forming,
development has been actively pushed forward for a high-ductile
high-tensile steel of a structure containing retained austenite
to utilize a strain-induced transformation of this retained
austenite.
As an example of high-tensile steel sheets, there is one
that has a composition including addition elements such as Si,
Mn, Ti, A1 and P, which is disclosed in Japanese Patent
Publication No. 3-51778. It is well known, however, that as
the Si content is increased, an Si oxide film is formed on the
surfaces of the steel sheet during an annealing process, thus
deteriorating the steel properties, such as chemical properties,
electro-galvanized coating adhesion, hot-dip galvanizability,
and hot-dip galvanized coating adhesion. Above all else, the
big problem is the inferior hot-dip galvanizability of
Si-containing high-tensile steel sheets, i.e., the applied zinc
does not adhere to some portions of the steel sheet" (so-called
"bare-spot") in hot-dip galvanizing, or the adhesion of the
coating is insufficient. When a steel sheet contains not less
than 0.1%) carbon by mass, there has been difficulty in carrying
out galvanizing or forming a stable galvanized layer even on
a continuous hot-dip galvanizing line, which includes a RTH (all
Radiant Tube Heating) type furnace or a NOF (Non Oxidizing
Furnace) type furnace.
As a method for increasing ductility and tensile strength
without increasing the Si content, a technique for achieving
high ductility and high tensile strength has been disclosed,
in which instead of increasing the Si content, the Al content
in the steel is positively increased to thereby prevent the
surface quality deterioration peculiar to the Si-added steel
and simultaneously make the retained austenite stable
(JP-A-5-171344).
However, because Al and Si are readily, oxidizable
elements, in addition to the Si oxide film, an Al oxide film
is formed during annealing, and as with the Si-added steel, it
has been impossible to prevent deteriorations in the hot-dip
galvanizability and the galvanized coating adhesion in the
Al-added steel sheet.
It is generally well known that Al is an element to
deteriorate weldability. To make an Al-added steel
practically applicable, it has become an imperative requirement
to improve its spot-weldability.
When a high-tensile steel sheet is used for automobiles,
after chemical treatment or electrodeposition coating, a top
coat is applied when necessary, and as demand is mounting for
rust resistance in recent years, the improvement of corrosion
resistance after an electrodeposition process is increasingly
important. However, a high-tensile steel sheet, which
contains a large amount of galvannealing elements with high
reactivity, is poorer in corrosion resistance than mild steel.
For this reason, if one tries to further improve corrosion
resistance, there is a problem of difficulty in increasing high
strength.
The present invention has been made to solve the above
problems in the prior art, and has as its object to provide a
coated steel sheet superior in coating adhesion even if the base
sheet is an Al-containing steel sheet, and also provide a method
for manufacturing this coated steel sheet.
DISCLOSURE OF THE INVENTION
To solve the above problems, according to the present
invention, there is provided a coated steel sheet which has a
coated layer on a surface of a steel sheet of a composition
containing not less than 0.1 mass% and under 3 mass% of Al,
wherein there is an AIN precipitate layer on the matrix side
near the interface between the steel sheet and the coated layer
or there is an oxide of Al in the steel matrix right under the
surface of the steel sheet.
Further, the coated layer preferably is a hot-dip
galvanized layer and contains 0.1~1.0 mass% of Al.
Further, the coated layer preferably is a Zn-Fe
galvanneal coating that further contains 7~15 mass% of Fe.
Further, the AlN precipitate layer preferably has a
thickness of not less than lµm and not more than 100µm.
In addition, the steel composition preferably further
contains one or two kinds selected from not less than 0.1 mass%
of Si and not less than 0.5 mass% of Mn.
Moreover, the steel composition preferably further
contains one or two kinds selected from not less than 0.01 mass%
and not more than 1 mass% of Mo and not less than 0.005 mass%
and not more than 0.2 mass% of Nb.
Furthermore, the steel composition preferably further
contains not less than 0.01 mass% and not more than 0.5 mass%
of Cu, not less than 0.01 mass% and not more than 1 mass% of
Ni, and not less than 0.01 mass% and not more than 1 mass% of
Mo.
Moreover, the steel composition preferably further
contains 0.03-0.25 mass% of C, 0.001~1.0 mass% of Si, 0.5~3.0
mass% of Mn, and 0.001~0.10 mass% of P.
Further in the steel matrix, there are preferably one or
more kinds selected from oxides of SiO2, MnO, FeSiO3, Fe2SiO4,
MnSiO3, Mn2SiO4, and P2O5.
Further, the amount of oxides in total per one side surface
is preferably 0.01~1.0 g/m2.
Further, the steel composition preferably contains
0.01~1.0 mass% of Mo and 0.005~0.2 mass% of Nb.
Further, the steel composition is preferably 0.01~0.5
mass% of Cu, 0.01~1.0 mass% of Ni, and 0.01~1.0 mass% of Mo.
Moreover, the coated layer is preferably galvannealed.
In addition, the Fe content in the galvannealed coated
layer is preferably 7~15% by mass.
On the other hand, a method for manufacturing a coated
steel sheet according to the present invention comprises the
steps of heating and holding a steel slab, and hot-rolling the
slab and hot-dip-galvanizing a hot-rolled steel sheet,
wherein the slab contains not less than 0.1 mass% under 3 mass%
of Al, and the above-mentioned holding is carried out in an
atmosphere containing not less than 1 vol% and not more than
20 vol% of O2 and not less than 70 vol" of N under the conditions
that meet an equation (1) shown below and the above-mentioned
galvanizing is performed by using a galvanizing bath with an
Al concentration in the bath is 0.14~0.24 mass% at a bath
temperature of 440~500°C.
{Heating and holding temp. ( °C) — (1050 + 25Al)} X heating and
holding time (min) = 3000 ........(1)
wherein Al denotes an Al content (mass%) in the steel.
Preferably, the steel sheet is galvanized by using a
galvanizing bath of Al concentration of 0.10~0.20 mass% in the
bath at a bath temperature of 440~500°C and the
hot-dip-galvanized layer is further subjected to a
galvannealing process at 460~550°C.
Further, preferably, cold-rolling is carried out between
the hot-rolling process and the hot-dip galvanizing process.
Moreover, the steel slab preferably further contains one
or two kinds selected from not less than 0.1 mass% of Si and
not less than 0.5 mass% of Mn.
Additionally, the slab preferably further contains one
or two kinds selected from not less than 0.01 mass% and not more
than 1 mass% of Mo and not less than 0.005 mass% and not more
than 0.2 massl of Nb.
Moreover, the slab preferably further contains not less
than 0.01 massV, and not more than 0.5 mass% of Cu and not less
than 0.01 mass% and not more than 1 mass% of Ni, and not less
than 0.01 mass% and not more than 1 mass% of Mo.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a picture showing an electron microscope
observation result of an AlN precipitate layer;
Fig. 2 is a picture showing AlN precipitate layer analyzed
by EPMA; and
Figs. 3A to 3D are graphs showing effects of holding
temperature and holding time on the coating adhesion and the
occurrence of the AlN precipitate layer when the slab was
heated.
BEST MODE FOR CARRYING OUT THE INVENTION
Description will be made of a coated steel sheet, and
particularly of a hot-dip galvanized steel sheet and a method
for manufacturing the hot-dip galvanized steel sheet.
(1) First Embodiment
Description will start with a chemical composition of a
steel sheet as a base sheet for coating as a first embodiment
of the present invention. Note that in the following
description, the contents of elements in steel are mentioned
only by percents, but they should all be construed as figures
in percents by mass.
(Not less than 0.1% under 3% of Al)
In this first embodiment, steel sheets that contain not
less than 0.1% of Al are used. The reason is as follows. So
long as the Al content in steel is under 0.1%, a decrease in
the coating adhesion caused by a surface segregation of Al is
less of a problem, or AlN is not formed, which will be described
later. Further, in this embodiment, from a viewpoint of
securing a strength-ductility balance, it is preferable to
provide a steel structure that contains retained austenite;
however, if the Al content is under 0.1%, the retained austenite
is unstable, so that the steel is required to contain not less
than 0.1% of Al, which is adequate from a point of view of
attaining a better strength-ductility balance. Note, however,
that with steel sheets of Al content of not less than 3.0 mass%,
as described later, even if AlN is formed in the surface layer
of the steel sheet, the amount of Al surface segregation during
annealing increases, and it is difficult to obtain an improved
quality of the coating adhesion even though one does what one
can do in formulating a better method of generating a nitride
layer. Consequently, the Al content is limited to under 3.0%.
(One or two kinds out of not less than 0.1% of Si and not less
than 0.5% of Mn)
Si and Mn may be contained since they are conducive to
high strength. Above all else, not less than 0.1% of Si and
not less than 0.5% of Mn are preferably contained from a
viewpoint of achieving high strength. However, Si content of
over 1.0% and Mn content of over 0 . 5% makes it difficult to secure
weldability and coating adhesion; therefore, preferably, the
upper limit of the Si content is limited to 1.0% and the upper
limit of Mn to 3.5%.
(One or two kinds out of not less than 0.01% and not more than
1% of Mo and not less than 0.005% and not more than 0.2% of Nb)
Mo and Nb reduce the grain size of the matrix structure
and retard the recrystallization, to thereby promote the
internal oxidation of Al in the temperature rising process. In
this way, Mo and Nb have an effect of suppressing the surface
segregation of Al. Therefore, Mo and Nb can be contained in
steel to obtain a better coating adhesion. This effect appears
at a Mo content of not less than 0.01% and the Nb content of
not less than 0.005%. However, when the Mo content is over 1%,
in hot-rolling in the production process of a base sheet for
a galvanized steel sheet, there appears a tendency for the
surface property to deteriorate. Further, when the Nb content
is over 0.2%, there is a tendency that the steel hardness rises
and the rolling property deteriorates . Therefore, preferably,
Mo is contained in a range of not less than 0.01% and not more
than 1%, and Nb in a range of not less than 0.005% and not more
than 0.2%. Mo and Nb may be added in the ranges mentioned above.
(Not less than 0.01% and not more than 0.5% of Cu, not less
than 0.01% and not more than 1% of Ni, not less than 0.01% and
not more than 18, of Mo)
When Cu, Ni and Mo are added, the coating adhesion is
improved. The improvement mechanism of the coating adhesion
by addition of Cu, Ni and Mo has not been clarified, but it has
been confirmed that when those elements are added together, but
not separately, the internal oxidation of Al is promoted to
thereby suppress the surface segregation of Al, and the coating
adhesion is improved.
As for other components, considering production cost and
workability of an automotive steel sheet, it is suitable to use
a steel sheet which contains 0 . 0005~0.25 mass% of C, 0.001~0.20
mass% of P, and 0.0001~0.01 mass% of S. Besides those elements,
to further control the strength-ductility balance, it is no
problem if a steel sheet is used which contains not more than
0.15 mass% of Ti, not more than 1 mass% of Cr, and 0.001-0.005
mass% of B to control the balance between strength and ductility
of steel sheet. The rest preferably consists of Fe and
unavoidable impurities.
Description will now be made of the AlN layer formed in
the surface layer, the AlN layer serving as an important factor
of this embodiment.
In this embodiment, an AlN precipitate layer where Al
exists chiefly as AlN is formed in the surface layer of a steel
sheet. For this reason, in the heating step before the
galvanizing process, the Al in steel in the surface layer is
fixed as nitride in the matrix and is inhibited from diffusing
to the surface region of the steel sheet.
It has been recognized that when an AlN precipitate layer
exists, there is an effect that Si and Mn, which are readily
oxidizable elements like Al, are inhibited from increasing
their densities in the surface layer when the steel is annealed,
though the reason is unknown. Therefore, even with steel sheets
which contain relatively large amounts of Si and Mn and
therefore the coating adhesion is liable to deteriorate or
"bare-spot" areas tend to occur, in the presence of an AlN
precipitate layer, favorable hot-dip galvanizability and
better coating adhesion can be obtained.
What is called the AlN precipitate layer here is a layer
in which 20% or more of Al in the basic steel exists as nitride.
When the amount of Al present as nitride is under 20%, the Al
present in a solid solution phase is over 80%, and the Al existing
in solid solution phase diffuses into the surface of the steel
sheet, and therefore the above-mentioned bettering effects of
coating adhesion is reduced.
The amount of Al that precipitated out as AlN is obtained
by a method as follows . For a predetermined thickness (insteps
of 5µm, for example) from the surface layer, a predetermined
amount of the AlN precipitate is dissolved by an electrolytic
method using 10w/v% of acetylacetone-lw/v% of tetramethyl
ammonium chloride-methanol, and insoluble residues are
analyzed, by which the presence of AlN can be conformed. The
residual AlN is decomposed by steam distillation, and by
separating and determining only the quantity of N, the quantity
of the N in the AlN precipitate can be determined. On the basis
of this value, the quantity of Al in the AlN precipitate can
be determined. Further, the quantity of a solid-solution Al
can be determined by evaporating the rest other than the residue
to dryness, again dissolving the residue in acid, and
calculating the quantity of Al by an atomic absorption method
compliant with JIS G 1257. From the above results, the
proportion of nitride of Al in the AlN precipitate layer can
be calculated.
Note that because the presence of AlN can be confirmed
by EPMA analysis of the sectional area of a steel sheet and by
analyzing both N and Al, the presence of AlN can be conformed
by EPMA analysis in a simple manner.
Fig. 1 is a picture showing an SEM electron microscope
observation result of a sectional area of a steel sheet where
an AlN precipitate layer is formed on the surface layer. Fig.
2 is a picture showing an analysis result of the presence of
Al by EPMA. According to Figs. 1 and 2, Al exists as nitride
in a columnar or angular form and is distributed in a region
10~20µm depth from the interface of the steel matrix, and it
is obvious that in that portion of the region where AlN did not
precipitate out, the quantity of solid solution of Al is not
much. This region corresponds to the AlN precipitate layer.
Therefore, the solid solution of Al is inhibited from diffusing
from this region to the surface during annealing, and therefore
the coating adhesion does not deteriorate. It is understood
that in an area much deeper than that region, the presence of
nitride is not recognized, but Al is present mostly in a solid
solution phase.
The thickness of the AlN precipitate layer is preferably
not less than 1µm and not more than 100µm. The reason is as
follows. If there is some amount of AlN precipitate layer in
the surface layer, an effect that prevents surface segregation
of Al will appear, and this effect becomes conspicuous when the
thickness of the AlN precipitate layer is 1µm or more. It is
practically difficult to form an AlN precipitate layer with a
thickness of over 100µm, and if the thickness is over 100µm,
the influence on the quality of material becomes not negligible.
By hot-dip galvanizing, a base sheet for a hot-dip
galvanized steel sheet which has the steel composition and the
AlN precipitate layer as described above, a hot-dip galvanized
steel sheet with excellent coating layer adhesion can be
obtained.
Description will be made of a method for manufacturing
a hot-dip galvanized steel sheet according to this embodiment.
As with an ordinary steel sheet for hot-dip galvanizing,
a steel sheet (a base sheet) for hot-dip galvanizing according
to this embodiment is manufactured by heating and holding a
steel slab made by continuous casting or the like, subjecting
the slab to a hot-rolling process or further to a cold-rolling
process. In the present invention, in order to prevent Al from
segregating at the surface in the annealing process before
hot-dip galvanizing, it is necessary to have an AlN precipitate
layer previously formed on the surface layer of the steel sheet
before or after annealing.
With regard to a method for forming an AlN precipitate
layer, the inventors hit upon a conception that by nitriding
the Al in the steel surface layer when the steel slab was heated
and held, it would be possible to make Al in the surface layer
exist as AlN in the subsequent hot-rolling, acid-cleaning and
cold-rolling processes. On the basis of the above conception,
the present inventors investigated the conditions for heating
and holding a steel slab.
Al is well known as an element that can be easily nitrided.
As a result of our study, it has become clear that Al is nitrided
more in preference over other elements when it is heated at a
high temperature in an atmosphere chiefly consisting of N2 and
including O2. The mechanism by which O2 promotes the nitriding
of Al has not necessarily been clarified. In an O2-bearing
atmosphere, oxides are formed in large amounts on the surface
of the steel and the oxides serve as a diffusion path of nitrogen,
a fact which is considered to be one factor of O2 assisting in
niriding Al. It has also been clarified that in order to
generate nitride of Al while the slab is being heated and held,
the O2 concentration is required to be at least 1 vol% or higher.
Raising the O2 concentration to 20 vol% or higher requires some
other method for blowing oxygen into a heating and holding
furnace and also accelerates oxidation of the steel matrix
itself; therefore, it is necessary to limit the O2 concentration
to not more than 20 vol%. It does not matter if CO and CO2,
other than the components O2 and N2, are mixed, but N2 needs to
be 70 vol% or higher to generate nitride of Al.
In an N2-bearing atmosphere, by heating and holding the
above-mentioned slab at a high heating and holding temperature
and in a prolonged heating and holding time, the Al in the surface
layer of the slab can be nitrided. At this time, if the amount
of Al in the steel is large, the heating and holding time to
nitride the Al becomes longer accordingly. In this respect,
on steels with varying Al contents, inquiry was made into the
effects of the heating and holding time and temperature before
hot-rolling on the adhesion of the hot-dip galvanized coating.
In practice, a slab of a composition containing 0.1~3%
of Al, 0.5% of Si and 2.2% of Mn was used, in an atmosphere of
3 vol% of O2 and the rest consisting of N2, the slab was hot-rolled
to a thickness of 2.8mm. The oxide scale formed on the surface
of an obtained hot-rolled steel sheet was removed by acid
cleaning, and then the steel sheet was cold-rolled to a
thickness of 1.6mm, annealed at 810~825°C, and subjected to
overaging at 400~460°C. Subsequently, the steel sheet was
hot-dip galvanized in a hot-dip Zn bath with an Al concentration
of 0.13 mass% and continuously treated by a galvannealing
process at 500°C.
Samples for evaluating the coating adhesion were taken
from a Zn-Fe galvanneal coated steel sheet. The coating
adhesion was evaluated as follows. A test specimen to which
a cellophane tape was attached was bent 90 degrees on the
tape-attached side and bent back, the tape was peeled off, and
the peeled-off amount of the coating per unit length was
measured in terms of counts of Zn by a fluorescent X-ray method.
Samples ranked first or second were classified as good (O, D)
and those ranked third and so on were classified as defective
(X) by referring to the criteria in Table 1.
The evaluation results are shown in Figs. 3A. to 3D.
According to Figs. 3A to 3D, before hot rolling, a slab is heated
and held under the conditions that the heating and holding
temperature, the heating and holding time and the Al content
in the steel meet equation (1) , by which arrangement a hot-dip
galvanized steel sheet with excellent coating layer adhesion
can be manufactured.
{Heating and holding temperature (°C) — (1050 + 25A1)} X heating
and holding time (mm) = 3000 ........ (1)
where Al denotes an Al content (mass%) in the steel.
As a result of observation of a cold-rolled steel sheet
to check the presence or absence of an AlN precipitate layer,
it was confirmed that an AlN precipitate layer was formed in
the surface layer when the above equation (1) was satisfied.
When a steel sheet with a chemical composition that
contains not less than 0.1% and under 3% of Al is subjected to
heating and holding before hot rolling in an atmosphere with
an O3 content of not less than 1 vol% and not more than 20 vol%
under the condition that meets the equation (1), a steel sheet

with an AlN precipitate layer in the surface layer can be
manufactured. Moreover, though containing Al and other
readily oxidizable elements such as Si and Mn, the steel sheet
has an excellent coating adhesion after it has been hot-dip
galvanized.
Note that the AlN formed by the above-mentioned method
is not only included in the steel of the surface layer but also
sometimes exists exposed on the surface of the steel matrix.
Even in such a case, the AlN have no effects on the ductility
and mechanical properties of the steel sheet nor has it effects
on the surface quality such as coating layer adhesion. It is
considered because the AlN precipitate layer is confined to the
uppermost of the surface layer and its exposure at the surface
of the steel matrix is limited to a very few parts thereof.
The hot-rolled steel sheet is obtained by hot rolling
after heating and holding under the above conditions, and the
steel sheet is then subjected to acid cleaning or acid cleaning
plus cold rolling and annealing, and furthermore the steel sheet
is hot-dip galvanized.
The acid cleaning of the hot-rolled steel sheet is done
to remove the oxide scale formed on its surfaces. The
conditions for acid cleaning are not limited to specific items,
but because the AlN precipitate layer is required to remain,
consideration must be given to prevent the steel matrix from
being dissolved in large amounts during acid cleaning. The acid
is preferably hydrochloric acid, but other acids such as
sulfuric acid may be used. The concentration of the acid is
preferably l~20 mass%. To prevent the steel matrix from
dissolving in large amounts, an inhibitor (dissolution
inhibitor) is preferably added.
Cold rolling may be performed if necessary to control the
mechanical properties and the thickness of a final product.
When cold rolling is carried out, the draft is preferably 30%
or higher to promote recrystallization in subsequent annealing.
However, if the draft is 80% or higher, large load is applied
to the rolling mill, making rolling difficult; therefore, the
draft is preferably 30~80%.
Annealing just before hot-dip galvanizing may be by a
method in which hot-dip galvanizing is performed successively
after annealing has been done by well-known so-called
continuous annealing, or by a method in which a steel sheet
annealed once (primary annealing) is cooled, and then the steel
sheet is acid-cleaned to activate its surface and also after
the surface oxide formed by primary annealing is removed by acid
cleaning, the steel sheet is heated again (secondary annealing)
and successively hot-dip galvanized. However, the annealing
process just before galvanizing preferably includes a step for
uniformly heating the steel sheet at least partially under a
reducing atmospheric condition chiefly consisting of H2-N2 with
a view to deoxidizing the Fe-based surface oxide film and
securing the hot-dip galvanized coating wettability. Or it is
no problem if a process may be employed in which an Fe-based
oxide film is formed in the temperature-rising process in an.
NOF (Nonoxidation furnace) type heating furnace, for example,
and the oxide film is deoxidized. Note that primary annealing
is preferably at 750~930°C to obtain an appropriate structure.
If the primary annealing temperature is higher than 930°C, the
readily oxidizable elements such as Si increases its
segregation at the surface which adversely affects the
galvanizability and the galvannealability. The secondary
annealing is preferably at 650°C or higher with a view to
deoxidizing the oxide film formed during acid cleaning, and
preferably at not less than 850°C with a view to preventing
the coarse-grain, for example, of the steel structure.
Acid cleaning after primary annealing is performed, for
example, by a method of light acid-cleaning at 60°C for several
seconds in a hydrochloric acid of about 5 mass's or so. Other
acids such as sulfuric acid may be used. Generally, acid
cleaning is preferably performed with acidity of pH = 1,
temperature of 40~90°C for 1~20 sec. If the temperature is
below 40°C and the time is less than 1 sec, the removal effect
of surface segregates cannot be obtained, and if the temperature
is higher than 90°C and the time is longer than 20 sec, excessive
acid cleaning occurs, which results in roughening of the
surface.
A steel sheet is provided with a strength-ductility
balance as follows . When annealing and hot-dip galvanizing are
performed continuously in a continuous annealing process, it
is desirable that after intercritical heating is finished,
while bainite transformation is made to take place by overaging
at 350~500°C for not less than two minutes to let segregates
of C appear in the austenite, and continuously performing
hot-dip galvanizing. When hot-dip galvanizing is performed
after primary annealing, cooling, acid cleaning, and secondary
annealing, preferably, after intercritical heating by primary
annealing, the steel sheet is quenched below 300°C at a rate
of not less than 40°C/s to obtain a hardened structure consisting
of a ferrite-martensite phase, and immediately before
galvanizing, a tempering process is carried out by heating to
725~840°C, and then cooling at a rate of not less than 5°C/s
to form a composite structure of ferrite-tempered
martensite-retained austenite, and finally hot-dip
galvanizing is performed.
As a method for forming the AlN precipitate layer,
description has been made of a method for adjusting the heating
and holding conditions before hot rolling. Incidentally, a
steel sheet for hot-dip galvanizing according to the present
invention can be manufactured by annealing the steel sheet in
an atmosphere of nitriding elements, such as an H2-N2 system
gas, mixed with trace amounts of CO and NH3 in the annealing
process just before hot-dip galvanizing.
Description will be made of a hot-dip galvanized steel
sheet according to this embodiment.
A hot-dip galvanized steel sheet according to this
embodiment can be obtained by hot-dip galvanizing a steel sheet
for hot-dip galvanizing purpose, which includes the
above-mentioned AlN precipitate layer. The AlN layer remains
on the matrix side near the interface between the steel sheet
and the hot-dip galvanized layer after the hot-dip galvanizing
process. The hot-dip galvanized steel sheet obtained as
described has a good coating adhesion because the readily
oxidizable elements such as Al, Si and Mn are inhibited from
segregating at the interface between the steel matrix and the
coating layer.
The hot-dip galvanized layer (hereafter referred to
simply as the coating layer} is preferably a coating layer of
a composition containing 0.1~1% of Al or an a Zn-Fe galvanneal
coating layer that further contains 7~15% of Fe in addition to
the above-mentioned chemical composition.
With a hot-dip galvanized steel sheet without
galvannealing the coating layer (this steel sheet is hereafter
referred to as GI), if the Al content in the coat layer is below
0.1%, the Fe-Zn galvannealing reaction shows rapid progress
during the galvanizing process; therefore, unevenness occurs
in the external appearance. With the GI, above all else, the
Al content is preferably not less than 0.2% to inhibit the
galvannealing reaction. When the Al content in the coating
layer is over 1%, in the galvanizing process, the Fe-Al alloy
layer becomes thick which is formed on the coating layer side
close to the interface between the coating and the steel matrix,
with the result that the weldability decreases.
If Pb, Sb or Ni, sometimes contained in trace amounts in
a galvanizing bath, exists in the coating layer in a range of
not more than 0.1% each, then there is no problem in terms of
characteristics of the steel. When the Fe eluates into the
galvanizing bath or the matrix Fe is mixed into the coating layer,
if its amount is not more than 0.1% or so, there is no problem.
Mg may be contained in a range not more than 5% to impart
corrosion resistance to the steel. Besides those elements
mentioned above, others are preferably Zn or unavoidable
impurities.
Even with a Zn-Fe galvanneal coated steel sheet whose
coating layer is galvannealed (hereafter referred to as GA) ,
the quantity of Al in the coating layer is required to be 0.1~1%.
The reason is as follows. If the Al content is below 0.1%, the
Fe-Zn galvannealing reaction progresses so rapidly in a
galvannealing process that the coating adhesion deteriorates;
on the other hand, if the Al content is more than 1%, the Fe-Al
alloy layer, which is formed on the coating layer side near the
interface between the coating and the steel matrix, becomes so
thick that the Fe-Zn galvannealing reaction is retarded. The
desirable Al concentration is not more than 0.3%). With a Zn-Fe
galvanneal coated steel sheet whose coating layer is
galvannealed, if the Fe content in the coating layer is under
1%, a soft Zn-Fe galvanneal layer is formed, resulting in a lower
slidability. Or, if the Fe content is over 15%, a hard and
brittle Fe-Zn galvanneal layer is formed on the coating layer
side near the interface between the steel matrix and the coating
layer, and the result is a poor coating adhesion. For this
reason, the Fe content in the Zn-Fe galvanneal coated steel
sheet is preferably 7~151. If Pb, Sb and Ni are contained in
amounts of not more than 0.1% each, there is no problem in
soldering properties. If Mg is contained in a range of not more
than 5% to secure corrosion resistance, there is no problem at
all. The rest preferably consists of Zn and unavoidable
impurities.
For hot-dip galvanizing, a well-known method can be
applied. For example, preferably, the bath temperature is
440~500°C and the Al concentration in the bath is 0.10~0.20%
when a galvannealing process is performed which will be
described later, or 0.14~0.247, when a galvannealing process is
not performed. Mg may be contained in the bath for better
corrosion resistance.
After hot-dip galvanizing, if the coating layer undergoes
a galvannealing process in a temperature range of 460~550°C,
this is most desirable. If the temperature is under 460°C, the
galvannealing reaction progresses slowly. Or if the temperature
is above 550°C, excess galvannealing occurs; therefore, a hard
and brittle Zn-Fe galvanneal layer is formed in large amounts
at the interface of the matrix, causing the coating adhesion
to deteriorate. Furthermore, if the steel is a steel with a
retained austenite phase formed in the steel, when the
galvannealing temperature is higher than 550°C, the retained
austenite decomposes, and the strength-ductility balance tends
to deteriorate. The coating layer weight has not been set, but
from a viewpoint of securing the corrosion resistance and
controlling the precision of coating weight, it is preferably
not less than 10g/m2, and not more than 120 g/m2 from a viewpoint
of workability.
(Embodiment)
Slabs of compositions shown in Table 2 are heated and held
in an N2 atmosphere of O2 densities as shown in Tables 3 and 4
in a heating furnace at temperatures and conditions shown in
Tables 3 and 4, and subsequently hot-rolled to a thickness of
2.8 mm and are coiled at 540~600°C. Subsequently, the skin scale
was removed by acid cleaning. Some of hot-rolled steel sheets
which have been acid-cleaned are cold-rolled into cold-rolled
steel sheets with a thickness of 1.6mm. Hot-rolled and cold
rolled steel sheets obtained undergo primary annealing and
overaginq under conditions shown in Tables 3 and 4, and are
hot-dip galvanized in a molten Zn bath at a bath temperature
of 460°C. Or, if they are subjected to secondary annealing,
they receive primary annealing and cooling, and then
acid-cleaned in a 5% HCl solution at 60°C. After this, the steel
sheet are heated at secondary annealing temped at mass shown in
Tables 3 and 4, and continuously they are hot-dip galvanized
in a molten Zn bath at a bath temperature of 460°C.
The Al concentration in the molten Zn bath is adjusted
as shown in Tables 5 and 6. The coating weight is adjusted to
50±5g/m for single side by gas wiping. When the coating layer
is galvannealed, the galvannealing process is performed at
460~610°C.
Obtained hot-dip galvanized steel sheets are evaluated
in terms of external appearance, coating adhesion, and
mechanical properties. Samples are taken from the produced
steel sheets, and the thickness was measured of the AlN
precipitate layer formed on the matrix side right under the
interface between the matrix and the coating layer, and the Al
concentration and the Fe concentration in the coating layer were
measured. Investigation results are shown in Tables 5 and 6.

In Tables 5 and 6, as coating kinds, a hot-dip galvanized
coating layer that has been galvannealed is designated as GA
and a hot-dip galvanized coating layer that has not been
galvannealed is designated as GI. With regard to kinds of base
sheets for coating, a case where a hot-rolled steel sheet is
used is designated as HOT, a case where a cold-rolled steel
sheet annealed once is used is designated as CR, and a case
where a cold-rolled steel sheet subjected to annealing - acid
cleaning - reheating is used is designated as CAL.
The external appearance was evaluated by visually
checking the galvanizability with reference to criteria as
follows.
o: Without any "bare-spot"
D: Generally no problem even though there are some "bare
spots"
X: "bare" spots occurred conspicuously
The coating layer adhesion was evaluated as follows.
A cellophane tape was attached to the surface of a specimen,
the tape-attached side was bent 90 degrees and bent back, the
tape was peeled off, the peeled-off amount of the coating per
unit length was measured in terms of counts of Zn by a
fluorescent X-ray method. Samples ranked first or second were
classified as good (o, A) and those ranked third and so on
were classified as defective (X) by referring to the criteria
in Table 1.
A hot-dip galvanized steel sheet (GI) that has not been
galvannealed was put to a ball impact test, and a cellophane
tape was attached to a processed part and the tape was peeled
off. Whether the coating layer was peeled off or not was
evaluated according to criteria as follows.
o: The coating layer did not peel off.
D: The coating layer peeled off a little.
X: The coating layer peeled off conspicuously.
In evaluation of mechanical properties, JIS-No.5
tension test specimens were collected, and from measured
tensile strength TS(MPa) and elongation E1 (%), if a result
of TS X E1 was not less than 20000 MPa • %, this was taken to
represent a good strength-ductility balance and the hot-dip
galvanized steel was determined to have a favorable mechanical
properties.
With regard to the Al concentration in the coating layer,
the coating was dissolved in an alkali, such as NaOH or KOH,
or in an acid, such as HCl or H2SO4, added with an inhibitor,
and its solution was analyzed and the concentration of Al was
determined by a plasma emission spectrometer (ICP).
Likewise, the Fe concentration in the coating layer was
measured by ICP by analysis and quantitative determination of Fe.
The thickness of the AlN precipitate layer was obtained
by analyzing the sectional surface of a galvanized steel sheet
by EPMA, and measuring the thickness of a ragion where there
were precipitates of AlN and the Al concentration in the matrix area is lower than the central portion of the steel sheet. The
Al concentration of the matrix area in the AlN precipitate
layer was obtained by analyzing the above-mentioned insoluble
residues.
From Tables 5 and 6, the hot-dip galvanized steel sheet
(GA or GI) is A or o in evaluation of the external appearance
and A or o in evaluation of coating adhesion; therefore, it
is understood that this galvanized steel sheet has favorable
galvanizability and coating adhesion. Furthermore, in
respect to mechanical properties, the steel sheet shows a
favorable strength-ductility balance of 20000 MPa • % or higher.
In contrast, in comparative examples 1, 2, 7, 8, 10 and
11, there is not AlN precipitate layer, and therefore the
external appearance and the coating adhesion are poor. In
comparative examples 3 and 13, in which the Al concentration
is low in the coating, the coating adhesion is poor. In
comparative examples 4, 5, 14 and 15 of Zn-Fe galvanneal coated
steel sheet, the Al concentration in the coating layer is high
in comparative examples 4 and 14 and the Fe concentration in
the coating layer is low, so that there is unevenness in the
galvannealing results. In comparative examples 5 and 15,
because of the high Fe concentration in the coating layer, the
coating adhesion is insufficient. In comparative examples 6
and 9, in which steel sheets of low Al content were used as
base sheets, it is obvious that the mechanical properties are
inferior. In comparative example 12, because the primary
annealing temperature is too high, the galvannealing reaction
in the coating layer did not progress sufficiently, and
moreover, the coating adhesion and mechanical properties are
deficient.
(2) Second Embodiment
Description will now be made of a chemical composition
of base steel sheet to undergo electroplating or chemical
treatment according to a second embodiment of the present
invention. Also in the second embodiment, the contents of
elements in the steel are expressed simply by percent (V,) which,
however, should all be construed to mean "in percent by mass
(mass%)".
(Al: Not less than 0.17, and under 37,)
In this embodiment, as in the first embodiment, steels
with an Al content of not less than 0.17, are used. The reason
is as follow: So long as the Al content is under 0.1%, because
the surface-segregated amount of Al is low, there are not much
of problems in the electrocoating adhesion and the unevenness
of electroplated coating or chemical treatment coating, or the
external appearance, and AlN is not formed, either. Also in
this embodiment, with a view to securing a strength-ductility
balance, preferably, the chemical composition contains
retained austenite, and if the Al content is under 0.1%, the
retained austenite is unstable; therefore, with a view to
obtaining a better strength-ductility balance of the steel
sheet, it is required that not less than 0.1% of Al should be
contained in the steel sheet. Note that in a steel sheet with
an Al content of not less than 3.0 mass%, even if AlN is formed
in the surface layer of a steel sheet, the surface segregated
Al is formed in large amounts during annealing, making it
difficult to secure a better coating adhesion despite the best
efforts that could be made to improve the method for forming
a nitride layer; therefore, the Al content in the steel is set
under 3.0%.
(One or two kinds out of not less than 0.1% of Si and not less
than 0.5% of Mn)
For the same reason as in the first embodiment, one or
two kinds out of Si and Mn are set in the ranges mentioned above.
(One or two kinds selected out of not less 0.01% and not more
than 1% of Mo, and not less than 0.005% and not more than 0.2%
of Nb)
For the same reason as in the first embodiment, one or
two kinds out of Mo and Nb are set in the ranges mentioned above.
(Not less than 0.01% and not more than 0.5% of Cu, not less
than 0.01% and not more than 1% of Ni, not less than 0.011% and
not more than 1% of Mo)
By adding Cu, Ni and Mo, the coating adhesion of the steel
sheet is improved. The mechanism of improving the
electrocoating adhesion and chemical properties by adding Cu,
Ni and Mo has not been clarified. But, the present inventors
have continued that when those elements are added together,
but not singly, the internal oxidation of Al is promoted during
annealing, and therefore Al is prevented from segregating in
the surface, thus improving the coating adhesion.
With regard to other components, considering production
cost and also workability when a steel sheet is used as an
automotive steel sheet, preferably, 0.005~0.25% of C,
0.001~0.20%, of P, and 0.0001~0.10% of S should be contained.
Besides these elements, to control a strength-ductility
balance of the steel sheet, it is permissible to contain not
more than 0.15% of Ti, not more than 1% of Cr and 0.001~0.005%
of B. The rest consists of Fe and unavoidable impurities.
Description will be made of the AlN precipitate layer
formed in the surface layer of a steel sheet, which is an
important point of this embodiment.
In this embodiment, as in the first embodiment, the AlN
precipitate layer is formed in the surface layer of the steel
sheet, and fixed in the form of nitride in the matrix, the Al
in the steel of the surface layer is prevented from diffusing
into the surface layer of the steel sheet in annealing or acid
cleaning.
Though the reason has not been clarified, it has been
confirmed that the presence of the AlN precipitate layer has
the effect of inhibiting Si and Mn as readily oxidizable
elements other than Al from segregating at the surface of the
steel during annealing. Therefore, even with steels which
contain relatively large amounts of Si and Mn and which tend
to cause a poor coating adhesion or bare spots, the presence
of an AlN precipitate layer secures better electroplated
coating properties and coating adhesion.
The cross section of a steel sheet having an AlN
precipitate layer formed in the surface layer is the same as
shown in Fig. 1 of the first embodiment (the result observed
by an electron microscope (SEM) , and the state of presence of
Al by EPMA is the same as shown in Fig. 2 of the first embodiment.
Therefore, the Al exists as nitride in a columnar or angular
form and is distributed in a region l0~20µm deep from the
interface of the steel matrix, and it is obvious that in that
portion of the region where AlN did not precipitate out, there
is not much of solid solution of Al. This region corresponds
to the AlN precipitate layer. Therefore, the solid solution
of Al is inhibited from diffusing from this region to the
surface during annealing, and therefore the coating adhesion
does not deteriorate. It is understood that in an area much
deeper than that region, the presence of nitride is not
recognized, but Al exists mostly in a solid solution phase.
For the same reason as in the first embodiment, in this
embodiment, the thickness of the AlN precipitate layer is
preferably not less than 1µm and not more than 100µm.
Description will now be made of a preferred method for
manufacturing a coated steel sheet according to the present
invention. Like with an ordinary steel sheet, this steel sheet
(a base sheet for an electroplating or chemical treatment
process) is manufactured by heating and holding a cast steel
slab (continuously-cast slab for example) for a predetermined
time and having the slab go through a hot-rolling process or,
if necessary, further subjecting it to a cold-rolling process.
In this invention, however, in order to prevent Al from
segregating at the surface layer in the annealing process
before electroplating or chemical treatment, an AlN
precipitate layer is previously formed in the surface layer
of the steel sheet before annealing or after acid cleaning.
The present inventors, to form this AlN precipitate
layer, carried out the above-mentioned heating and holding of
the cast steel slab in an atmosphere containing not less than
1 vol% and not more than 20 vol% of O2- and not less than 70
vol% of N2 like in the first embodiment.
By carrying out the above-mentioned heating and holding
of the cast steel slab in an N2-containing atmosphere at a
raised holding temperature and for a prolonged holding time,
the Al in the surface layer of the steel slab can be nitirided.
In this case, if the Al content is high in the cast slab, the
heating and holding time necessary for nitridation is
prolonged accordingly. Regarding steels with varying Al
contents, investigation was made into the effects that heating
and holding time and temperature before hot rolling have on
the electroplated coating adhesion and the chemical properties,
and details are described as follows.
A cast steel slab of a composition containing 0.1~3% of
Al, 0 . 5% of Si and 2.2% of Mo was heated and held in an atmosphere
of 70 vol% of O2 and the rest consisting of of N2 was hot-roxled
into a street sheet of a thickness of 2.8 mm. The oxide scale
on the surface of an obtained hot-rolled steel sheet was
removed by acid cleaning, and then the steel sheet was
cold-rolled to a 1.6 mm thickness, and annealed at 810~825°C,
overaged at 400~460°C, and then subjected to
electro-galvanizing and Zn phosphating by well-known methods,
respectively.
An obtained electro-galvanized steel sheet was
evaluated in coating adhesion by an OT bending cast as follows.
In the OT bending test, an electro-galvanized steel
sheet was folded in twofold without leaving no gap with the
side under evaluation of the coating adhesion facing outside,
a cellophane tape was attached to the folded portion and peeled
off, and the amount of the coating adhering to the cellophane
tape was visually inspected. Evaluation was made according
to the criterion 1.
(Criterion 1):
O: The coating did not peel off.
D: The coating slightly peeled off to a level of no problem.
X: The coating peeled off conspicuously.
An obtained zinc-phosphated steel sheet was visually
inspected to see if there was any unevenness in adhesion of
the zinc phosphate film, and evaluated according to criterion
2 as follows.
(Criterion 2)
O: The coating weight is free of unevenness.
D: The coating weight was slightly uneven but no problem.
X: The coating weight was conspicuously uneven.
In those evaluations, if those which were evaluated as
O or A in both of electroplated coating adhesion and chemical
properties are classified as o and those which were evaluated
as X in one or both of electroplated coating adhesion and
chemical properties are classified as X, then the evaluation
results of this embodiment are the same as those in Figs. 3A
to 3D showing the evaluation of the coating adhesion in the
first embodiment.
Therefore, as is obvious from Figs. 3A to 3D, by heating
and holding a cast steel sheet before hot rolling under the
conditions that the heating and holding temperature, the
heating and holding time and the Al content all meet Eq. (1),
in other words, under the conditions that fall within the upper
area of the border line between the o-mark area and the X~mark
area, an electro-galvanized steel sheet can be manufactured
with excellent coating adhesion.
{Heating & holding temperature (°C)-(1050 + 2SA1)} X heating
& holding time (min) = 3000 ...... (1)
where Al denotes the Al content (mass%) in the steel.
It could be confirmed that when Eq. (1) is satisfied, the
Al precipitate layer is formed in the surface layer of the steel
sheet.
As has been described, with a cast steel sheet of a
composition that contains not less than 0.1% and under 3% of
Al, by heating and holding before hot rolling under conditions
that meet Eq. (1) in an atmosphere containing not less than 1
vol% and not more than 20 vol% of O2, a steel sheet having an
AlN precipitate layer formed in the surface layer can be
manufactured, and even with a steel sheet containing readily
oxidizable elements such as Si and Mn, besides Al, it is
possible to achieve better electro-galvanized coating
adhesion and chemical properties.
A hot-rolled steel sheet that has been hot-rolled after
heated and held under the above-mentioned conditions is, after
acid cleaning or after acid cleaning, cold rolling, and
annealing, subjected to electroplating and chemical treatment
processes.
In this embodiment, acid cleaning after hot rolling is
done to remove the oxide scale formed on the surface, but
acid-cleaning conditions are not specified. However, because
an AlN precipitate layer needs to remain, consideration is
required to prevent the matrix from dissolving in large amounts
during acid cleaning. The acid to be used for cleaning is
preferably hydrochloric acid, but other acids such as sulfuric
acid may be used. The acid concentration is preferably 1~20
mass% . To prevent the matrix from dissolving in large amounts,
an inhibitor (dissolution inhibitor) may be added in the acid
cleaning liquid.
In this embodiment, cold rolling is carried out when
necessary to control the mechanical properties and the sheet
thickness of a final product. Cold rolling is preferably
performed with a draft of not less than 30% to promote
recrystallization in subsequent annealing. Note that when
the draft is not less than 80%, load on the rolling mill is
so large that rolling becomes difficult, so that ihe draft is
preferably 30~80%.
Further in this embodiment, annealing may be carried out
by a well-known continuous annealing method. Annealing may
be performed not only on cold-rolled steel sheets but also on
hot-rolled steel sheets. To achieve a better balance between
strength and ductility of steel sheet, when be a annealing by
a continuous annealing method and electro-galvanizing are
carried out continuously, it is preferable to perform
overaging at 350~500°C for two minutes or longer after
intercritical heating, and while having bainite
transformation to progress, make the carbon segregate in the
austenite, and subsequently carry out electro-galvanizing.
When electro-galvanizing is carried out after primary
annealing, cooling, acid cleaning, and secondary annealing,
it is preferable to perform intercritical heating by primary
annealing, then quenching the steel sheet down to 300°C or lower
at a rate of 40°C/s or higher to thereby form a. hardened
structure composed of ferrite/martensite phases, and just
before galvanizing, and then tempering the steel sheet by
heating to 725~840°C and cooling at a rate of 5°C/s or higher
to thereby form a composite structure ferrite, tempered
martensite and retained austenite.
The technology for forming the AlN precipitate layer,
which has been described, is to control conditions for heating
and holding before hot rolling. However, to manufacture a
coated steel sheet according to this embodiment, this
technology for controlling the heating and holding conditions
may not be adopted. For example, the above-mentioned coated
can be manufactured by a method of annealing in an atmosphere
of nitriding elements, such as an H2-N2 system gas, mixed with
trace amounts of CO and NH3 in the annealing process.
As electroplating applied to a steel sheet for coating
according to this embodiment, electro galvanized coating, in
which the chief component is Zn, is most suitable. For example,
besides pure-zinc electroplating, zinc-alloy electroplating
that contains elements, such as Fe, Ni, Co and Mo, may be cited.
In addition, it is possible to use a zinc-based electroplated
coating which has inorganic compounds or organic compounds
dispersed or separated out in a zinc-based electroplated
coating. As a chemical treatment process, an ordinary method,
such as zinc-phosphating may be applied.
A coated steel sheet according to this embodiment,
though subjected to electroplated coating or chemical
treatment, the coating adhesion, coating weight and crawling
of the electroplated coating, and the coarsening of
crystalline grains by chemical treatment are improved to a
great extent.
(Embodiment)
A cast steel slab of a composition shown in Table 7 was
heated and held in a heating furnace under the conditions shown
in Table 8 and subsequently hot-rolled to a thickness of 2.8
mm and wound up in a coil at 540~600°C. After this, the skin
scale was removed from the strip by acid cleaning. Some of
acid-cleaned hot-rolled steel sheet is cold-rolled into a
cold-rolled strip with a thickness of 1.6 mm, annealed at
800~850°C, and overaged at 400~500°C, and cooled.
An obtained hot-rolled strip or cold-rolled strip as a
base sheet was coated by any one of Zn phosphating, pure-zinc
electroplated coating, electro zinc-nickel alloy coating, and
electro zinc-iron coating by a well-known method. Base sheets
were measured to determine the thickness of the AlN precipitate
layer and the solid solution rate of Al in the AlN precipitate
layer. An electroplated steel sheet was subjected to the OT
bending test mentioned above, and the coating adhesion was
evaluated. The electroplated coating property or the chemical
properties was decided from external appearance by visual
examination to see if there was external unevenness, such as
unevenness of coating weight, and evaluated according to
Criterion 2.
As for mechanical properties, JIS-specified No. 5
tension test specimens were taken from the strip, and tensile
test was conducted to measure tensile strength (TS (MPa)) and
elongation (El (%)). From measured values, TS X El was
obtained, and if the value was 20,000 (MPa • %) or larger, this
was decided to show a favorable strength-ductility balance of
the steel sheet, and the mechanical properties were evaluated
as good.
From Fig. 8, it is obvious that in embodiments of the
invention in which electroplating was performed, steel sheets
are superior in the coating adhesion and the external
appearance, and exhibit excellent mechanical properties. It
is also evident that steel sheets in embodiments of the
invention in which chemical treatment was carried out show
superb external appearance and offers favorable mechanical
properties.

(3) Third Embodiment
Description will be made of a chemical composition
of a high-strength steel sheet and a base sheet for a
high-strength hot-dip galvanized steel sheet according to a
third embodiment of the present invention. Also in the third
embodiment, the contents of elements in the steel are expressed
simply by percent (%) which, however, should all be construed
to mean "in percents by mass (massl)".
(not less than 0.1% and under 3.0% of Al)
For the same reason as in the first embodiment, the Al
content is in the above-mentioned range.
(C: 0.03-0.25%)
The C content needs to be not less than 0.03% to secure
a desired structure. However, a large amount of C degrades
weldability, and therefore the C content should be limited to
more than 0.25%.
(Si: 0.001-1.0%)
To obtain desired strength and structure, not less than
0.001% of Si is added. If Si, like with Al, is present as an
internal oxide in the surface layer, the problem of surface
treatability can be avoided. However, If the Si content in
the steel is over 1.0%, even though Si is present in the surface
layer but as its oxide in an inner area of the steel sheet,
the post-painting corrosion resistance of the steel sheet
which was coated is low. For this reason, the upper limit of
Si content is 1.0%.
(Mn: 0.5~3.0%)
To obtain a desired strength, Mn is added in an amount
of 0.5% or more. However, if the added amount is over 3%, the
weldability deteriorates, so that the Mn content is limited
to not more than 3.0%.
(P: 0.001~0.10%)
Though P is an element which is used to achieve high
strength without aggravating deep drawing property; however,
the addition of an excessive amount of P delays a galvannealing
reaction or deteriorates secondary fabrication embrittlement,
so that the P content is limited to not more than 0.10%. The
lower limit is 0.001%, a level of unavoidable impurity content.
Steel sheets according to the present invention, in
addition to the indispensable elements mentioned above, may
contain the following components where necessary.
(Mo: 0.01~1.0%, Nb: 0.005~0.2%)
Mo and Nb reduce the grain size of the matrix structure
and delay the recrystallization, to thereby promote the
internal oxidation of Al in the temperature rising process,
and are preferably added to obtain better coating property and
coating adhesion. When Mo and Nb are added together, however,
if the Mo content is over 1.0%, the surface properties of a
hot-rolled steel sheet shows a tendency to deteriorate, or if
the Mo content is under 0.01%, the intended effect is less
likely to be obtained. On the other hand, when Nb is added
at a content of over 0.2%, the hardness tends to rise and the
ductility tends to deteriorate, but if the content is under
0.005%, the effect is small. Therefore, preferably, the Mo
content is 0.01~1.0%, and the Nb content is 0.005~0.21%
(Cu: 0.01~0.5%, Ni: 0.01~1.0%,; Mo: 0.01~1.0%)
Cu, Ni and Mo are elements desirable for obtaining better
coating adhesion/ and only when they are added together, the
internal oxidation is promoted during annealing, and therefore
they are prevented from segregating in the surface, thus
improving the coating adhesion. However, when they are in
large amounts, there is a tendency for the surface properties
of the steel sheet to deteriorate, so that their added amounts
need to meet the conditions : 0.01~0.5% of Cu, 0.01~l.0% of Ni,
and 0.01-1.0% of Mo.
As for other chemical components, considering an
application as steel sheets for automobiles, to improve the
strength-ductility balance, other elements may bo added when
necessary in the following ranges: not more than 0.15% of Ti,
not more than 1% of Cr, and 0.001~0.005% of B.
The rest other than the above-mentioned elements are
preferably Fe and unavoidable impurities.
Description will next be made of the internal oxide layer
to be possessed by a high strength steel sheet and a
high-strength hot-dip galvanized steel sheet according to this
embodiment.
In this embodiment, an oxide layer needs to be formed
not in the surface of a steel sheet, but as a so-called internal
oxide layer right below the surface of the matrix. As the
amount of the oxide existing in the surface of a steel sheet
increases, not only the surface-treatability and the coating
adhesion but also the weldability and post-painting corrosion
resistance deteriorate. The region right below the surface
(surface layer) at which the internal oxide layer preferably
extends generally in a range of 0.1~100µm from the surface of
the steel sheet. If the thickness of the region where the Al
oxide exists is less than 0.1µm, the formed amount of the oxide
is so little that the surface oxidation of Al cannot be
inhibited. On the other hand, if the range is greater than
100µm, there is a worry that the mechanical properties of the
steel sheet itself deteriorates.
By making the internal oxidation take place, the Al oxide
not only exists as the internal oxidation layer in the
crystalline grains right below the surface of the matrix, but
also comes to exist in large amounts in the grain boundaries.
The Al oxides existing at the grain boundaries have the effect
of inhibiting the corrosion reaction liable to progress from
the grain boundaries. The oxides existing in the grains also
have the effect of inhibiting the corrosion reaction from
progressing from the grain boundaries into the grains. The
details of this mechanism are unknown. The above-mentioned
effects are enhanced by coexistence of other oxides; therefore,
to have the Al oxides coexist with oxides of Fe, Si, Mn and
P or the like is desirable for the improvement of the corrosion
resistance. Among the oxides of those elements are SiO2, MnO,
FeSiO3, Fe2SiO4, MnSiO3, Mn2SiO4 and P2O5.
The coexistence of those oxides contributes to the
outstanding coating adhesion during press working. It is
presumed that the oxide layers existing in adequate amounts
serve to absorb compressive stresses in press working.
Therefore, the presence of an Al oxide and other oxides is
effective in additionally improving the coating adhesion.
Moreover, the presence of the Al oxide as the internal
oxide layer secures an improved spot welding property. The
reason is considered as follows. Because the Al oxide that
worsens the weldability is fixed as the oxide in the steel and
does not exist in the surface of the steel sheet, a substantive
amount of Al solid solution is decreased and th weldability
is thereby improved.
As has been described, in a steel sheet according to this
embodiment, the internal oxide layer is required to exist right
below the surface of the steel sheet, and to obtain the
above-mentioned effects, the amount of oxides needs to be
0.01g/m2 for each side. However, when the amount of oxides
is over 1.0g/m2, the internal oxidation progresses so much as
to deteriorate the surface treatability and the coating
adhesion, and moreover the roughened surface worsens the
external appearance and degrades the corrosion resistance.
Note that the amount of the internal oxides can be known
by measuring the amount of oxygen in the steel; however, if
a coated layer has already been formed, such as a coating layer,
then the amount of oxygen in the steel is measured after the
coated surface is removed. As for a method for removing the
coating layer, it is possible to use a solution consisting of
an aqUeous solution of 20wt% of NaOH and 10wt% of
triethanolamine and an aqueous solution of 35wt% of H2O2 mixed
in a volume ratio of 195:7 or a dilute HCl solution containing
an inhibitor. Or, other acid or alkali may be used. Note that
attention should be taken to prevent the surface of the steel
sheet from oxidizing after the coating layer has been removed.
When measuring the amount of oxygen in the steel, the amount
of oxygen in the base sheet for the steel sheet needs to be
subtracted; therefore, after the coating layer has been
removed, the amount of oxygen of only the surface layer is
calculated by subtracting the amount of oxygen existing in the
steel obtained from a specimen, the surfaces of both sides of
which have been removed by 100µm or more from the surface by
mechanical grinding, and then by converting the calculated
amount of oxygen into that per unit area, the internal oxide
amount is obtained. The amount of oxygen in the steel can be
obtained by measuring by "Impulse Furnace Melting-Infrared
Absorption", for example. The kinds of oxides can be
identified by using extraction replicas of the cross section
of the steel sheet, and by analyzing them by TEM observation
and EDX. If the amount of oxides formed is so small and it
is difficult to identify, the Br2-methanol method may be used
to extract and ICP analysis may be employed.
The above-mentioned internal oxide layer can be formed
by setting a coiling temperature (CT) after hot-rolling at a
high temperature of not lower than 640°c, or by annealing on
a continuous annealing line (CAL) or on a continuous hot-dip
galvanizing line (CGL) , and in this process by setting the dew
point (DP) of the atmosphere in the annealing furnace on a
rather higher side. In the former case, the internal oxide
layer is formed by oxygen supplied from the skin scale, or in
the latter case, the internal oxide layer is formed by oxygen
formed when H2O in the atmosphere decomposes at the surface
of the steel sheet. Therefore, when the coiling temperature
CT after hot rolling has to be low, the internal oxides may
be formed in the annealing furnace. Above all else, Al is
liable to form internal oxides, so oxidation occurs even at
an ordinary dew point of about (DP = -40~-30°C) , and even when
an added amount is as much as close to 2%, surface segregation
can be impeded sufficiently. However, when the dew point is
below -50°C, internal oxidation becomes less liable to occur.
Therefore, when a steel sheet is coiled at a high coiling
temperature CT, the dew point of the atmosphere in annealing
matters little, but when a steel sheet is coiled at a low CT,
the dew point preferably not lower than -45°C, and more
preferably not lower than -40°C. With regard to Si, Mn and
P in the surface layer, internal oxides of those elements are
formed by setting a high CT or by controlling the dew point
in continuous annealing.
A high strength steel sheet according to the present
invention can be manufactured by using a high CT or by
controlling the dew point in continuous annealing as described
above. Moreover, if a high strength steel sheet according to
the present invention is hot-dip galvanized, a hot-dip
galvanized steel sheet according to this embodiment can be
manufactured.
Next, description will be made of suitable conditions
for annealing and hot-dip galvanizing when manufacturing steel
sheet according to this embodiment.
With regard to annealing conditions on a continuous
annealing line (CAL), it is preferable from a viewpoint of
obtaining high strength that, after recrystallization is made
to occur by heating the steel sheet to an intercritical
temperature (a +g), the steel sheet is overaged at 350~500°C
for two minutes or longer to make C segregate in the austenite,
and bainite transformation is made to occur. When hot-dip
galvanizing a steel sheet, hot-dip galvanizing is carried out
on a steel sheet on which recrystallization and overaging have
been carried out, or after the above-mentioned intercritical
annealing has been done on a continuous hot-dip galvanizing
line (CGL), subsequently a hot-dip galvanizing process may be
performed. In the category of hot-dip galvanized steel sheets,
a hot-dip galvanized steel sheet featuring high strength and
high ductility can be obtained by performing the
above-mentioned intercritical annealing on a steel sheet on
a CAL line, quenching 300°C or lower at a rate of 40°C/sec or
higher to produce a hardened structure consisting of ferrite
and martensite, and then again annealing the steel sheet at
725~840°C on the CGL line and cooling at a rate of 5°C/sec to
obtain a steel sheet of a composite structure of ferrite,
tempered martensite and retained austenite, and subsequently
hot-dip galvanizing the steel sheet, which is the so-called
two-step annealing method.
As the annealing furnaces for CAL and CGL, all radiant
heating tube (RTH) furnaces of so-called full-reducing
atmosphere may be used. For the temperature-rising process,
it is possible to use a non-oxidizing-atmosphere heating
furnace (NOF) or a direct-firing furnace (DFF).
As for a method for applying this embodiment to a hot-dip
galvanized steel sheet, a well-known method may be used. For
example, preferably, the bath temperature is 440~5G0°C, and
the Al concentration in the bath is 0.10~0.20% when a
galvannealing process is carried out, or about 0 .14~0.24% when
a galvannealing process is not carried out. If the Al
concentration is too low, the coating adhesion is inferior in
both cases mentioned above. On the other hand, if the Al
concentration is too high, the weldability is poor when the
galvannealing process is not executed or the galvannealing
reaction is delayed when the galvannealing process is carried
out. To improve the corrosion resistance, Mg may be added to
the galvanizing bath. The coating weight is not specified,
but from a viewpoint of securing the corrosion resistance and
controlling the coating weight, the coating weight is
preferably not less than 10g/m2 or from a viewpoint of
workability, the coating weight is preferably not more than
120g/m2.
Following hot-dip galvanizing, a galvannealing process
may be performed if necessary. The temperature at which the
galvannealing process is carried out is preferably in a range
of 460~550°C. At under 460°C, the galvannealing reaction
progresses slowly, but at 550°C or higher, excess galvannealing
occurs, and a hard and brittle Zn-Fe galvanneal layer is formed
so much at the interface between the coating layer and the
matrix, thus not only deteriorating the coating adhesion, but
decomposing the retained austenite layer and aggravating the
strength-ductility balance. Meanwhile, when the Fe content
in the coating layer after the galvannealing process is under
7%, a soft Zn-Fe galvanneal layer is formed at the surface of
the coating layer, thereby worsening the slidablity. On che
other hand, the Fe content of over 15% is not preferable because
the hard and brittle Fe-Zn galvanneal layer is formed at the
interface of the matrix in the coating layer, lowering the
coating adhesion.
A high strength steel sheet according to this embodiment
may not only be hot-dip galvanized but also may be coated with
hot-dip Zn-5%A1 coating, hot-dip Zn-55%A1 coating, hot-dip Al
coating, or the like. The kind of a steel sheet to which this
embodiment is applied, whether cold-rolled or hot-rolled, does
not matter so long as desired mechanical propert, es can be
obtained.
(Embodiment 1)
A steel slab of a chemical composition shown in Table
9 was heated at 1150°C for 25 minutes in a heating furnace,
then hot-rolled to a thickness of 2 . 8mm, and coiled at 450~780°C
to obtain a hot-rolled strip. Subsequently, with the skin
scale removed by acid cleaning, the strip was cold-rolled to
a thickness of 1.4mm, and subjected to a continuous annealing
annealed at 800~850°C for recrystallization, and overaged at
400~500°C to thereby finish a cold-rolled sheet.
This cold-rolled strip was further subjected to various
kinds of coating, such as electro-galvanizing, electro Zn-Ni
electroplating or Zn phosphating, and the steel sheet was
evaluated in external appearance, coating adhesion (only for
electroplated sheets), and corrosion resistance (only for
Zn-phosphated sheets). The electroplated coating weight was
20g/m2 and the chemical treatment weight was 2g/m2.
The properties of steel sheets obtained as described are
evaluated as follows:
External appearance: Bare spots or the uneven adhesion were
observed visually, and specimens without flaws are decided as
good (o) .
Coating adhesion: Electroplated steel sheets were
subjected to a ball impact test, and then a cellophane tape
was attached to the processed parts and peeled off. Whether
or not the coating layer was peeled off was visually observed,
and "without bare spots" was classified as o, "there are
somewhat bare spots" was classified as D, and "bare spots
occurred conspicuously" was classified as X.
Corrosion resistance: Zn-phosphated steel sheets were
elctrodeposited, a cross was engraved with a knife, and test
specimens were dipped in a 5% NaCl or 55°C salt water for 240
hours, taken out and dried, and tape peeling test was performed

on cross-cut portions, and the peeling width was measured.
Those with a peeling width of less than 3.5mm were classified
as good (O) , those with a width of 3. 5mm~under 4mm were
classified as rather good (A), and those with a width of not
less than 4mm were classified as bad (X).
For cold-rolled steel sheets yet to be coated, the
weldability was evaluated as follows.
Weldability test: Two test specimens were spot-welded
together by using a dome-tipped 6-mm dia. welading electrode
under conditions of electrode pressure of 4.3k%, welding
current of 8kA, squeeze time for 25 cycles, setup time for 3
cycles, welding time for 13 cycles, and holding time for 1
cycle; subsequently, a maximum tensile load in a tensile shear
test (TSS) according to JIS Z3136 and a maximum tensile load
in a cross joint tensile test (CTS) according to JIS Z3137 were
measured. Those test specimens for which ductility ratio
(CTS/TSS) was not less than 0.25 and the tensile load (TSS)
was not less than the standard tensile shear load (1162N) for
a thickness of 1.4mm were classified as excellent (O) , and
those not meeting the above conditions were classified as
inferior (X).
On cold-rolled steel sheets before sent to coating, the
amounts of internal oxides were measured by the
above-mentioned method, and the internal oxides were
identified. If an oxide existed in a range up to O.1µn from
the surface, such a case was determined as "presence of oxide".
The test results are shown en bloc in Table 10. As is
clear from this Table, high tension steel sheets according to
the present invention, regardless of large contents of Al and
Si, invariably exhibit excellent surface treatability,
coatability, spot-weldability, and post-painting corrosion
resistance.
(Embodiment 2)
A steel slab of chemical composition shown in Table 9
same as in Embodiment 1 was heated at 1150°C for 25 minutes
in a heating furnace, then hot-rolled to a thickness of 2.8mm,
and coiled at 450~780°C to obtain a hot-rolled strip. After
this, after its skin scale had been removed by acid cleaning,
the strip was cold-rolled to a thickness of 1.2mm, and then
annealed under conditions shown in Table 12 in a CGL line, and
subsequently hot-dip galvanized and subjected to a
galvannealing process at 450~570°C when necessary. The
galvanizing bath temperature was held at 450~460°C, and as for
the galvanizing bath composition, three different
compositions were used: in addition to a Zn bath with Al content
of 0.13~0.20 mass%, a Zn bath with Al content of 5 mass% and
a Zn bath with Al content of 4 mass% and Mg content of 1.5 mass%
were used. The coating weight was adjusted to 50±5g/m2 for
each single side by gas wiping.
An obtained hot-dip galvanized steel sheet was analyzed
to determine the amount of internal oxide and identify oxides
as in Embodiment 1. Also, the external appearance, the degree
of galvannealing (only on galvannealed steel sheets), the
coating adhesion and the corrosion resistance were examined.
Degree of galvannealing: The coating layer was dissolved
in a mixed solution of an aqueous solution of 20wt% of NaOH
and 10wt% of triethanolamine and an aqueous solution of 35wt%
of H2O2 mixed in a volume ratio of 195:7, and the solution is
analyzed by ICP to measure the Fe content (%).
External appearance evaluation: The external appearance
was visually checked to find bare spots or unevenness of
coating.
Coating adhesion:
(Non-alloyed hot-dip galvanized steel sheet) After put
to a ball impact test, a cellophane tape was attached to a
processed part of the steel sheet and the tape was peeled off.
The test specimens were visually inspected to see if there is
any peeled-ff coating layer. Those specimens on which the
coating did not peel off were classified as o, those specimens
with the coating peeled off a little were classified as A, and
those specimens on which the coating peeled off conspicuously
were classified as X.
(Alloyed hot-dip galvanized steel sheet) A test specimen
to which a cellophane tape was attached was bent 90 degrees
on the tape-attached side and bent back, and the tape was peeled
off; subsequently, the amount of the peeled-off coating per
unit length was measured in terms of counts of Zn by a
fluorescent X-ray. The number of counts of Zn was evaluated
referring to the criteria in Table 11. For measurement by
fluorescent X-ray, an Rh bulb was used-under condition of 40kV
and 50mA for 120 sec.
Corrosion resistance: After the surfaces of a steel sheet
manufactured by the above method were subjected to a chemical
treatment process and an electrodeposition process, in test
specimens was inscribed a cross with a knife, and a test
specimen was put to a CCT test for a total of 50 cycles, one
cycle consisting of a series of steps shown below, a
tape-peel-off test was conducted on the cross-inscribed
portions and the peeling-off width of the coating film was
measured. A decision was given as follows: a case where the
peeling-off width was under 4mm was classified as, good (o),
a case where the width was 4mm or larger was classified as
defective (o) .
One cycle consists of wetting (2 hrs) - salt water spray
(2 hrs) - drying (1 hr) - wetting (6 hrs} - drying (2 hrs) -
wetting (6 hrs) - drying (2 hrs) - low temperature (3 hrs).
A cold-rolled steel sheet yet to be galvanized was
evaluated in terms of weldability as follows.
Two test specimens were spot-welded together by using
a dome-tipped 6-mm-dia. Welding electrode under conditions of
electrode pressure of 3.1kN, welding current of 7kA, squeeze
time for 25 cycles, setup time for 3 cycles, welding time for
13 cycles, holding time for 1 cycle; subseguently, a maximum
tensile load in a tensile shear test (TSS) according to JIS
Z3136 and a maximum tensile load in a cross joint tensile test
(CTS) according to JIS Z3137 were measured. Those test
specimens for which the ductility ratio (CTS/TSS) was not less
than 0.25 and the tensile load (TSS) was not less than the
standard tensile shear load (8787N) for a thickness of 1.2mm
were classified as excellent (o), and those not meeting the
above conditions were classified as inferior (X).
The test results are shown en bloc in Table 12. As is
clear from this Table, hot-dip galvanized steel sheets
according to the present invention, regardless of no small
contents of Al and Si, all exhibit excellent coating adhesion,
spot-weldability, and post-painting corrosion resistance.
INDUSTRIAL APPLICABILITY
In the automotive industry, for example, the use of
high-tensile steel sheets is increasing rapidly with a view
to reducing car weight for better fuel economy and improved
crashworthiness. The high-tensile steel sheet has a steel
composition including addition elements such as Si, Mn, Ti,
Al and P. It is well known, however, that as the Si content
is increased, an Si oxide film is formed on the surfaces of
the steel sheet during annealing, thus deteriorating the steel
properties, such as chemical properties, electro-galvanized
coating adhesion, hot-dip galvanizability and coating
adhesion. Above all else, the big problem is the inferior
hot-dip galvanizability of Si-containing high-tensile steel
sheets. To be more specific, when a steel sheet is hot-dip
galvanized, its poor wettability causes the applied zinc not
to adhere to some parts of the steel sheet, which are the
so-called "bare spots", or an insufficient adhesion occurs in
which the coating separates during press working. As a method
for achieving high ductility and high tensile strength without
increasing the Si content, there is a technique by which to
positively increase the Al content in the steel to thereby
decrease the Si content, the surface quality deterioration
peculiar to the Si-added steel can be prevented and
simultaneously the retained austenite can be made stable.
However, Al and Si being both readily oxidizable elements,
an Al oxide film is also formed in addition to the Si oxide
film during annealing, and therefore the problems of
deterioration in hot-dip galvanizability and coating adhesion
have not been solved.
According to a coated steel sheet and a method for
manufacturing this steel sheet in the present invention, the
diffusion of Al into the surface layer of the steel sheet is
prevented/ the amount of Al solid solution in the surface layer
is decreased, and desired steel structure and mechanical
properties can be secured. Moreover, the surface treatability,
hot-dip galvanizability, post-painting corrosion resistance,
and weldability can be improved. Furthermore, even if the
steel sheet has a high Al content, a coating can be formed with
excellent adhesion properties.
We Claim .-
1. A coated steel sheet having a coated layer on a surface of a steel sheet of a composition
containing not less than 0.1 mass % and under 3 mass % of Al, wherein a following condition A or
B is met:
A: An AlN precipitate layer exists on a matrix side near an interface between said steel
sheet and said coated layer
B: Oxide of Al exists in said matrix right under said surface of said steel sheet.
2. A coated steel sheet as claimed in claim 1, wherein said coated layer is a hot-dip galvanized
layer containing not less than 0.1 mass % and not more than 1.0 mass % of Al.
3. A coated steel sheet as claimed in claim 2, wherein said coated layer is a Zn-Fe galvanneal
coating that further contains not less than 7 mass % and not more than 15 mass % of Fe.
4. A coated steel sheet as claimed in claim 2 or 3, wherein there is an AlN precipitate layer on
the matrix side near an interface between said steel sheet and said coated layer and said AlN
precipitate layer has a thickness of not less than 1 urn and not more than 100 µm.
5. A coated steel sheet as claimed in claim 2 or 3, wherein said steel composition further
contains one or two kinds selected from not less man 0.1 mass % of Si and not less man 0.5mass%
of Mn
6. A coated steel sheet as claimed in claim 2 or 3, wherein said steel composition further
contains one or two kinds selected from not less than 0.01 mass % and not more than 1 mass % of
Mo and not less man 0.005 mass % and not more than 0.2 mass % of Nb.
7. A coated steel sheet as claimed in claim 2 or 3, wherein said steel composition further
contains not less than 0.01 mass % and not more than 0.5 mass % of Cu, not less than 0.01 mass %
and not more man 1 mass % of Ni, and not less man 0.01 mass % and not more man 1 mass % of
Mo.
8. A coated steel sheet as claimed in claim 2, wherein said steel composition further contains
not less man 0.03 mass % and not more man 0.25 mass % of C, not less man 0.001 mass % and
not more than 1.0 mass % of Si, not less than 0.5 mass % and not more than 3.0 mass % of Mn,
and not less than 0.001 mass % and not more than 0.10 mass % of P.
9. A coated steel sheet as claimed in claim 8, wherein in said steel matrix, there are one or
more kinds selected from oxides of SiO2, MnO, FeSiO3, Fe2SiO4, MnSiO3, Mn2SiO4, and P2O5.
10. A coated steel sheet as claimed in claim 8 or 9, wherein the amount of oxides in total per
one side surface is not less than 0.01 g/m2 and not more than 1.0 g/m2.
11. A coated steel sheet as claimed in claim 8 or 9, wherein the steel composition further
contains not less than 0.01 mass % and not more than 1.0 mass % of Mo and not less than 0.005
mass % and not more man 0.2 mass % of Nb.
12. A coated steel sheet as claimed in claim 8 or 9, wherein the steel composition farther
contains not less man 0.01 mass % and not more than 0.5 mass % of Cu, not less than 0.01 mass %
and not more than 1.0 mass % of Ni, and not less than 0.01 mass % and not more than 1.0 mass %
of Mo.
13. A coated steel sheet as claimed in claim 8 or 9, wherein the coated layer is a hot-dip
galvanized layer and is galvannealed.
14. A coated steel sheet as claimed in claim 8 or 9, wherein the Fe content in the galvannealed
coated layer is not less than 7 mass % and not more than 15 mass %.
15. A method for manufacturing a coated steel sheet comprising the steps of heating and
holding a steel slab and hot-rolling said slab, and hot-dip-galvanizing a steel sheet, wherein said
slab contains not less than 0.1 mass % and under 3 mass% of Al, and said holding is carried out in
an atmosphere containing not less than 1 volume % and not more than 20 volume % of O2 and not
less man 70 volume % of N2 under the conditions that meet an equation (1) shown below and said
galvanizing is performed by using a galvanizing bam with an Al concentration in the bath is not
less than 0.14 mass % and not more than 024 mass % at a bath temperature of not less than
440°C and not more than 500°C.
{Heating and holding temp(ºC) - (1050 + 25A1) x heating and holding
time(min)= 3000............(1);
wherein Al denotes an Al content (mass%) in the steel.
16. A method for manufacturing a coated steel sheet as claimed in claim 15, wherein said steel
sheet is galvanized by using a galvanizing bath of Al concentration of not less than 0.10 mass %
and not mote than 0.20 mass % in the bath at a bath temperature of not less man 440° C and not
more man 500° C and the hot-dip-galvanized layer is subsequently subjected to a galvanealtng
process at not less man 460° C and not more than 550° C.
17. A method for manufacturing a coated steel sheet as claimed in claim 15 or 16, wherein said
steel slab further contains one or two lands selected from not less than 0.1 mass % of Si and not
less than 0.5 mass % of Mn.
18. A method for manufacturing a coated steel sheet as claimed in claim 15 or 16, wherein said
slab further contains one or two kinds selected from not less than 0.01 mass % and not more than 1
mass % of Mo and not less man 0.005 mass % and not more man 02 mass % of Nb.
19. A method for manufacturing a coated steel sheet as claimed in clam 15 or 16, wherein said
slab further contains not less than 0.01 mass % and not more than 0.5 mass % of Cu, not less man
0.01 mass % and not more than 1 mass % of Ni, and not less than 0.01 mass % and not more man 1
mass % of Mo.
A coated steel sheet having a coated layer on surfaces
of a steel sheet of a composition containing not less than 0.1
mass% and under 3 mass% of Al, wherein a following condition
A or B is met:
A: An AlN precipitate layer exists on a matrix side near an
interface between said steel sheet and said coated layer
B: Oxide of Al exists in said matrix right under said surfaces
of said steel sheet.

Documents:

337-KOLNP-2004-CORRESPONDENCE.pdf

337-KOLNP-2004-FORM 27.pdf

337-KOLNP-2004-FORM-27.pdf

337-kolnp-2004-granted-abstract.pdf

337-kolnp-2004-granted-claims.pdf

337-kolnp-2004-granted-correspondence.pdf

337-kolnp-2004-granted-description (complete).pdf

337-kolnp-2004-granted-drawings.pdf

337-kolnp-2004-granted-examination report.pdf

337-kolnp-2004-granted-form 1.pdf

337-kolnp-2004-granted-form 2.pdf

337-kolnp-2004-granted-form 26.pdf

337-kolnp-2004-granted-form 3.pdf

337-kolnp-2004-granted-form 5.pdf

337-kolnp-2004-granted-reply to examination report.pdf

337-kolnp-2004-granted-specification.pdf

337-kolnp-2004-granted-translated copy of priority document.pdf


Patent Number 223055
Indian Patent Application Number 337/KOLNP/2004
PG Journal Number 36/2008
Publication Date 05-Sep-2008
Grant Date 03-Sep-2008
Date of Filing 12-Mar-2004
Name of Patentee JFE STEEL CORPORATION
Applicant Address 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011
Inventors:
# Inventor's Name Inventor's Address
1 SUZUKI, YOSHITSUGU C/O. JFE STEEL CORPORATION 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011
2 KYONO, KAZUAKI C/O. JFE STEEL CORPORATION 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011
PCT International Classification Number C23C 2/06, 2/28
PCT International Application Number PCT/JP03/02147
PCT International Filing date 2003-02-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2002-270,281 2002-09-17 Japan
2 2002-307,635 2002-09-17 Japan
3 2002-056,139 2002-03-01 Japan
4 2002-229,586 2002-08-07 Japan