TECHNICAL FIELD
[0001] The present invention relates to a ferrite-based stainless steel (ferritic stainless
steel sheet) that is used in exhaust gas-condensate environments (environments of
exhaust gas condensate water) and a method for manufacturing the same. Examples of
members that are exposed to exhaust gas-condensate environments include automobile
mufflers, exhaust heat recovery devices, and exhaust gas recirculation apparatuses
such as exhaust gas recirculation (EGR) coolers.
BACKGROUND ART
[0003] Recently, in the automotive field, individual components included in exhaust gas
have acted as causes of air pollution and environmental pollution, and thus tightening
of regulations has been underway. Therefore, in order to decrease the amount of CO
2 exhausted from automobiles and improve gas mileage, not only improvement in engine
efficiencies by means of high-efficiency combustion, idling stop function, and the
like and weight reduction by means of material substitution, but also improvements
by means of energy source diversification due to the usage of hybrid electric vehicles
(HEV), biofuel vehicles, hydrogen/fuel cell vehicles (FCV), electrical vehicles (EV),
and the like have become necessary.
[0004] Regarding these requirements, efforts have also made to improve gas mileage by mounting
a heat exchanger that recovers exhaust heat, that is, an exhaust heat recovery device
mainly in hybrid electric vehicles. In the exhaust heat recovery device, exhaust gas
heat is transferred to cooling water by means of a heat exchange, and heat energy
is recovered and reused; and as a result, the temperature of the cooling water is
increased. Thereby, performance for heating the inside of vehicles is improved, and
gas mileage performance is improved by shortening the time required for warming up
engines. The exhaust heat recovery devices are also referred to as exhaust heat recirculation
systems.
[0005] In addition, other efforts to install an exhaust gas recirculation apparatus that
recirculates exhaust gas have also been made. Examples of the exhaust gas recirculation
apparatuses include EGR coolers. In the EGR cooler, exhaust gas from engines is cooled
using engine cooling water or air, and then the cooled exhaust gas is returned to
the intake side and is re-combusted. Thereby, the combustion temperature is lowered,
and the amount of NOx which is harmful gas is decreased.
[0006] For heat exchange portions in the above-described exhaust heat recovery devices or
EGR coolers, a favorable heat efficiency is required, and a favorable thermal conductivity
is required. In addition, high corrosion resistance against exhaust gas condensate
water is required because the portions come into contact with exhaust gas. Particularly,
since engine cooling water flows through these parts, in the case where holes are
generated due to corrosion, there may be a risk of serious accidents. In addition,
materials being used have a thin sheet thickness in order to increase the heat exchange
efficiency. Therefore, materials having higher corrosion resistance than that of members
in the downstream portion of exhaust systems are required.
[0007] Conventionally, among members mainly including mufflers in the downstream portion
of exhaust systems, for portions particularly requiring corrosion resistance, a ferritic
stainless steel containing 17% or more of Cr such as SUS430LX, SUS436J1L, or SUS436L
has been used. For materials of exhaust heat recovery devices or EGR coolers, corrosion
resistance that is higher than or equal to that of the above-described ferritic stainless
steel is required.
[0008] In addition, EGR coolers are, generally, assembled by brazing, and thus parts being
used need to have high brazing properties (brazeability). Here, in order to improve
brazeability, the wettability of the surfaces is important. Ti is more easily oxidized
than Fe and Cr and Ti forms an oxide film with poor wettability on the surface. Therefore,
the amount of Ti is desirably set to be low. Furthermore, similar to Ti, Al forms
an oxide film with poor wettability on the surface. Recently, there has been a demand
for a steel in which the amount of Al as well as the amount of Ti is low. In addition,
since the surface roughness of a steel sheet also has a great influence on wettability,
it is also extremely important to control surface properties by controlling manufacturing
conditions.
[0009] In addition, when the temperature of a brazing thermal treatment is high, the temperature
reaches approximately 1.200°C, and, in this high-temperature environment, crystal
grains in a stainless steel grow and coarsen. Since the coarsening of crystal grains
has an influence on mechanical characteristics such as thermal fatigue and the like,
a stainless steel on which a brazing thermal treatment is carried out needs to have
characteristics in which crystal grains do not easily coarsen even at high temperatures.
[0010] As described above, a steel that is used in the EGR coolers needs to have high corrosion
resistance and favorable brazeability.
[0011] Patent Document 1 discloses an inexpensive ferritic stainless steel material which
is used as muffler-constituting members or water-warming device members that form
welded portions and has high corrosion resistance. This ferritic stainless steel material
contains C: 0.025% or less, Si: 2% or less, Mn: 1% or less, P: 0.045% or less, S:
0.01% or less, Cr: 16% to 25%, Al: less than 0.04%, and N: 0.025% or less, and further
contains one or more element selected from Ni: 1% or less, Cu: 1% or less, Mo: less
than 1%, Nb: 0.5% or less, Ti: 0.4% or less, and V: 0.5% or less, with a remainder
of Fe and inevitable impurities. The ferritic stainless steel material has an oxide
film in which the composition of an outermost layer contains a total amount of Si
and Cr of 15 atom% to 40 atom% and 5 atom% of Fe in terms of the atomic ratio including
oxygen on the surface, and the composition of the outermost layer is measured by an
X-ray photoelectron spectrometry (XPS).
[0012] Patent Document 2 discloses a ferritic stainless steel with high brazeability in
the case where the ferritic stainless steel is brazed in an environment of a high
temperature and a low oxygen partial pressure as is the case with Ni brazing and Cu
brazing. This ferritic stainless steel contains C: 0.03% or less, N: 0.05% or less,
C+N: 0.015% or more, Si: 0.02% to 1.5%, Mn: 0.02% to 2%, Cr: 10% to 22%, Nb: 0.03%
to 1%, and Al: 0.5% or less, with a remainder of Fe and inevitable impurities. Furthermore,
the ferritic stainless steel contains an amount of Ti that satisfies Expression: Ti-3N≤0.03
and Expression: 10(Ti-3N)+Al≤0.5 or further contains, as a substitute for a part of
Fe, one or more of Mo: 3% or less, Ni: 3% or less, Cu: 3% or less, V: 3% or less,
W: 5% or less, Ca: 0.002% or less, Mg: 0.002% or less, and B: 0.005% or less.
[0013] Patent Document 3 discloses a ferritic stainless steel for a automobile exhaust system
member having favorable resistance to initial rusting at a low cost without impairing
the intrinsic functions of automobile exhaust system members such as high-temperature
strength, resistance against scale spallation, formabiliy, corrosion resistance against
exhaust gas condensate water, and corrosion resistance against salt damage environments.
This ferritic stainless steel contains, by mass%, C: ≤0.0100%, Si: 0,05% to 0.80%,
Mn: ≤0.8%, P: ≤0.050%, S: ≤0.0030%, Cr: 11.5% to 13.5%, Ti: 0.05% to 0.50%, Al: ≤0.100%,
and N: ≤0.02% with a remainder of Fe and inevitable impurities. The number of inclusions
containing Ca per square millimeter of an arbitrary cross-section is less than 10,
and furthermore, preferably, the proportion of the number of Mn-based sulfides to
the total number of Ti-based sulfides and the Mn-based sulfides is 50% or less.
[0014] Patent Document 4 discloses a ferritic stainless steel having excellent localized
corrosion resistance. This ferritic stainless steel contains, by mass%, C: 0.030%
or less, N: 0.030% or less, Si: 0.30% or less, Mn: 0.30% or less, P: 0.040% or less,
S: 0.020% or less, Cr: 16% to 26%, Al: 0.015% to 0.5%, Ti: 0.05% to 0.50%, Nb: 0.05%
to 0.50%, and Mo: 0.5% to 3.0%, with a remainder of Fe and inevitable impurities.
When the ratio of the amount of Al to the amount of Si is represented by Al/Si, the
following expression (1) is satisfied.

[0015] Patent Document 5 discloses a ferritic stainless steel with high corrosion resistance.
This ferritic stainless steel contains, by mass%, C: 0.030% or less, N: 0.030% or
less, Si: 0.01% to 0.50%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less, Cr:
12% to 25%, Nb: 0.01% to 1.0%, V: 0.010% to 0.50%, Ti: 0.60% or less, and Al: 0.80%
or less, with a remainder of Fe and inevitable impurities. The following expression
(A) is satisfied, furthermore, polishing marks with an arithmetic average roughness
value Ra of the surface in a range of 0.35 µm to 5.0 µm are provided, and the color
difference L* value of the surface is 70 or more.

[0016] However, the inventions disclosed by Patent Documents 1 to 5 are not capable of having
both of excellent corrosion resistance against exhaust gas condensate water and excellent
brazeability.
PRIOR ART DOCUMENTS
Patent Documents
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0018] The present invention aims to provide a ferrite-based stainless steel (ferritic stainless
steel sheet) with high resistance to corrosiveness caused by exhaust gas and condensation
(corrosion resistance against exhaust gas condensate water) and high brazing properties
(brazeability) in environments in which the ferritic stainless steel is used for automobile
mufflers, exhaust heat recovery devices, EGR coolers, or the like, and a method for
manufacturing the same.
Means for Solving the Problem
[0019] The features of the present invention intended to solve the above-described problems
is as described below.
- (1) A ferritic stainless steel with high corrosion resistance against exhaust gas
condensate water and high brazeability, containing, by mass%:
C: 0.001% to 0.030%;
Si: 0.01% to 1.00%;
Mn: 0.01% to 2.00%;
P: 0.050% or less;
S: 0.0100% or less;
Cr: 11.0% to 30.0%;
Mo: 0.01 % to 3.00%;
Ti: 0.001% to 0.050%;
Al: 0.001% to 0.030%;
Nb: 0.010% to 1.000%; and
N: 0.050% or less,
with a remainder being Fe and inevitable impurities,
wherein an amount of Al, an amount of Ti, and an amount of Si (mass%) satisfy Al/Ti≥8.4Si-0.78.
- (2) The ferritic stainless steel with high corrosion resistance against exhaust gas
condensate water and high brazeability according to (1), further containing, by mass%,
any one or more of:
Ni: 0.01% to 3.00%;
Cu: 0.050% to 1.500%;
W: 0.010% to 1.000%;
V: 0.010% to 0.300%,
Sn: 0.005% to 0.500%,
Sb: 0.0050% to 0.5000%, and
Mg: 0.0001% to 0.0030%.
- (3) The ferritic stainless steel with high corrosion resistance against exhaust gas
condensate water and high brazeability according to (1) or (2), further containing,
by mass%, any one or more of:
B: 0.0002% to 0.0030%;
Ca: 0.0002% to 0.0100%;
Zr: 0.010% to 0.300%;
Co: 0.010% to 0.300%,
Ga: 0.0001% to 0.0100%,
Ta: 0.0001% to 0.0100%, and
REM: 0.001% to 0.200%.
- (4) The ferritic stainless steel with high corrosion resistance against exhaust gas
condensate water and high brazeability, according to any one of (1) to (3),
wherein, when a rolling direction is represented by an L direction, a direction perpendicular
to the rolling direction is represented by a C direction, a direction inclined at
45° with respect to the rolling direction is represented by a V direction, and arithmetic
average roughness values of a steel surface in the respective directions are respectively
represented by RaL, RaC, and RaV (unit: µm), (RaL+RaC+2RaV)/4≤0.50 and |(RaL+RaC-2RaV)/2|≤0.10 are satisfied.
- (5) The ferritic stainless steel with high corrosion resistance against exhaust gas
condensate water and high brazeability according to any one of (1) to (4), wherein
an amount of change in grain size number (GSN) before and after a thermal treatment
at 1.150°C for 10 minutes in a vacuum atmosphere of 50 Pa or lower is 5.0 or less.
- (6) The ferritic stainless steel with high corrosion resistance against exhaust gas
condensate water and high brazeability according to any one of (1) to (5) which is
used in automobile mufflers, exhaust heat recovery devices, and EGR coolers that are
automobile parts exposed to exhaust gas-condensate environments.
- (7) A method for manufacturing a ferritic stainless steel with high corrosion resistance
against exhaust gas condensate water and high brazeability, the method including:
a step of cold-rolling a steel having the chemical components according to any one
of (1) to (3), wherein, in the cold rolling step, in a final pass, the steel is rolled
using a roll with a roll roughness of #60 or more under conditions where a rolling
reduction in the final pass is set to 15.0% or less and a cold rolling speed in the
final pass is set to 800 m/min or less.
- (8) The method for manufacturing a ferritic stainless steel with high corrosion resistance
against exhaust gas condensate water and high brazeability according to (7), the method
further including: a step of annealing a cold-rolled steel sheet, wherein the annealing
step includes: a step of maintaining the steel sheet at a temperature of 650°C to
950°C for 5.0 s or longer; and a step of maintaining the steel sheet at a temperature
of 950°C to 1.050°C for 80.0 s or shorter.
Effects of the Invention
[0020] According to the present invention, it is possible to provide a ferritic stainless
steel with high corrosion resistance against exhaust gas condensate water and high
brazeability in the case where the ferritic stainless steel is used in automobile
parts exposed to exhaust gas-condensate environments (environments of exhaust gas
condensate water) such as automobile mufflers, exhaust heat recovery devices, EGR
coolers, or the like.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a view showing a relationship between the amounts of Si, Al, and Ti in
steel sheets and the results of the condensate water corrosion test.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
[0022] Hereinafter, embodiments of the present invention will be described in detail with
reference to the accompanying drawings.
[0023] In order to improve brazeability, the present inventors produced steels in which
the amount of Al or the amount of Ti was decreased to a variety of concentrations
under a variety of cold rolling conditions or a variety of annealing conditions of
cold-rolled sheets. Then, corrosion resistance, brazeability, surface roughness, and
an amount of change in crystal grain size before and after a brazing thermal treatment
were investigated. As a result, it was found that the brazeability is improved as
the concentration of Al or the concentration of Ti in a steel is decreased. However,
regarding improvement of corrosion resistance against exhaust gas condensate water,
no effects were developed in a method in which the concentration of Al or the concentration
of Ti in a steel was simply decreased. It has been found that, when the balance among
the concentration of Al, the concentration of Ti, and the concentration of Si is optimized,
brazeability is improved, and corrosion resistance against exhaust gas condensate
water is improved. Furthermore, detailed studies were made regarding geometric surface
properties having an influence on the spreading of brazing filler metal. As a result,
it was found that, in the case where the average values of surface roughness in a
rolling direction, a direction perpendicular to the rolling direction, and a direction
inclined at 45° with respect to the rolling direction are small, and the difference
between the surface roughness values is small, the brazeability is further improved.
In addition, it was found that the amount of change in crystal grain size before and
after a brazing thermal treatment is decreased by controlling the annealing conditions
of cold-rolled sheets and controlling the precipitation state of a Laves phase such
as Fe
2Nb and the like in a steel. Hereinafter, the study results by the inventors will be
described.
[0024] Since automobile mufflers, exhaust heat recovery devices, and exhaust gas recirculation
apparatuses such as EGR coolers are exposed to exhaust gas-condensate environments,
there is a demand for corrosion resistance, particularly, corrosion resistance against
exhaust gas condensate water (corrosion resistance against condensate water, resistance
to condensate water corrosion). The present researchers produced steel sheets with
a variety of compositions and carried out tests of corrosion resistance against condensate
water. The results are shown in FIG. 1 in which the horizontal axis indicates the
amount of Si in the steel sheet and the vertical axis indicates the amount ratio af
Al/Ti in the steel sheet (both by mass%). Regarding the determination standard in
the condensate water corrosion test, the maximum corrosion pit depth of 100 µm was
used as a boundary value, and 100 µm was the maximum corrosion pit depth of the sample
in which the notable growth of corrosion pits was confirmed under the test conditions
used in examples described below. A steel in which the maximum corrosion pit depth
was 100 µm or more was evaluated as C (bad) and plotted with a reference sign "X"
in FIG. 1. A steel in which the maximum corrosion pit depth was less than 100 µm was
evaluated as B (good) and plotted with a reference sign "O" in FIG. 1. The solid line
in FIG. 1 indicates Al/Ti=8.4Si-0.78.
[0025] From FIG. 1, it is found that, in the case where the amounts (mass%) of Al, Ti,
and Si in a steel does not satisfy the relationship of Al/Ti=8.4Si-0.78, corrosion
resistance against condensate water greatly degrades. From this result, it is found
that the amounts of Al, Ti, and Si desirably satisfy the relationship of Al/Ti=8.4Si-0.78.
[0026] As a result of investigating inclusions present in a steel which did not satisfy
the relationship of Al/Ti=8.4Si-0.78, it was found that, mainly, a Ti-based oxide
was present. On the other hand, it was found that inclusions present in a steel which
satisfied the relationship of Al/Ti-8.4Si-0.78 was mainly Al
2O
3-MgO. In addition, CaO-Al
2O
3 was present in a deformed form in the rolling direction so as to surround Al
2O
3.
[0027] Since the Ti-based oxide is a hard inclusion, the Ti-based oxide does not deform
together with the base material during cold rolling, and voids are likely to be formed
in the interfaces between the inclusions and the base material. The formed voids are
considered to serve as starting points of pitting corrosion and degrade the corrosion
resistance against condensate water of the steel.
[0028] Al
2O
3-MgO is also a hard inclusion, but it is considered that no voids are formed in the
interfaces between the inclusions and the base material due to the deformation of
CaO-Al
2O
3 in the rolling direction which is present in the vicinity of Al
2O
3-MgO, and the corrosion resistance against condensate water does not deteriorate.
[0029] In addition, Si increases the activity of Ti; and thereby, Si assists the generation
of the Ti-based oxide. Therefore, it is desirable to decrease the amount of Si in,
particularly, low-Al materials (materials with a small amount of Al).
[0030] As described above, when the relationship of Al/Ti=8.4Si-0.78 is satisfied, Al
2O
3-MgO inclusions which do not serve as starting points of corrosion are preferentially
generated. However, since Al, Ti, and Si are effective elements for deoxidation, in
the case where the amounts of these elements are decreased, there is a concern of
an increase in the concentration of O in the steel. In this case, Mg is added to perform
deoxidation; and thereby, the formation of oxides in the steel is inhibited, and furthermore,
it is possible to prevent the deterioration of corrosion resistance against condensate
water.
[0031] Meanwhile, in order to improve brazeability, it is necessary to decrease the amounts
of Al and Ti. Therefore, it is necessary to decrease the amounts of Al and Ti being
added to a molten steel. In the case where the added amount of Al is decreased, the
concentration of O in the molten steel increases, and the reaction of [S]+(CaO)→(CaS)+[O],
which is a desulfurization reaction, does not proceed. Therefore, it is necessary
to use low-S ferro chrome (with a small amount of S) as a raw material and decrease
the concentration of S in the molten steel in advance.
[0032] In addition, Table 1 shows the relationships between the cold rolling conditions
in the final pass and the arithmetic average roughness values in the respective directions
and the brazeability. Steel Nos. in Table I are the same as Steel Nos. in Tables 3A
to 3D shown below. Brazeability was evaluated as described below. 0.2 g of Ni brazing
filler metal was placed on the surface of a steel sheet produced by a method described
below and was heated at 1,200°C for ten minutes in a vacuum atmosphere of 5×10
-3 torr. Next, the test specimen was cooled to normal temperature, and the area of the
brazing filler metal (brazing filler metal area) in the heated test specimen was measured.
A steel in which the brazing filler metal area after heating was 2.5 times or more
the brazing filler metal area before heating was evaluated as A (excellent). A steel
in which the brazing filler metal area after heating was 2 times (twice) or more to
less than 2.5 times the brazing filler metal area before heating was evaluated as
B (good). A steel in which the brazing filler metal area after heating was less than
2 times (twice) the brazing filler metal area before heating was evaluated as C (bad).

[0033] From Table 1, it is found that, in the case where the following conditions (1) to
(3) are satisfied, either one or both of the absolute value of (Ra
L+Ra
c+2Ra
v)/4 and the absolute value of (Ra
L+Ra
C-2Ra
V)/2 decrease, and brazeability is improved.
- (1) The roughness of a roll being used in the final pass of cold rolling is set to
#60 or more.
- (2) The rolling reduction in the final pass is set to 15.0% or less.
- (3) The cold rolling speed in the final pass is set to 800 m/min or less.
[0034] Particularly, it is found that, in the case where (Ra
L+Ra
C+2Ra
V)/4≤0.50 and |(Ra
L+Ra
C-2Ra
V)/2|≤0.10 are satisfied, brazeability, is improved. Preferably, (Ra
L+Ra
C+2Ra
V)/4≤0.30 and |(Ra
L+Ra
C-2Ra
V)/2|≤0.05 are satisfied. The smaller the values of these indexes are, the more preferable
it is; and therefore, it is not necessary to provide the lower limit values of these
indexes. However, the lowest value of (Ra
L+Ra
c+2Ra
v)/4 which can be realistically achieved is 0.02, and the lowest value of |(Ra
L+Ra
C-2Ra
V)/2 which can be realistically achieved is 0.005.
[0035] It is known that surface roughness has an extremely great influence on wettability.
However, the surface of a stainless steel exhibits repellent against brazing filler
metal, and there have been a number of indefinite points regarding the relationship
between the two-dimensional surface properties of the surface of a stainless steel
sheet and brazing filler metal being used for brazing or the spreading properties
of brazing filler metal. As the surface of a stainless steel is roughened, the repellent
against brazing filler metal increases; and therefore, brazeability become poor. In
the present embodiment, it was found that a decrease in surface roughness in one direction
does not sufficiently improve the two-dimensional spreading of brazing filler metal
and the spreading properties of brazing filler metal can be extremely improved by
controlling roughness on a sheet surface in multiple directions.
[0036] That is, when the average value of roughness on a sheet surface (in-plane roughness)
is decreased and the difference in roughness on the sheet surface (in-plane roughness)
is decreased, the two-dimensional spreading of brazing filler metal becomes easy (the
brazing filler metal can easily spread in two-dimensional directions). Specifically,
(Ra
L+Ra
c+2Ra
v)/4 is an index indicating the average value of arithmetic average roughness values
in three directions, and |(Ra
L+Ra
C-2Ra
V)/2| is an index indicating the difference between arithmetic average roughness values
in three directions. Brazeability is improved by setting the average value of arithmetic
average roughness values in three directions to be 0.50 or less and setting the difference
between the arithmetic average roughness values in three directions to be 0.10 or
less.
[0037] As a method for decreasing the values of (Ra
L+Ra
C+2Ra
V)/4 and |(Ra
L+Ra
C-2Ra
V)/2|, there is a method for controlling the pass schedule of the cold rolling step
in a process for manufacturing a stainless steel sheet. In the cold rolling step of
a stainless steel sheet, generally, multi-pass rolling is carried out using a Sendzimir
rolling machine; and thereby, a stainless steel sheet with a predetermined sheet thickness
is manufactured. At this time, paraffinum liquidum or water-soluble oil is used as
a lubricant. In the present embodiment, the final pass is carried out under the above-described
conditions (1) to (3). That is, the final pass is carried out using a roll with a
roll roughness of #60 or more, the rolling reduction in the final pass is set to 15.0%
or less, and the cold rolling speed in the final pass is set to 800 m/min or less.
In such a case, preferred surface properties defined in the present embodiment are
realized. In the multi-pass rolling using a Sendzimir rolling machine, a flat surface
is formed by transferring cold rolling roll marks while eliminating defects (shot
blast flaws, intergranular corrosion grooves, pickling pits, and the like) on the
surface of a base material.
[0038] In the preferred surface properties defined in the present embodiment, the average
value of arithmetic average roughness values in three directions and the difference
between arithmetic average roughness values in three directions are smaller than predetermined
values. In the case where the surface of a roll being used in the final pass is rough,
the grinding marks of the roll are transferred, and the surface of a stainless steel
also becomes rough, and thus, in the final pass, a roll with a roughness of #60 or
more is used. The roll roughness is more desirably #80 or more. In the case where
the roll roughness is more than #1,000, further improvement of the effect cannot be
expected, and thus the roll roughness is desirably set to #1,000 or less.
[0039] In addition, when the rolling reduction in the final pass increases, the contact
arc length between the steel sheet in a roll caliber too! and the roll becomes long,
and thus it becomes difficult to discharge rolling oil from the roll caliber tool.
In the case where the rolling oil is not easily discharged, the rolling oil in the
roll caliber tool generates a hydrostatic pressure, and two-dimensional recesses are
likely to be generated on the surface of the steel sheet. Thereby, the values of (Ra
L+Ra
C+2Ra
V)/4 and |(Ra
L+Ra
C-2Ra
V)/2| are likely to increase. In addition, depending on the amount of rolling oil or
the surface properties of the original sheet, a galling phenomenon called heat scratches
occurs when the steel sheet is rolled at a high rolling reduction, and, conversely,
the surface roughness becomes rough. In the present embodiment, the occurrence of
heat scratches is prevented while accelerating the discharge of rolling oil in the
roll caliber tool. Thereby, the difference between roughness values in the respective
directions is decreased by decreasing the roughness values, particularly, in directions
other than the rolling direction. In order to achieve what has been described above,
the rolling reduction in the final pass is desirably set to 15.0% or less. The rolling
reduction in the final pass is more desirably 14.5% or less, and, when productivity
or steel sheet shapes are taken into account, the rolling reduction is desirably 10.0%
or more. The rolling reduction in the final pass is more desirably 12.0% or more.
[0040] Additionally, the rolling speed (cold rolling speed) in the final pass in the present
embodiment is desirably set to 800 m/min or less. In the inlet of the roll caliber
tool, the rolling oil remains in surface recesses that remain in the rolled material,
the oil is discharged in the roll caliber tool, and thus roll marks are transferred
to the steel sheet. However, in the case where the rolling speed is fast, sufficient
time is not obtained for discharging the oil, thus, recesses are insufficiently eliminated,
and it becomes difficult to decrease the roughness, particularly, at recess portions.
In order to sufficiently discharge the rolling oil in the recess portions, sufficiently
transfer a flat roll in a two-dimensional manner, and reduce the anisotropy of roughness,
the cold rolling speed in the final pass is desirably set to 800 m/min or less. The
cold rolling speed in the final pass is more desirably 600 m/min or less and still
more desirably 500 m/min or less. When productivity, steel sheet shapes, and surface
gloss are taken into account, the cold rolling speed in the final pass is desirably
150 m/min or more.
[0041] Furthermore, other conditions in the cold rolling may be set in consideration of
the sheet thickness or surface finishing of products, and, in the case where steel
sheets are rolled in one direction using a tandem rolling machine which is an ordinary
steel rolling machine, the conditions in the present embodiment may be applied to
the final stand. In addition, the rolling oil may be paraffinum liquidum or water-soluble
oil.
[0042] Table 2 shows the annealing conditions of the cold-rolled sheets and grain size numbers
(GSN) before and after a brazing thermal treatment. Steel Nos. in Table 2 are the
same as Steel Nos. in Tables 3A to 3D shown below. The grain size number was evaluated
as described below. A steel sheet produced using a method described below was cut
so that a surface parallel to the rolling direction could be observed and was implanted
in a resin. The grain size number was measured using an optical microscope and a cutting
method.

[0043] From Table 2, it is found that, in the case where the steel sheet is maintained at
a temperature of 650°C to 950°C for shorter than 5.0 s or in the case where the steel
sheet is maintained at a temperature of 950°C to 1,050°C for longer than 80.0 s, the
amount of change in grain size number before and after the brazing thermal treatment
(the amount of a grain size number changed by the brazing thermal treatment) becomes
greater than 5.0. The great change of the grain size number before and after the brazing
thermal treatment leads to a great change in the mechanical properties of a stainless
steel before and after the brazing thermal treatment, and there is a fear of causing
an accident or the like of components, and thus it is desirable to avoid the great
change of the grain size number between before and after the brazing thermal treatment.
In the present embodiment, when an amount of change in grain size number before and
after the brazing thermal treatment is 5.0, the mechanical properties greatly change.
Therefore, the amount of change in grain size number before and after the brazing
thermal treatment is desirably decreased to 5.0 or less. The amount of change in grain
size number before and after the brazing thermal treatment is more desirably 4.0 or
less. Since the amount of change in grain size number before and after the brazing
thermal treatment is preferably low, it is not necessary to set the lower limit value.
However, since it is difficult to set the amount of change in grain size number to
zero, the lower limit value is desirably set to more than zero.
[0044] In the present embodiment, it was found that, when a Laves phase such as Fe
2Nb is finely precipitated in a steel, this phase serves as a pinning factor, and the
amount of change in grain size number before and after the brazing thermal treatment
decreases. The temperature at which the Laves phase is precipitated is 650°C to 950°C.
and the temperature at which the Laves phase dissolves is 950°C to 1,050°C. Therefore,
during the annealing of the cold-rolled sheet, it is necessary to maintain the cold-rolled
sheet in a temperature range of 650°C to 950°C for a long period of time and maintain
the cold-rolled sheet in a temperature range of 950°C to 1,050°C for a short period
of time. In the present embodiment, the annealing step preferably includes a step
of maintaining the steel sheet at a temperature of 650°C to 950°C for 5.0 s or longer
and a step of maintaining the steel sheet at a temperature of 950°C to 1,050°C for
80.0 s or shorter. It was found that, in such a case, it becomes possible to sufficiently
precipitate the fine Laves phase which is effective for pinning crystal grains. The
annealing step more desirably includes a step of maintaining the steel sheet at a
temperature of 650°C to 950°C for 8.0 s (seconds) or longer and a step of maintaining
the steel sheet at a temperature of 950°C to 1.050°C for 60.0 s (seconds) or shorter.
In addition, when productivity is taken into account, the holding time during which
the steel sheet is maintained at a temperature of 650°C to 950°C is preferably 50
s or shorter. When the appropriate recrystallization of the structure after cold rolling
is taken into account, the holding time during which the steel sheet is maintained
at a temperature of 950°C to 1,050°C is preferably 10 s or longer.
[0045] Hereinafter, the chemical composition of a steel defined in the present embodiment
will be described in more detail. Meanwhile, "%" indicates "mass%".
[0046] C: Since C degrades intergranular corrosion resistance and workability, it is necessary
to decrease the amount of C at a low level. Therefore, the amount of C is set to 0.030%.
However, an excessively low amount of C assists the coarsening of crystal grains during
brazing and increases refinement costs, and thus the amount of C is desirably set
to 0.001 % or more. The amount of C is more desirably 0.004% to 0.020%.
[0047] Si: Si is a useful deoxidation element, but Si increases the activity of Ti; and
thereby, Si assists the generation of a hard Ti-based oxide. Therefore, the amount
of Si is set to 0.01 % to 1.00%. The amount of Si is more desirably 0.10% to 0.60%.
[0048] Mn: Mn is a useful deoxidation element, but in the case where an excess amount of
Mn is added, Mn deteriorates corrosion resistance, and thus the amount of Mn is set
to 0.01% to 2.00%. The amount of Mn is more desirably 0.10% to 1.00%.
[0049] P: P is an element that deteriorates workability and weldability, and thus it is
necessary to limit the amount of P. Therefore, the amount of P is set to 0.050% or
less. The amount of P is more desirably set to 0.030% or less.
[0050] S: S is an element that deteriorates corrosion resistance, and thus it is necessary
to limit the amount of S. Therefor, the amount of S is set to 0.0100% or less. The
amount of S is more desirably set to 0.0050% or less.
[0051] Cr: Examples of possible corrosive environments include atmospheric environments,
cooling water environments, exhaust gas-condensate environments, and the like. In
order to ensure corrosion resistance in the above-described environments, at least
11.0% or more of Cr is required. As the amount of Cr is increased, the corrosion resistance
is improved, but the workability and manufacturability are degraded, and thus the
amount of Cr is set to 30.0% or less. The amount of Cr is more desirably 15.0% to
23.0%.
[0052] Mo: In order to improve corrosion resistance against condensate water, 0.01% or more
of Mo is required. However, in the case where an excess amount of Mo is added, workability
is degraded and costs are increased due to the expensive price of Mn, and thus the
amount of Mo is set to 3.00% or less. The amount of Mo is more desirably 0.10% to
2.50%.
[0053] Ti: Ti forms an oxide film with poor wettability on the surface and degrades brazeability.
Therefore, the amount of Ti is set to 0.001% to 0.050%. The amount of Ti is more desirably
0.001% to 0.030%.
[0054] Al: Al has a deoxidation effect or the like, Al is a useful element for refinement,
and Al has an effect of improving moldability. In order to stably obtain these effects,
0.001 % or more of Al is preferably included. However, in the case where a large amount
of Al is included, an oxide film with poor wettability is formed on the surface, and
brazeability is impaired. Therefore, the amount of Al is set to 0.030% or less. The
amount of Al is more desirably 0.001% to 0.015%.
[0055] Nb: Since carbonitrides of Nb prevents the coarsening of crystal grains due to heating
during brazing and thus a decrease in the strength of members is prevented, Nb is
an important element. In addition, Nb is useful for improving high-temperature strength
or improving the intergranular corrosion resistance of welded portions, but in the
case where an excess amount of Nb is added, workability or manufacturability is degraded,
and thus the amount of Nb is set to 0.010% to 1.000%. The amount of Nb is more desirably
0.100% to 0.600%.
[0056] O: O is an element that is inevitably included in a stainless steel. In the present
embodiment, it is not necessary to particularly limit the amount of O. However, when
O is present in the base material of a stainless steel, there is a possibility that
O causes the formation of inclusions such as oxides and degrades a variety of characteristics
such as ductility or corrosion resistance. Therefore, the amount of O is desirably
decreased to be 0.020% or less. The amount of O is more desirably 0.010% or less.
[0057] N: N is a useful element for pitting corrosion resistance, but N degrades intergranular
corrosion resistance and workability, and thus it is necessary to decrease the amount
of N at a low level. Therefore, the amount of N is set to 0.050% or less. The amounts
of N is more desirably 0.030% or less.
[0058] What has been described above is the chemical composition which serves as the basic
of the ferritic stainless steel of the present embodiment; however, in the present
embodiment, the ferritic stainless steel may further include the following elements
as necessary.
[0059] Ni: In order to improve corrosion resistance, 3.00% or less of Ni may be included.
In order to stably obtain the effects, the amount of Ni needs to be 0.01% or more.
The amount of Ni is more desirably 0.05% to 2.00%.
[0060] Cu: In order to improve corrosion resistance. 1.500% or less of Cu may be included.
In order to stably obtain the effects, the amount ofCu needs to be 0.050% or more.
The amount of Cu is more desirably 0.100% to 1.000%.
[0061] W: In order to improve corrosion resistance, 1.000% or less of W may be included.
In order to stably obtain the effects, the amount of W needs to be 0.010% or more.
The amount of W is more desirably 0.020% to 0.800%.
[0062] V: In order to improve corrosion resistance, 0.300% or less of V may be included.
In order to stably obtain the effects, the amount of V needs to be 0.010% or more.
The amount of V is more desirably 0.020% to 0.050%.
[0063] Sn: In order to improve corrosion resistance, 0.500% or less of Sn may be included.
In the case where Sn is included, the amount of Sn is desirably 0.005% or more at
which the effects can be obtained stably. The amount of Sn is more desirably 0.01%
to 0.300%.
[0064] Sb: In order to improve general corrosion resistance, 0.5000% or less of Sb may be
included. In the case where Sb is included, the amount of Sb is desirably 0.0050%
or more at which the effects can be obtained stably. The amount of Sb is more desirably
0.0100% to 0.3000%.
[0065] Mg: Mg has a deoxidation effect or the like and is a useful element for refinement.
In addition, Mg minimizes the structure and Mg is also useful for improving workability
and toughness, and 0.0030% or less of Mg may be included as necessary. In the case
where Mg is included, the amount of Mg is desirably 0.0001% or more at which the effects
can be obtained stably. The amount of Mg is more desirably 0.0001% to 0.001%.
[0066] Meanwhile, the total amount of one or more of Ni, Cu, W, V, Sn, Sb, and Mg is desirably
6% or less from the viewpoint of an increase in costs.
[0067] B: B is a useful element for improving secondary workability, and 0.0030% or less
of B may be included. In the case where B is included, the amount of B is desirably
0.0002% or more at which the effects can be obtained stably. The amount of B is more
desirably 0.0005% to 0.0010%.
[0068] Ca: Ca is added in order for desulfurization, but in the case where an excess amount
of Ca is added, a water-insoluble inclusion CaS is generated and corrosion resistance
is degraded. Therefore, 0.0002% to 0.0100% of Ca may be added. The amount of Ca is
more desirably 0.0002% to 0.0050%.
[0069] Zr: In order to improve corrosion resistance, 0.300% or less of Zr may be included
as necessary. In the case where Zr is included, the amount of Zr is desirably 0.010%
or more at which the effects can be obtained stably. The amount of Zr is more desirably
0.020% to 0.200%.
[0070] Co: In order to improve secondary workability and toughness, 0.300% or less of Co
may be included as necessary. In the case where Co is included, the amount of Co is
desirably 0.010% or more at which the effects can be obtained stably. The amount of
Co is more desirably 0.020% to 0.200%.
[0071] Ga: In order to improve corrosion resistance and hydrogen embrittlement resistance,
0.0100% or less of Ga may be included as necessary. In the case where Ga is included,
the amount of Ga is desirably 0.0001% or more at which the effects can be obtained
stably. The amount of Ga is more desirably 0.0005% to 0.0050%.
[0072] Ta: In order to improve corrosion resistance, 0.0100% or less of Ta may be included
as necessary. In the case where Ta is included, the amount of Ta is desirably 0.0001%
or more at which the effects can be obtained stably. The amount of Ta is more desirably
0.0005% to 0.0050%.
[0073] REM: Since REM has a deoxidation effect or the like, REM is a useful element for
refinement, and 0.200% or less of REM may be included as necessary. In the case where
REM is included, the amount of REM is desirably 0.001% or more at which the effects
can be obtained stably. The amount of REM is more desirably 0.002% to 0.100%.
[0074] Here, rare earth elements (REM) refer to, according to the ordinary definition, two
elements of scandium (Sc) and yttrium (Y) and fifteen (lanthanoid) elements from lanthanum
(La) to lutetium (Lu). REM is one or more elements selected from these rare earth
elements, and the amount of REM refers to the total amount of rare earth elements.
[0075] In a manufacturing method of the present embodiment, basically, an ordinary method
for manufacturing a steel sheet made of a ferritic stainless steel is applied. For
example, molten steel having the above-described chemical composition is produced
using a converter or an electric furnace and is refined using an AOD furnace, a VOD
furnace, or the like. After that, a slab is produced using a continuous casting method
or an ingot casting method and then the slab is subjected to steps of hot rolling,
annealing of hot-rolled sheets, pickling, cold rolling, finishing annealing, and pickling;
and thereby, the ferritic stainless steel of the present embodiment is manufactured.
The annealing of hot-rolled sheets may not be carried out as necessary. The cold rolling,
the finishing annealing, and the pickling may be repeated.
[0076] However, as described above, in the cold rolling step, in order to control the surface
roughness, steel sheets are desirably rolled using a roll with a roll roughness of
#60 or more in the final pass under conditions in which the rolling reduction in the
final pass is set to 15.0% or less and the cold rolling speed in the final pass is
set to 800 m/min or less. In addition, in order to precipitate the Laves phase such
as Fe
2Nb in steel, the annealing step of the cold-rolled sheet desirably includes a step
of maintaining the steel sheet at a temperature of 650°C to 950°C for 5.0 s or longer
and a step of maintaining the steel sheet at a temperature of 950°C to 1,050°C for
80.0 s or shorter. That is, in the annealing step, it is desirable to set the holding
time during which the steel sheet is maintained at a temperature of 650°C to 950°C
to 5.0 s or longer and set the holding time during which the steel sheet is maintained
at a temperature of 950°C to 1,050°C to 80.0 s or shorter.
EXAMPLES
[0077] The present invention will be described in more detail using examples.
[0078] Steels with a composition shown in Tables 3A and 3B was produced, the steels were
subjected to hot rolling to a sheet thickness of 4 mm, the steels were annealed at
1,050°C for one minute, and then the steels were pickled. After that, the steels were
ere subjected to cold rolling to a sheet thickness of 1 mm. Particularly, the cold
rolling was carried out under conditions where the roll roughness in the final pass
of cold rolling, the rolling reduction, and the cold rolling speed were set to the
values as shown in Table 3C. In the annealing of cold-rolled sheets, the holding time
at a temperature of 650°C to 950°C and the holding time at a temperature of 950°C
to 1,050°C were respectively controlled as shown in Table 3C.
[0079] After that, test specimens with a 100 mm width and a 100 mm length were cut out from
the produced steel sheets. The arithmetic average roughness values of the steel surface
in the respective directions of the rolling direction (L direction), the direction
perpendicular to the rolling direction (C direction), and the direction inclined at
45° with respect to the rolling direction (V direction) were measured using a surface
roughness and shape measurement instrument. The measurement length was set to 4.0
mm, the measurement speed was set to 0.30 mm/s, and the cut-off length was set to
0.8 mm. In each of the directions, the average value of three measurement results
was used as the arithmetic average roughness value in that direction.
[0080] In addition, the produced steel sheets were cut so that a surface parallel to the
rolling direction could be observed and were implanted in a resin. The grain size
number (GSN) was measured using the cutting method.
[0081] In addition, test specimens with a 60 mm width and a 100 mm length were cut out from
the produced steel sheets, and Ni brazing filler metal (0.2 g) was placed on the surface
of each of the test specimens and was heated at 1,200°C for ten minutes in a vacuum
atmosphere of 5×10
-3 torr. Next, the test specimen was cooled to normal temperature, and an area of the
brazing filler metal (brazing filler metal area) on the surface of the test specimen
after heating was measured. Test specimens in which the brazing filler metal area
after heating was 2.5 times or more the brazing filler metal area before heating was
evaluated as A (excellent). Test specimens in which the brazing filler metal area
after heating was 2 times (twice) or more to less than 2.5 times the brazing filler
metal area before heating was evaluated as B (good). Test specimens in which the brazing
filler metal area after heating was less than 2 times (twice) the brazing filler metal
area before heating was evaluated as C (bad). After that, the steel sheets which had
been subjected to a brazing thermal treatment were cut so that a surface parallel
to the rolling direction could be observed and were implanted in a resin. The grain
size number (GSN) was measured using the cutting method.
[0082] In addition, test specimens with a 25 mm width and a 100 mm length were cut out from
the cold-rolled steel sheets, and then all the surfaces of the test specimens were
wet-polished using Emery paper of up to #600. These test specimens were evaluated
by half-immersion tests.
[0083] Imitation condensate water used in the half-immersion tests was produced as described
below. An aqueous solution containing 300 ppm of Cl
-, 1,000 ppm of SO
42-, and 1,000 ppm of SO
32- was produced using hydrochloric acid, sulfuric acid, and ammonium sulfite as reagents.
After the addition of the reagents, the pH was adjusted to 2.0 using ammonia water;
and thereby the imitation condensate water was obtained. A jig was adjusted so that
approximately half of the test specimen was immersed in the imitation condensate water
at an angle of 55°. The half of the test specimen was immersed in the imitation condensate
water using this jig, and the imitation condensate water was heated to 80°C. The test
was carried out for 168 hours, and the solution was renewed everyday on week days.
[0084] For corrosion evaluation, the maximum corrosion pit depth was used. After the end
of the tests, the corroded product was removed using an aqueous solution of di-ammonium
hydrogen citrate, and the depth of the position in which the test specimen was corroded
deepest was measured using a focal depth method. With regard to the determination
standard in the half-immersion tests, it was confirmed that growth of corrosion pits
became significant under these test conditions in the case where the maximum corrosion
pit depth was 100 µm. Therefore, 100 µm was used as the boundary value. A steel in
which the maximum corrosion pit depth was less than 100 µm was evaluated as B (good).
A steel in which the maximum corrosion pit depth was 100 µm or more was evaluated
as C (bad).
[0086] The test results are shown in Tables 3D and 3E. It is found from Table 3 D that steels
of Invention Examples were excellent in terms of brazeability and corrosion resistance
against condensate water. In addition, it is found from Table 3E that, in the case
where the amounts of components were outside the ranges of the present embodiment,
the corrosion resistance against condensate water deteriorated except for cases in
which the amount of Al or Ti was outside the range of the present embodiment. It is
found that, in the case where the amount of Al or Ti was outside the range of the
present embodiment, brazeability became poor. In addition, it is found that, even
when the amounts of the respective components were within the ranges of the present
embodiment, in the case where the amounts of Al, Ti, and Si did not satisfy the relationship
of Al/Ti=8.4Si-0.78, a hard Ti-based oxide was generated in a steel, voids serving
as starting points of pitting corrosion were formed in the inclusion/base material
interfaces, and corrosion resistance against condensate water deteriorated.
[0087] In addition, in Steel Nos. A1 to A14, the roughness of a roll that was used in the
final cold rolling (the final pass of the cold rolling) was set to #60 or more, the
rolling reduction in the final pass was set to 15.0% or less, and the cold rolling
speed in the final pass P was set to 800 m/min or less. It is found that steels manufactured
under the above-described conditions satisfied both (Ra
L+Ra
C+2Ra
V)/4≤0.50 and |(Ra
L+Ra
C-2Ra
V)/2|≤0.10 and brazeability, became more favorable. In addition, in Steel Nos. A1 to
A14 of Invention Examples, in the annealing step of the cold-rolled sheets, the holding
time of the steel sheet at 650°C to 950°C was set to 5.0 s or longer, and the holding
time of the steel sheet at 950°C to 1,050°C was set to 80.0 s or shorter. It is found
that, in steels manufactured under the above-described conditions, the amount of change
in grain size number before and after the brazing thermal treatment became 5.0 or
less.
Industrial Applicability
[0088] The ferritic stainless steel with high corrosion resistance against exhaust gas condensate
water of the present invention is suitable as members that are used in exhaust gas
recirculation apparatuses such as automobile mufflers, exhaust heat recovery devices,
and exhaust gas recirculation (EGR) coolers.