Hot Stamp Molded High Strength Component Having Excellent Corrosion Resistance After Coating And Method For Manufacturing Same
Abstract:
Provided is a hot stamp molded high strength component having excellent corrosion resistance after coating in which the propagation of cracks generated in a plating layer during hot stamp machining is inhibited when an Al plated steel plate has undergone hot stamp machining without the addition of special component elements for inhibiting the generation of cracks in the Al plating layer. This hot stamp molded high strength component having excellent corrosion resistance after coating has an alloy plating layer that includes an Al Fe intermetallic compound phase on the surface of the steel plate the hot stamp molded high strength component characterized in that the alloy plating layer is formed from a plurality of intermetallic compound phases the average section length of crystal grains of the phases containing 40 to 65 mass% of Al in the plurality of intermetallic compound phases is 3 to 20 µm the average value of the thickness of the Al Fe alloy plating layer is 10 to 50 µm and the ratio of the standard deviation of the thicknesses of the Al Fe alloy plating layer in relation to the average value of the thicknesses satisfies the following formula: 0 < standard deviation of the thicknesses/average value of the thicknesses < 0.15.
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Notices, Deadlines & Correspondence
c/o NIPPON STEEL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
2. KUSUMI Kazuhisa
c/o NIPPON STEEL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
3. ABE Masayuki
c/o NIPPON STEEL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
4. KUROSAKI Masao
c/o NIPPON STEEL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
Specification
DESCRIPTION
Title of Invention: Hot Stamped High Strength Part
Excellent in Post painting anticorrosion property and
5 Method of Production of Same
Technical Field
[OOOl] The present invention relates to an aluminum
plated high strength part which is excellent in post
10 painting anticorrosion property which is produced by
press forming at a high temperature, that is, by hot
stamping, and is suitable for members in which strength
is required such as auto parts and other structural
members, more specifically relates to a high strength
15 part which is formed by hot stamping which is suppressed
in propagation of cracks which form in the aluminum
plating layer when hot stamping aluminum plated high
strength steel sheet and which is excellent in post
painting anticorrosion property, and a method of
20 production of the same.
Background Art
[0002] In recent years, in applications of steel sheet
for automobile use (for example, automobile pillars, door
impact beams, bumper beams, etc.) and the like, steel
sheet in which both high strength and high formability
are achieved has been desired. As one means for dealing
with this, there is TRIP (transformation induced
plasticity) steel which utilizes the martensite
transformation of residual austenite. Using this TRIP
steel, it is possible to produce high strength steel
sheet which is excellent in formability and which has a
1000 MPa class or so strength, but securing formability
with very high strength steel sheet of further higher
strength, for example, 1500 MPa or more, has been
difficult.
[ 0 0 0 3 ] In view of this situation, the forming method
which has been focused on most recently as a method for
securing high strength and high formability has been hot
stamping (also called hot pressing, hot stamping, die
quenching, press quenching, etc.) This hot stamping heats
the steel sheet to the 800°C or higher austenite region,
then forms it by a die when hot to thereby improve the
formability of the high strength steel sheet and, after
forming it, cools it in the press die to quench it and
thereby obtain a shaped part of the desired quality.
[ 0 0 0 4 ] Hot stamping is promising as a method for
forming very high strength members, but usually includes
a step of heating the steel sheet in the atmosphere. At
this time, oxides (scale) form on the steel sheet
surface, so a later step of removing the scale becomes
necessary. In this regard, in such a later step, there
was the problem of the need for measures from the
viewpoint of the descaling ability and environmental load
etc.
[OOOS] As art to alleviate this problem, the art of
using aluminum plated steel sheet as the steel sheet for
hot stamped member use so as to suppress the formation of
scale at the time of heating has been proposed (for
example, see PLTs 1 and 2) .
[0006] Aluminum plated steel sheet is effective for
the efficient production of a high strength shaped part
by hot stamping. Aluminum plated steel sheet is usually
pressed formed, then painted. The aluminum plating layer
after heating at the time of hot stamping changes to an
intermetallic compound up to the surface. This compound
is extremely brittle. If subjected to a severe forming
operation by hot stamping, the aluminum plating layer
easily cracks. Further, the phases of this intermetallic
compound have more electropositive potential than the
matrix steel sheet, so there was the problem that the
corrosion of the steel sheet material is started from the
cracks as starting points and the post painting
anticorrosion property falls.
[0007] To avoid the drop in the post painting
anticorrosion property due to the formation of cracks in
the aluminum plating layer, adding Mn to this
intermetallic compound is extremely effective, so an
aluminum plated steel sheet which is improved in post
painting anticorrosion property by addition of 0.1% or
more of Mn in the aluminum plating layer has been
proposed (for example, see PLT 3) .
[ 0 0 0 8 ] The art which is described in PLT 3 adds
specific ingredient elements in the aluminum plating
layer to prevent cracks from forming in the aluminum
plating layer, but is not art which prevents cracks from
forming in the aluminum plating layer without addition of
specific ingredient elements into the aluminum plating
layer.
[ 0 0 0 9 ] Further, aluminum plated steel sheet has been
proposed where, if adding elements to the matrix steel of
the aluminum plated steel sheet to give
Ti+O.lMn+O.lSi+O.lCr>0.25, these elements promote
diffusion between A1-Fe so that even if cracks are formed
in the aluminum plating layer, an Fe-A1 reaction proceeds
from around them and therefore the steel sheet material
is prevented from being exposed and the corrosion
resistance is improved (for example, see PLT 4).
[ 0 0 10 ] However, the art which is described in PLT 4
does not try to prevent cracks from forming at the
aluminum plating layer.
Citations List
Patent Literature
[ 0011 ] PLT 1: Japanese Patent Publication No. 2003-
181549A
PLT 2: Japanese Patent Publication No. 2003-49256A
PLT 3: Japanese Patent Publication No. 2003-34855A
PLT 4: Japanese Patent Publication No. 2003-34846A
Summary of Invention
Technical Problem
[0012] The present invention was made in consideration
of this situation and has as its object the provision of
a hot stamped high strength part in which the propagation
of cracks which form at the aluminum plating layer when
hot stamping aluminum plated steel sheet is suppressed
and the post painting anticorrosion property is excellent
even without adding special ingredient elements which
suppress formation of cracks in an aluminum plating
layer. Further, it has as its object the formation of a
lubricating film at the aluminum plating layer surface to
improve the formability at the time of hot stamping
aluminum plated steel sheet and suppress the formation of
cracks in the aluminum plating layer. Furthermore, it has
as its object the provision of a method of production of
a hot stamped high strength part.
Solution to Problem
[0013] The inventors engaged in intensive research to
solve the above problems and completed the present
invention. In general, an aluminum plated steel sheet for
hot stamped member use is formed with an aluminum plating
layer at one or both surfaces of the steel sheet by hot
dipping etc. The aluminum plating layer may contain, by
mass%, Si: 2 to 7% in accordance with need and is
comprised of a balance of A1 and unavoidable impurities.
[ 0 0 14 1 When an aluminum plating layer of aluminum
plated steel sheet before hot stamping contains Si, it is
comprised of an A1-Si layer and Fe-Al-Si layer from the
surface layer. To hot stamp an aluminum plated steel
sheet, first, the aluminum plated steel sheet is heated
to a high temperature to make the steel sheet an
austenite phase. Further, the aluminum plated steel sheet
which is converted to austenite is press formed hot, then
the shaped aluminum plated steel sheet is cooled. The
aluminum plated steel sheet can be made a high
temperature to make it soften once and facilitate the
subsequent press forming. Further, the steel sheet may be
heated and cooled so that it is quenched and an
approximately 1500 MPa or higher mechanical strength is
realized.
[0015] In the heating step of this aluminum plated
steel sheet for hot stamped member use, inside the
aluminum plating layer (when including Si), the A1-Si and
the Fe from the steel sheet mutually diffuse thereby
changing as a whole to an A1-Fe compound (intermetallic
compound). At this time, in the A1-Fe compound, a phase
which contains Si also is partially formed. This compound
(intermetallic compound) is extremely brittle. If shaping
it under severe conditions in hot stamping, cracks will
form in the aluminum plating layer. Further, these phases
have a potential more electropositive than the matrix
steel sheet, so corrosion of the steel sheet material
will begin from the cracks as starting points and the
shaped part will be reduced in post painting
anticorrosion property. Therefore, suppression of the
cracks which form in the aluminum plating layer after hot
stamping improves the post painting anticorrosion
property of the part which is formed by hot stamping.
[0016] In hot stamping, it is not possible to avoid
the formation of cracks in the aluminum plating layer,
but the inventors took note of the fact that if it were
possible to arrest the propagation of cracks of the
aluminum plating layer which formed in hot stamping
inside of the aluminum plating layer, the cracks would
not reach the matrix steel sheet. They discovered that
this would enable prevention of corrosion of the steel
sheet material and prevention of a detrimental effect on
the post painting anticorrosion property of the hot
stamped part. The inventors engaged in intensive research
on arresting the propagation of cracks of an aluminum
plating layer for cracks which formed in the aluminum
plating layer. As a result, they discovered that if
controlling the mean linear intercept length of crystal
grains of an intermetallic compound phase which contains
A1 in 40 to 65% among the crystal grains of the plurality
of intermetallic compound phases based on A1-Fe which are
formed at the surface of the steel sheet (below,
sometimes simply referred to as the "mean linear
intercept length") to 3 to 20 p , it is possible to
arrest the propagation of cracks which form in the
aluminum plating layer. Further, they discovered that by
further forming a lubrication film which contains ZnO at
the aluminum plating layer surface, it is possible to
secure a lubricating property at the time of hot stamping
and possible to prevent surface defects and formation of
cracks. Furthermore, they discovered a steel sheet
composition which is suitable for hot stamping.
[ 0 0 17 1 Furthermore, the inventors discovered that the
thickness of the A1-Fe alloy plating layer has an effect
on the state of spattering at the time of spot welding
and discovered that to obtain stable spot weldability, it
is important reduce the deviation of the plating
thickness (standard deviation), make the average value of
thickness of the A1-Fe alloy plating layer 10 to 50 p ,
and make the ratio of the average value of thickness to
the standard deviation of thickness (standard deviation
of thickness/average value of thickness) 0.15 or less.
[ 0 0 18 ] The present invention was completed based on
these discoveries and has as its gist the following:
[0019] (1) A hot stamped high strength part which is
excellent in post painting anticorrosion property,
comprising an alloy plating layer comprising an A1-Fe
intermetallic compound phase on the surface of the steel
sheet,
the alloy plating layer is comprised from phases of a
plurality of intermetallic compounds,
a mean linear intercept length of crystal grains of a
phase containing Al: 40 to 65 mass% among the phases of
the plurality of intermetallic compounds is 3 to 20 p ,
an average value of thickness of the A1-Fe alloy plating
layer is 10 to 50 pm, and
a ratio of the average value of thickness to the standard
deviation of thickness of the A1-Fe alloy plating layer
satisfies the following relationship:
O a-phase -> FeA13 phase
-> Fe2A15 phase. By going through the transformations,
crystal grains are formed again, so the greater the
transformations which are gone through, the smaller the
mean linear intercept length tends to become. That is,
the mean linear intercept length becomes smaller with the
a-phase than the FeA13 phase and with the P-phase than the
a-phase.
[0045] The method of measurement of a mean linear
intercept length in an alloy plating layer is to polish
any cross-section of a hot stamped part, then etch it by
2 to 3 vo1% of Nital and examine the result by a
microscope. For the examination, a polarization
microscope is used. The polarization angle is adjusted so
that the contrast of the crystal grains becomes the
clearest. At this time, the layer of a compound whose
contrast appears light at the surface layer side
consecutively from the layer of a compound whose contrast
appears dark is a phase of Al: 40 to 65%. This phase is a
phase which has the property of arresting the crack
propagation and is a phase which affects the post
painting anticorrosion property and the plating
workability. As shown in FIGS. 3 (a) to (b) , in particular
when the plating thickness is thin (40 g/m2 per side), due
to the effect of the dark contrast phase, the mean linear
intercept length of Al: 40 to 65% phase is difficult to
measure. Therefore, in this Description, the mean linear
intercept length of the crystal grains in the alloy
plating layer is defined as the mean linear intercept
length which is measured in the direction parallel to the
steel sheet surface. The mean linear intercept length is
found by the line segment method. As shown in FIG. 3(a),
the mean linear intercept length is found by drawing a
line parallel to the steel sheet surface in the plating
layer, counting the number of grain boundaries which this
line passes through, and dividing the measured length by
the number of grain boundaries. It is possible to
calculate the grain size from this mean linear intercept
length, but calculation of the grain size requires that
the shape of the grains be known. In steel sheet, crystal
grains can be assumed to be spherical, but the
intermetallic compounds which are formed at the surface
like in the present invention are unknown in crystal
grain shape, so the mean linear intercept length was
used.
[0046] Note that, in actual measurement, in the
polarization micrographs of FIGS. 3(a) to (d), the grain
boundaries are unclear, so as shown in FIGS. 5(a) and
(b), the crystal grain boundaries were traced in the
polarization micrographs of FIGS. 3(a) and (c) to clarify
the crystal grain boundaries.
[0047] The reason for limiting the mean linear
intercept length of a phase which contains Al: 40 to 65%
after the aluminum plating layer is alloyed to 3 to 20 p
will be explained. A small grain size is preferable as a
crack propagation arrest property of a phase which
contains Al: 40 to 65%, but the steel sheet for hot
stamping member use has to be heated once to the
austenite region. For this reason, this steel sheet is
generally heated to 850°C or more, so the aluminum plating
layer which is alloyed in this heating step ends up with
crystal grains growing to 3 p or more. Therefore,
usually making the crystal grain size less than 3 pm is
extremely difficult. If the mean linear intercept length
exceeds 20 p and the grain size becomes larger, the
aluminum plating layer falls in workability and the
phenomenon of powdering becomes greater. Furthermore, the
crack propagation arrest property of a phase which
contains Al: 40 to 65% no longer functions and cracks can
no longer be arrested by the crystal grains.
[ 0 0 4 8 ] Therefore, in the present invention, the mean
linear intercept length of a phase which contains Al: 40
to 65% was limited to 3 to 20 p , preferably it is 5 to
17 pm.
[0049] Next, the effects of the aluminum plating
conditions and heating conditions at the time of hot
stamping on the mean linear intercept length will be
explained.
[OOSO] FIG. 4 is a view which shows the effects of the
aluminum plating conditions and the heating conditions at
the time of hot stamping on the mean linear intercept
length. In FIG. 4, the abscissa shows the Larson-Miller
parameter (LMP) of the heating conditions at the time of
hot stamping.
The Larson-Miller parameter (LMP) is expressed by
LMP=T (20+logt)
(wherein, T: absolute temperature (K), t: time (hrs)).
Here, T is the heating temperature of the steel sheet,
while "t" is the holding time in the heating furnace
after reaching the target temperature. LMP is an
indicator which is used in general for treating the
temperature and time in a unified manner in heat
treatment and phenomena such as creep where the
temperature and time have an effect. This parameter can
also be used for the growth of crystal grains. In the
present invention, LMP summarizes the effects of
temperature and time on the mean linear intercept length
of crystal grains, so the heat treatment conditions at
the time of hot stamping can be described by just this
parameter.
[OOSl] The symbols which are described in FIG. 4 will
be explained. A and B show aluminum plating conditions. A
means a 7% Si bath of a bath temperature of 660°C, while B
means a 11% Si bath of a bath temperature of 640°C. These
are typical conditions whereby an a-AlFeSi phase and a PAlFeSi
phase are produced at the time of aluminum
plating. Further, "5°C/s" and "50°C/s" mean the
temperature elevation rates at the time of hot stamping.
5OC/s corresponds to usual furnace heating, while 50°C/s
corresponds to infrared heating, ohmic heating, and other
rapid heating. Here, the "temperature elevation rate"
means the average temperature elevation rate from the
start of temperature elevation to a temperature 10°C lower
than the target temperature. If comparing the aluminum
plating conditions A and B, the trend is that forming an
a-AlFeSi phase at the time of the conditions A, that is,
aluminum plating, gives a mean linear intercept length
greater than the conditions B. It was learned that it is
necessary to limit the range of heating conditions at the
time of hot stamping to a narrower range (LMP=20000 to
23000). If the LMP is less than 20000, the diffusion of
the A1-Si plating layer with the steel sheet is
insufficient and an unalloyed A1-Si layer remains, so
this is not preferred. Further, in the plating conditions
A of FIG. 4, comparing the temperature elevation rates of
5OC/sec and 50°C/sec, it is shown that even with such a
narrow range, if increasing the temperature elevation
rate at the hot stamping, the structure becomes finer.
The temperature elevation rate is preferably 4 to
200°C/sec(s) in range. If the temperature elevation rate
is slower than 4OC/sec, this means that the heating step
takes time and means that the hot stamping falls in
productivity. Further, if faster than 200°C/sec, control
of the temperature distribution in the steel sheet
becomes difficult. Both are not preferred. Establishing
suitable aluminum plating conditions and hot stamping
conditions enables the mean linear intercept length to be
made 3 to 20 pm.
[0052] As explained above, by making the mean linear
intercept length of the crystal grains of a phase
containing Al: 40 to 65% in the layer of the
intermetallic compounds mainly comprised of A1-Fe which
is formed at the surface of the steel 3 to 20 p, it is
possible to arrest the propagation of cracks which form
at the plating layer due to hot stamping inside the
plating layer. Due to this, it is possible to suppress
corrosion of the steel sheet matrix due to cracks in the
plating layer and possible to obtain high strength auto
parts which are excellent in post painting anticorrosion
property and other hot stamped parts.
[0053] The hot stamped high strength parts of the
present invention further may have a surface film which
contains ZnO at the surface of the alloy plating layer
mainly comprised of A1-Fe.
100541 The hot stamped high strength part of the
present invention has the extremely hard A1-Fe
intermetallic compounds formed at the plating layer of
the steel sheet surface at the time of hot stamping. For
this reason, working defects are formed at the surface of
the shaped part due to contact with the die at the time
of press forming in the hot stamping. There is the
problem that these working defects because the cause of
cracks in the plating layer. The inventors discovered
that by forming a surface film which has excellent
lubricity at the surface of the aluminum plating layer,
it is possible to suppress the working defects of a
shaped part and the occurrence of cracks in the plating
layer and discovered that it is possible to improve the
formability at the time of hot stamping and the corrosion
resistance of a shaped part.
[0055] The inventors engaged in intensive studies on a
surface film which has lubricity which is suitable for
hot stamping and as a result discovered that providing
the surface of the aluminum plating layer with a
lubricating surface film layer which contains ZnO (zinc
oxide), it is possible to effectively prevent working
defects of the shaped part surface and cracks in the
plating layer.
[0056] ZnO is included in the surface film layer at
one side of the aluminum plated steel sheet in an amount,
converted to mass of Zn, of 0.3 to 7 g/m2. More
preferably, it included in 0.5 to 4 g/m2. If the content
of ZnO is, converted to mass of Zn, 0.1 g/m2 or more, the
effect of improvement of the lubricity and effect of
prevention of segregation (effect of enabling uniform
thickness of aluminum plating layer) etc. can be
effectively exhibited. On the other hand, when the
content of ZnO exceeds, converted to mass of Zn, 7 g/m2,
the total thickness of the aluminum plating layer and
surface film layer becomes too thick and the weldability
or painting adhesion falls.
[0057] FIG. 6 is a view which shows the relationship
between the amount of deposition of Zn on the aluminum
plated steel sheet surface and the coefficient of dynamic
friction. The content of ZnO in the surface film layer
was changed to evaluate the lubricity at the time of hot
stamping. This lubricity was evaluated by the following
test. First, different test materials of the aluminum
plated steel sheet which has an ZnO film layer (150x200
mrn) were heated to 900°C, then were cooled down to 700°C.
The test materials were subjected to loads from above
through steel balls. Further, the steel balls were slid
out over the test materials. At this time, the pullout
load was measured by a load cell. The ratio of the
pullout load/push-in load was made the coefficient of
dynamic friction. The results are shown in FIG. 6. If the
coefficient of dynamic friction is smaller than 0.65, it
is evaluated as good. It is learned that in a region
where the amount of deposition of Zn is generally 0.7 g/m2
or more, the coefficient of dynamic friction is
effectively kept low and the hot lubricity can be
improved.
[0058] A surface film layer which contains ZnO can be
formed, for example, by applying a paint which contains
ZnO and baking or drying it after applying for curing so
as to enable formation over the aluminum plating layer.
As the method of applying a ZnO paint, for example, the
method of mixing a predetermined organic binder and a
dispersion of ZnO powder and applying it to the surface
of the aluminum plating layer, a method of painting by
powder painting, etc. may be mentioned. As the method of
baking and drying after applying, for example, a hot air
furnace, induction heating furnace, near infrared ray
furnace, or other method or a method combining the same
may be mentioned. At this time, depending on the type of
the binder which is used for applying, instead of baking
and drying after applying, for example, curing by
ultraviolet rays or electron beams etc. is possible. As
the predetermined organic binder, for example, a
polyurethane resin or polyester resin etc. may be
mentioned. However, the method of forming the ZnO surface
film layer is not limited to these examples and can be
formed by various methods.
[0059] Such a surface film layer which contains ZnO
can improve the lubricity of an aluminum plated steel
sheet at the time of hot stamping, so working defects of
the plating layer and cracks in the plating layer at the
surface of the shaped part can be suppressed.
[0060] ZnO has a melting point of approximately 1975°C
or higher compared with the aluminum plating layer (the
melting point of aluminum is approximately 660°C) etc.
Therefore, even when working steel sheet at for example
800°C or more such as when working a coated steel sheet by
the hot stamping method etc., the surface film layer
which contains this ZnO will not melt. Therefore, even if
heating of the aluminum plated steel sheet causes the
aluminum plating layer to melt, the state where the ZnO
surface film layer covers the aluminum plating layer to
be maintained, so it is possible to prevent the thickness
of the melted aluminum plating layer from becoming
uneven. Note that, uneven thickness of the aluminum
plating layer of a hot stamped high strength part easily
occurs, for example, in the case of heating by a furnace
where the blank is oriented vertically with respect to
the direction of gravity or the case of heating by ohmic
heating or induction heating. However, this surface film
layer can prevent uneven thickness of the aluminum
plating layer when such heating is performed and enables
aluminum plating layer to be formed thicker.
[0061] In this way, an ZnO surface film layer exhibits
the effects of improving the lubricity and making the
thickness of the aluminum plating layer uniform etc. so
can improve the formability at the time of press forming
in hot stamping and the corrosion resistance after press
forming .
Further, the aluminum plating layer can be made uniform
in thickness, so can be rapidly heated by ohmic heating
or induction heating enabling a higher temperature
elevation rate. This is effective for making the mean
linear intercept length of the crystal grains of an
intermetallic compound phase which contains Al: 40 to 6
5mass% 3 to 20 pm.
[0062] Furthermore, this ZnO surface film layer never
causes a drop in the spot weldability, paint adhesion,
post painting anticorrosion property, and other
performance. The post painting anticorrosion property is
rather further improved by imparting a surface film
layer.
[0063] Next, the inventors studied the composition of
ingredients for steel sheet for obtaining the aluminum
plated steel sheet for rapidly heated hot stamped member
use provided with both excellent corrosion resistance and
excellent productivity. As a result, since the hot
stamping was performed with the pressing and quenching
simultaneously by the die, they obtained the ingredients
for the steel sheet which are explained below from the
viewpoint of the aluminum plated steel sheet for hot
stamped member use containing ingredients enabling easy
quenching and thereby giving hot stamped parts which have
a 1000 MPa or more high strength after hot stamping.
[0064] Below, the reasons for limiting the ingredients
of the steel sheet in the present invention will be
explained. Note that, the % of the ingredients mean
mass%.
[0065] C: 0.1 to 0.5%
The present invention provides a hot stamped part which
has a 1000 MPa or more high strength after shaping. To
obtain high strength, the steel has to be rapidly cooled
after hot stamping to transform it to a structure of
mainly martensite. From the viewpoint of improvement of
the hardenability, an amount of C of at least 0.1% is
necessary. On the other hand, if the amount of C is too
great, the toughness of the steel sheet remarkably falls,
so the workability falls. For this reason, the amount of
C is preferably 0.5% or less.
100661 Si: 0.01 to 0.7%
Si promotes a reaction between the A1 and Fe in the
plating and has the effect of raising the heat resistance
of the aluminum plated steel sheet. However, Si forms a
stable oxide film during the recrystallization annealing
of the cold rolled steel sheet at the steel sheet
surface, so is an element which obstructs the properties
of the aluminum plating. From this viewpoint, the upper
limit of the amount of Si is made 0.7%. However, if
making the amount of S less than 0.01%, the fatigue
property deteriorates, so this is not preferable.
Therefore, the amount of Si is 0.01 to 0.7%.
[0067] Mn: 0.2 to 2.5%
Mn is well known as an element which raises the
hardenability of steel sheet. Further, it is also an
element which is necessary for preventing hot
embrittlement due to the unavoidably entering S. For this
reason, 0.2% or more has to be added. Further, Mn raises
the heat resistance of steel sheet after aluminum
plating. However, if over 2.5% of Mn is added, the part
which is hot stamped after quenching falls in impact
properties, so 2.5% is made the upper limit.
[0068] Al: 0.01 to 0.5%
A1 is suitable as a deoxidizing element, so 0.01% or more
may be included. However, if included in a large amount,
coarse oxides are formed and the mechanical properties of
the steel sheet are impaired, so the upper limit of the
amount of A1 is made 0.5%.
[0069] P: 0.001 to 0.1%
P is an impurity element which is unavoidably included in
steel sheet. However, P is a solution strengthening
element. It can raise the strength of the steel sheet
relatively inexpensively, so the lower limit of the
amount of P was made 0.001%. However, if recklessly
increasing the amount of addition, the toughness of the
high strength material is lowered and other detrimental
effects appear, so the lower limit of the amount of P was
made 0.1%.
[ 0 0 7 0 ] S: 0.001 to 0.1%
S is an unavoidably included element. It forms inclusions
of MnS in the steel. If the MnS is large in amount, the
MnS forms starting points of fracture, obstructs
ductility and toughness, and becomes a cause of
deterioration of workability. Therefore, the amount of S
is preferably as low as possible. The upper limit of the
amount of S was made 0.1% or less, but reducing the
amount of S more than necessary is not preferable from
the viewpoint of manufacturing costs, so the lower limit
was made 0.001%.
[0071] N: 0.0010% to 0.05%
N easily bonds with Ti or B, so has to be controlled so
as not to decrease the effects targeted by these
elements. An amount of N of 0.05% or less is allowable.
Preferably, the amount of N is 0.01% or less. On the
other hand, reduction more than necessary places a
massive load on the steelmaking step, so 0.0010% should
be made the target for the lower limit of the amount of
N.
[0072] Next, the ingredients which can be selectively
contained in the steel will be explained.
[0073] Cr: over 0.4% to 3%
Cr is also an element which generally raises the
hardenability. It is used in the same way as Mn, but also
has a separate effect when applying an aluminum plating
layer to steel sheet. If Cr is present, for example, when
box annealing the steel after applying the aluminum
plating layer so as to alloy the aluminum plating layer,
the plating layer and the steel sheet matrix easily alloy
with each other. When box annealing the aluminum plated
steel sheet, A1N is formed in the aluminum plating layer.
A1N suppresses the alloying of the aluminum plating layer
and leads to peeling of the plating, but addition of Cr
makes formation of A1N difficult and makes alloying of
the aluminum plating layer easier. To obtain these
effects, the amount of Cr is over 0.4%. However, even if
adding Cr in an amount of over 3%, the effect becomes
saturated. Further, the cost also rises. In addition, the
aluminum plating property falls. Therefore, the upper
limit of the amount of Cr is 3%.
[0074] Mo: 0.005 to 0.5%
Mo, like Cr, has the effect of suppressing the formation
of AlN, which causes peeling of the plating layer, formed
at the interface of the plating layer and the steel sheet
matrix when box annealing the aluminum plating layer.
Further, it is a useful element from the viewpoint of the
hardenability of the steel sheet. To obtain these
effects, an amount of Mo of 0.005% is necessary. However,
even if adding over 0.5%, the effect becomes saturated,
so the upper limit of the amount of Mo is 0.5%.
[0075] B: 0.0001 to 0.01%
B also is a useful element from the viewpoint of the
hardenability of steel sheet and exhibits its effect at
0.0001% or more. However, even if adding over 0.01%, the
effect becomes saturated and, further, casting defects
and cracking of the steel sheet at the time of hot
rolling occur etc. and the manufacturability otherwise
drops, so the upper limit of the amount of B is 0.01%.
Preferably, the amount of B is 0.0003 to 0.005%.
[0076] W: 0.01to 3%
W is a useful element from the viewpoint of the
hardenability of steel sheet and exhibits its effect at
0.01% or more. However, even if over 3% is added, the
effect becomes saturated and, further, the cost also
rises, so the upper limit of the amount of W is 3%.
[0077] V: 0.01 to 2%
V, like W, is a useful element from the viewpoint of the
hardenability of steel sheet and exhibits its effect at
0.01% or more. However, even if V us added in an amount
over 3%, the effect becomes saturated and, further, the
cost also rises, so the upper limit of the amount of V is
2%.
[ 0 0 7 8 ] Ti: 0.005 to 0.5%
Ti can be added from the viewpoint of fixing the N. By
mass%, Ti has to be added in an amount of approximately
3.4 times the amount of N, but N, even if decreased, is
present in 10 ppm or so, so the lower limit of the amount
of Ti was made 0.005%. Further, even if excessively
adding Ti, the hardenability of the steel sheet is caused
to fall or the strength is also caused to fall, so the
upper limit of the amount of Ti is 0.5%.
[0079] Nb: 0.01 to 1%
Nb, like Ti, can be added from the viewpoint of fixing
the N. By mass%, Nb has to be added in an amount of
approximately 6.6 times the amount of N, but N, even if
decreased, is present in 10 ppm or so, so the lower limit
of the amount of Nb was made 0.01%. Further, even if
excessively adding Nb, the hardenability of the steel
sheet is caused to fall or the strength is also caused to
fall, so the upper limit of the amount of Nb is 18,
preferably 0.5%.
[ 0 0 8 0 1 Further, as ingredients in a steel sheet, even
if Ni, Cu, Sn, Sb, are further included, the effect of
the present invention is not obstructed. Ni is a useful
element from the viewpoint of not only the hardenability
of steel sheet, but also the low temperature toughness
which in turn leads to improvement of the impact
resistance. It exhibits this effect at 0.01% or more of
Ni. However, even if adding Ni in over 5%, the effect
becomes saturated and the cost rises, so N may be added
in the range of 0.01 to 5%. Cu is also a useful element
from the viewpoint of not only the hardenability of steel
sheet, but also the toughness. It exhibits this effect at
0.1% or more of Cu. However, even if adding Cu in over
3%, the effect becomes saturated and the cost rises. Not
only that, deterioration of the slab properties and
cracks and defects in the steel sheet at the time of hot
rolling are caused, so Cu should be added in 0.01 to 3%
in range. Furthermore, Sn and Sb are both elements which
are effective for improving the wettability and
bondability of the plating with respect to the steel
sheet. An amount of 0.005% to 0.1% can be added. If both
are amounts of less than 0.005%, no effect can be
recognized, while if over 0.1% is added, defects easily
are caused at the time of production and, further, a drop
in toughness is caused, so the upper limits of the amount
of Sn and the amount of Sb are 0.1%.
[ 0 0 8 1 ] Further, the other ingredients are not
particularly prescribed. Sometimes Zr, As, and other
elements enter from the iron scrap, but if in the usual
range, they do not affect the properties of the steel
which is used for the present invention.
[0082] Next, the method of production of a hot stamped
high strength part will be explained.
[0083] The aluminum plated steel sheet for hot stamped
member use which is used in the present invention is
produced by taking cold rolled steel sheet which has been
obtained by hot rolling steel, then cold rolling it, and
plating it on a hot dipping line with an annealing
temperature of 670 to 760°C and a furnace time in the
reducing furnace of 60 sec or less to treat the steel
sheet with aluminum plating which contains Si: 7 to 15%.
It is effective to make the skin pass rolling rate after
aluminum plating 0.1 to 0.5%.
100841 The annealing temperature of the hot dipping
line has an effect on the shape of the steel sheet. If
the annealing temperature is raised, the steel sheet
easily warps in the C direction. As a result, at the time
of aluminum plating, the difference in plating coating
deposition amounts at the center part of the steel sheet
in the width direction and near the edges will easily
become larger. From this viewpoint, the annealing
temperature is preferably 760°C or less. Further, if the
annealing temperature is too low, the temperature of the
sheet when being dipped in the aluminum plating bath
falls too much and dross defects easily are caused, so
the lower limit of the annealing temperature is 670°C.
[0085] The furnace time in the reducing furnace
affects the aluminum plating properties. Si, Cr, Al, and
other elements which oxidize more easily than Fe easily
oxidize in the reducing furnace at the steel sheet
surface and obstruct the reaction between the aluminum
plating bath and the steel sheet. In particular, if the
furnace time in the reducing furnace is long, this effect
becomes remarkable, so the furnace time is preferably 60
sec or less. Note that the lower limit of the furnace
time is not particularly defined, but 30 sec or more is
preferable.
[0086] After the aluminum plating, for shape
adjustment etc., the sheet is rolled by skin pass
rolling, but the rolling rate at this time affects the
alloying of the aluminum plating layer at the time of hot
stamping. Due to the rolling, strain is introduced into
the steel sheet and plating layer. This is believed to be
a result of this. If the rolling rate is high, the alloy
layer after hot stamping tends to become smaller in
crystal grain size, but it is not preferable if the
rolling rate is made too low since the alloy layer which
is produced is given cracks. For this reason, the rolling
rate is preferably made 0.1 to 0.5%.
[ 0 0 8 7 ] Further, after the aluminum plating, box
annealing can be performed to make the aluminum plating
layer alloyed. At this time, to promote the alloying, the
steel preferably is made to include Cr, Mo, etc. The box
annealing is for example performed at 650°C for 10 hours
or SO.
[ 0 0 8 8 ] The thus obtained aluminum plated steel sheet
can be rapidly heated in the subsequent hot stamping step
by a 50°C/sec or more temperature elevation rate. Further,
rapid heating is effective for making the mean linear
intercept length of the crystal grains in a phase
containing Al: 40 to 65% in the A1-Fe alloy layer 3 to 20
pm. The heating system is not particularly limited. The
usual furnace heating or an infrared type of heating
system using radiant heat may be used. Further, it is
also possible to use ohmic heating or high frequency
induction heating or another heating system using
electricity which enables rapid heating by a temperature
elevation rate of 50°C/sec or more.
[0089] The upper limit of the temperature elevation
rate is not particularly defined, but when using the
above ohmic heating or high frequency induction heating
or other heating system, due to the performance of the
systems, 300°C/sec or so becomes the upper limit.
[0090] Further, at this heating step, the peak sheet
temperature is preferably made 850°C or more. The peak
sheet temperature is made 850°C or more so as to heat the
steel sheet to the austenite region and promote
sufficient alloying of the aluminum plating layer up to
the surface.
[009l] Next, the aluminum plated steel sheet in the
heated state is hot stamped to a predetermined shape
between a pair of top and bottom forming dies. After
being formed, it is held stationary at the press bottom
dead center for several seconds to quench it by cooling
by contact with the forming dies and thereby obtain the
hot stamped high strength part of the present invention.
[0092] The hot stamped part was welded, chemically
converted, painted by electrodeposition, etc. to obtain
the final product. Usually, cationic electrodeposition
painting is used. The film thickness becomes 1 to 30 pn
or so. After the electrodeposition painting, an
intermediate painting, top painting, and other painting
are sometimes also applied.
Examples
[0093] Below, examples will be used to explain the
present invention in further detail.
Example 1
After the usual hot rolling step and cold rolling step, a
cold rolled steel sheet of the steel ingredients such as
shown in Table 1 (sheet thickness 1.4 mrn) was covered by
hot dip aluminum plating containing Si. For the hot dip
aluminum plating, a nonoxidizing furnace-reducing furnace
type of line was used. After the plating, gas wiping was
used to adjust the plating coating deposition amount to a
total for the two sides of 160 g/m2, then the sheet was
cooled. At this time, as the plating bath composition,
there were (A) : A1-7%Si-2%Fe, bath temperature 660°C, and
(B) : Al-11%Si-2%Fe, bath temperature 640°C. The plating
bath conditions correspond to the phases at the aluminum
plating conditions A and B of FIG. 4. It should be noted
that the Fe in the bath is unavoidable Fe which is
supplied from the plating equipment and strips in the
bath. Further, the annealing temperature was made 720°C
and the furnace time in the reducing furnace was made 45
sec. The aluminum plated steel sheet was generally good
in appearance with no nonplating defects etc.
[0094] The thus prepared test piece was evaluated for
post painting anticorrosion property. The hot stamping
was performed using a usual furnace heating means. The
temperature elevation rate of the aluminum plated steel
sheet was approximately 5'C/sec. A 250x300 mrn large test
piece was heated in the air. The piece was elevated in
temperature over approximately 3 minutes, then was held
for approximately 1 minute, then removed from the furnace
and cooled down to approximately 700°C in temperature,
formed into a hat shape, and cooled in the die. At this
time, the cooling rate was approximately 200°C/sec. As
shown in Table 2, the heating temperature of the test
piece was changed in various ways to control the
structure of the aluminum plating layer after alloying.
[0095] The vertical wall part of the hat shaped part
was cut out to 50x100 mm and evaluated for post painting
anticorrosion property. The chemical conversion solution
PB-SX35 made by Parkerizing used for chemical conversion,
then the cationic electrodeposition paint Powernix 110
made by Nippon Paint was painted to give an approximately
20 pm thickness. After that, a cutter was used to crosscut
this film, then a composite corrosion test defined by
the Society of Automobile Engineers of Japan (JASO M610-
92) was performed for 180 cycles (60 days). The extent of
blistering from a cross-cut (maximum blistering at the
cross-cut (maximum blister width at one side) was
measured. At this time, the blister width of general
rust-proof steel sheet, that is, GA (hot dip galvannealed
steel sheet) (amount of deposition of 45 g/m2 at one side)
was 5 mm.
[0096] The post painting anticorrosion property was
evaluated as "very good" with a blister width of 4 mm or
less, as "good" with a blister width of over 4 mm to 6
mm, and as "poor" with a blister width of over 6 mm.
[0097] Regarding evaluation of the spot weldability,
this has to be performed by a flat sheet, so a 400x500 mm
plate shaped die was used. The usual furnace heating
means was used, 400x500 mm aluminum plated steel sheet
was heated by a temperature elevation rate of
approximately 5OC/sec in the air, the sheet was evaluated
in temperature over approximately 3 minutes, then was
held for approximately 1 minute, then was taken out of
the furnace, cooled in the air down to approximately 700°C
in temperature, then quenched in the die. 30 mm of the
two edges of the aluminum plated steel sheet, plated by
A1 on a hot dipping line, in the width direction were cut
off. The rest was used for the tests. After hot stamping,
the part was quenched, then a 30x50 mm weld test piece
was cut out and measured for suitable weld current range
by a pressure of 500 kgf and electrification for 10
cycles (60Hz). At this time, the lower limit current was
made 4dt ("t" is the sheet thickness), while the upper
limit current was made the spattering. The upper limit
current value - lower current value was made the suitable
weld current range.
[0098] The spot weldability was evaluated as "good"
when over the suitable weld current range 2 kA and "poor"
when the suitable weld current range 2 kA or less.
[0099] Further, after Nital etching, the test piece
was examined in cross-section and the average value of
thickness, the standard deviation of thickness (deviation
in plating thickness), and the ratio of the average value
of thickness to the standard deviation of thickness
(standard deviation/average) were found for the plating
thickness. Further, the alloy layer structure was
examined and the mean linear intercept length of the
crystal grains of a phase which contains Al: 40 to 65
mass% was measured. At this time, the test piece was cut
out from the flange part with little deformation at the
hat shaped part.
[ 0 10 0 ] Note that, the average value of plating
thickness and the standard deviation of plating thickness
were determined by sampling 20 x 30 mm test pieces at
positions 50 mm from the two edges of the steel sheet in
the width direction, the center, and intermediate
positions between the positions 50 mm from the two edges
and the center, that is, a total of five locations. The
test pieces were cut, examined in cross-section,
calculated for thickness at the front and back, measured
for thickness at 10 points, and calculated for average
value of thickness and standard deviation.
[OlOl] The aluminum plating conditions, hot stamping
conditions, mean linear intercept length, average value
of thickness, and results of evaluation of the post
painting anticorrosion property and weldability are
described in Table 2.
[0102] Further, simultaneously, the cross-sectional
hardness was measured by a Vicker's hardness meter (load
1 kgf), but values of a hardness of 420 or more were
obtained at all measured locations.
[ 0 10 3 ] Table 1
Steel ingredients (mass%)
C
0.22
Si
0.19
Mn
1.24
A1
0.04
P
0.02
S
0.014
N
0.005
Ti
0.02
B
0.003
Cr
0.12
[0104] Table 2
[OlOS] As shown by the results of evaluation of Table
2, test pieces of the aluminum plating conditions A and B
were both hot stamped under the same conditions, but
differences were observed in the obtained alloy layer
structures (mean linear intercept lengths). Examples with
large mean linear intercept lengths fell relatively in
post painting anticorrosion property. The reason is
believed to be the plating cracks.
[0106] That is, the invention examples were all
excellent in post painting anticorrosion property and
spot weldability, but in the comparative examples where
the mean linear intercept lengths failed to satisfy the
requirements of the present invention (Nos. 4, 5, lo),
the post painting anticorrosion property was inferior.
Samples plated with A1 by the conditions of A were used
for rapid heating and quenching in a flat plate die. The
heating method used a near infrared heating furnace. The
temperature elevation rate at that time was 50°C/sec. The
peak sheet temperature and the holding conditions were
also changed to investigate the structures of the plating
layers at that time. The results and the results of Table
2 are summarized in FIG. 4. It is shown that the mean
linear intercept length is dependent on the plating
conditions and the heating conditions.
[0107] Example 2
Cold rolled steel sheets of the various steel ingredients
(A to I) which are shown in Table 3 (sheet thickness 1 to
2 mrn) were used for aluminum plating in the same way as
in Example 1. In this example, the annealing temperature
and the reducing furnace time at this time were changed.
As the aluminum plating bath composition, by mass%, Si:
9% and Fe: 2% were contained. The bath temperature was
660°C and the deposition after plating was adjusted by the
gas wiping method to a total of the two surfaces of 160
g/m2.
[OlOS] After this, a method similar to Example 1 was
used to make the heating temperature at the time of hot
stamping 950°C for quenching. After that, the post
painting anticorrosion property and the spot weldability
were evaluated. The method of evaluation was the same as
in Example 1. The Vicker's hardness was 420 or more in
5 all cases.
[ 0 11 0 ] Table 4
I
4
P
I
No.
1
Steel
A
7
8
9
10
11
12
Sheet
thickness
(mm)
1.2
D
E
F
G
H
I
Annealing
temp.
("C)
740
1.6
1.6
1.6
2.0
1.2
1.6
Reducing
time
(s~c)
4 0
7 2 0
730
740
7 4 0
740
7 4 0
Plating
thickness
average
(pm)
2 8
5 0
5 0
5 0
6 5
4 0
5 0
Plating
thickness
standard
deviation
2.5
2 9
2 8
2 8
2 8
2 8
Standard
deviation/
average
0.09
3.3
3.2
3.0
4.4
2.6
Mean
linear
intercept
length
(pm)
12
2 8
0.11
0.11
0.11
0.16
0.10
Post painting
anticorrosion
property
Very Good
Good
12
13
12
12
12
Inv. ex.
Spot
weldability
Good
Remarks
Inv. ex.
Very Good
Very Good
Very Good
Poor
Very Good
Good
Good
Good
Poor
Good
Inv. ex.
Inv. ex.
Inv. ex.
Comp. ex.
Inv. ex.
[0111] In Example 2, the ingredients of the steel
used, the sheet thickness, and the aluminum plating bath
components were changed. As shown by the results of
evaluation of Table 4, a trend was observed where if the
sheet thickness becomes larger, the standard deviation of
the plating thickness becomes larger and, further, if the
annealing temperature becomes higher, the standard
deviation of the plating thickness becomes larger. If the
standard deviation is large, the suitable weld current
range is narrow and spattering was easily generated in
spot welding. Further, in a system of ingredients with
high Si such as the Steel Ingredients G, if the furnace
time in the reducing furnace is long (65 sec), nonplating
defects are deemed to occur and the post painting
anticorrosion property fell.
[0112] That is, as shown by the results of evaluation
of Table 4, the invention examples were all excellent in
post painting anticorrosion property and spot
weldability, but in a comparative example where the ratio
of the average value of thickness to the standard
deviation of thickness (standard deviation/average)
exceeds 0.15 (No. 4), the spot weldability was inferior.
Further, in a comparative example where the reducing
furnace time was long and the standard deviation/average
exceeded 0.15 (No. lo), both the post painting
anticorrosion property and spot weldability were
inferior.
[0113] Example 3
The aluminum plated steel sheets of Nos. 2 and 5 of Table
4 of Example 2 were box annealed to alloy the aluminum
plating layers. At this time, No. 2 corresponded to the
Steel Ingredients A and No. 5 to the Steel Ingredients B.
These differed in the amounts of Cr in the steel. At this
time, in No. 2 (Steel Ingredients A), at the time of box
annealing, A1N was formed near the interface of the
aluminum plating layer and the steel sheet and the
aluminum plating layer could not be sufficiently alloyed.
In No. 5 (Steel Ingredients B), alloying was possible.
Using No. 5, an ohmic heating means was used to raise the
temperature by a temperature elevation rate of 200°C/sec
up to 950°Cf then the sheet was quenched without holding.
5 The box annealing caused the aluminum plating layer to
become alloyed, so even after ohmic heating, the
thickness of the A1-Fe alloy layer was constant. The post
painting anticorrosion property and spot weldability were
evaluated by similar methods to Example 1, whereupon the
10 post painting anticorrosion property was evaluated as
being "very good" and the spot weldability as being
"good", that is, excellent properties were shown. The
Vicker's hardness was also shown to be 482.
[ 0 11 4 1 Example 4
15 The steel of Table 1 of Example 1 was used for aluminum
plating under the aluminum plating conditions B of
Example 1. At this time, the plating coating deposition
amount was adjusted to a total of the two sides of 80 to
160 g/m2. Furthermore, after the aluminum plating, a
20 mixture of a finely dispersed ZnO aqueous solution
(Nanotech Slurry made by C.I. Kasei) and a urethane-based
water-soluble resin was coated by a roll coater and dried
at 80°C. At this time, the amounts of deposition of the
ZnO film were, converted to Zn, 0.5 to 3 g/m2. These test
25 pieces were hot stamping and quenched.
[0115] As the hot stamping conditions at this time, in
addition to the furnace heating which is shown in Example
1, an infrared heating furnace was also used. The holding
time in the case of furnace heating was 60 sec, while in
30 the case of infrared heating was also 60 sec. Note that,
the temperature elevation rate in the infrared heating
was approximately 19OC/sec. The thus prepared test piece
was evaluated by the same method as in Example 1. The
results of evaluation at this time are shown in Table 5.
35 The Vicker's hardness was 420 or more in all cases.
[0116] Table 5
[0117] Test pieces given a ZnO film exhibited excellent post painting anticorrosion
property even with a small deposition amount. Further, the spot weldability was also
excellent.
CLAIMS
Claim 1. A hot stamped high strength part which is
excellent in post painting anticorrosion property,
comprising an alloy plating layer comprising an A1-Fe
intermetallic compound phase on the surface of the steel
sheet,
said alloy plating layer is comprised from phases of a
plurality of intermetallic compounds,
a mean linear intercept length of crystal grains of a
phase containing Al: 40 to 65 mass% among said phases of
the plurality of intermetallic compounds is 3 to 20 pm,
an average value of thickness of said A1-Fe alloy plating
layer is 10 to 50 pm, and
a ratio of the average value of thickness to the standard
deviation of thickness of said A1-Fe alloy plating layer
satisfies the following relationship:
O