BACKGROUND OF THE INVENTION
[0001] The present invention relates to a ferritic stainless steel material for use as automobile
exhaust gas passage components, in particular to a ferritic stainless steel material
for use as automobile exhaust gas passage components, which has excellent heat resistance
and low-temperature toughness favorable for exhaust gas upstream passage components
where the material temperature may be over 900°C or further over 950°C, for example,
exhaust manifolds, catalyst converters, front pipes and the like.
[0002] Heretofore, two typical ferritic steel species are used properly for automobile exhaust
gas passage components, depending on the service temperature range of the components.
One is a steel species such as typically SUS429 steel mainly applied to the components
of which the maximum ultimate temperature of the material may be on a level of 750°C;
and the other is a steel species such as typically SUS444 steel mainly applied to
the components of which the maximum ultimate temperature of the material may be on
a level of 850°C.
[0003] For satisfying the recent requirements for emission control and mileage regulation,
exhaust gas temperatures tend to be higher, and on the presumption that the material
temperature in exhaust gas passage upstream components may actually rise up to about
1000°C, the requirements for heat-resistant materials may be expected to increase
for those components. Conventional SUS444 steel (18Cr-2Mo-0.5Nb steel) would be difficult
to apply to the components that are exposed to such high temperatures. In order that
the materials are durable to use at such high temperatures, those merely having high
tensile strength at high temperatures are not enough and it is a matter of importance
that the 0.2 % yield strength of the materials at high temperature, which is an index
of the stress under which the materials begin to undergo plastic deformation, is high.
[0004] With the increase in various devices to be fitted in an engine room, the limitation
to the housing space for exhaust gas components is increasing more than before. Accordingly,
exhaust gas passage upstream components are required to have excellent workability
into various shapes. In particular, not only as plates but also as pipes, the components
are required to have excellent workability durable to severe working into complicated
shapes. Further, exhaust gas passage components are also required to have good low-temperature
toughness.
[0005] Heretofore, various ferritic stainless steels having improved heat resistance such
as those mentioned below have been developed and are being put into practical use.
[0006] Patent Reference 1 shows a ferritic stainless steel of which the composition and
the texture are so controlled that it may surely have a sufficient amount of solid
solution Nb so as to be durable to use in a temperature range over 900°C and may have
a tensile strength of 20 MPa at 950°C. However, this has no description relating to
0.2 % yield strength, and the durability of the steel in a case where the material
temperature has actually risen up to about 1000°C is not confirmed. In this, any special
consideration is not taken for thermal fatigue resistance and low-temperature toughness.
[0007] Patent Reference 2 shows a ferritic stainless steel having excellent high-temperature
strength at 900°C and having excellent low-temperature toughness. However, this has
no description relating to 0.2 % yield strength, and in this, the measures for sufficiently
securing the durability in a case where the material temperature has actually risen
up to 1000°C or so could not be said to be always satisfactory.
[0008] Patent Reference 3 describes a ferritic stainless steel having good high-temperature
strength at 950°C and good workability. However, this shows nothing relating to 0.2
% yield strength, and in this, it is not certain as to whether or not the material
could be actually durable to exposure to about 1000°C or so. No special consideration
is taken for low-temperature toughness.
[0009] Patent Reference 4 shows an Fe-Cr alloy of which the thermal expansion coefficient
is lowered. However, there is taken no intension of improving the high-temperature
strength of the material in a temperature range of about 1000°C or so.
[0010] Patent Reference 5 describes a ferritic stainless steel having excellent thermal
fatigue resistance and good low-temperature toughness. In this, however, the material
was evaluated for the high-temperature strength in terms of the 0.2 % yield strength
thereof at 600°C, and its durability is not clear in a case where the material temperature
has actually risen up to about 1000°C.
[0011] Patent Reference 6 shows a ferritic stainless steel for exhaust gas system components
to be used at a temperature of not lower than 700°C. Regarding high-temperature strength,
however, this shows only the tensile strength data of the material at 600°C and 850°C,
and it is not clear as to whether or not the material could be resistant to exposure
to temperatures of 1000°C or so. In addition, this has no description relating to
low-temperature toughness.
Patent Reference 1: JP 2959934
Patent Reference 2: JP 2696584
Patent Reference 3: JP 3468156
Patent Reference 4: JP 2005-206944A
Patent Reference 5: JP 2006-117985A
Patent Reference 6: JP 2000-303149A
[0012] A method capable of stably realizing a material that exhibits excellent durability
when used at a temperature over 900°C and satisfies both good low-temperature toughness
and good workability is not as yet established (see the above Patent References).
SUMMARY OF THE INVENTION
[0013] An object of the present invention is to provide a ferritic stainless steel material
for automobile exhaust gas passage components, which simultaneously satisfies 0.2
% yield strength at high temperature of 1000°C, thermal fatigue resistance, low-temperature
toughness and workability all on a high level and which, even when used under the
condition where the material temperature actually reaches a high-temperature range
of higher than 900°C and even higher than 950°C, still exhibits excellent durability.
[0014] To attain the object as above, the invention provides a ferritic stainless steel
material having excellent heat resistance and low-temperature toughness for automobile
exhaust gas passage components, which has a composition essentially containing, in
terms of % by mass, at most 0.03 % of C, at most 1 % of Si, from 0.6 to 2 % of Mn,
at most 3 % of Ni, from 10 to 25 % of Cr, from 0.3 to 0.7 % of Nb, from more than
1 to 2 % of Cu, from 1 to 2.5 % of Mo, from 1 to 2.5 % of W, at most 0.15 % of Al,
from 0.03 to 0.2 % of V, and at most 0.03 % of N, and optionally containing at least
one of Ti and Zr in an amount of less than 1 % in total, or further containing at
least one of B in an amount of at most 0.02 % and Co in an amount of at most 2 %,
or further containing at least one of REM (rare earth element) and Ca in an amount
of at most 0.1 % in total, with a balance of Fe and inevitable impurities, the composition
satisfying the following formulae (1) and (2), and which has a texture where the total
amount of Nb and Mo existing as a precipitation phase is at most 0.2 % by mass:

[0015] In the above formulae (1) and (2), the element code is substituted with the content
of the corresponding element expressed in terms of % by mass.
[0016] "Ferritic stainless steel material for automobile exhaust gas passage components"
means a steel material processed for final annealing under heat at a temperature higher
than 1000°C (for example, from 1050 to 1100°C) (this may be simply referred to as
"final annealing") in a process of producing automobile exhaust gas passage components.
For example, in case where a steel sheet is welded and formed intro a pipe, then shaped
and worked, and thereafter processed for final annealing, the pipe after the final
annealing corresponds to the ferritic stainless steel material for automobile exhaust
gas passage components as referred to herein. In case where a steel sheet is processed
for final annealing, the steel sheet after the final annealing, and the pipe, cylindrical
casing or the like obtained by further working the final annealed sheet correspond
to the ferritic stainless steel material for automobile exhaust gas passage components.
[0017] Of the above-mentioned steel materials, those for use for exhaust gas components
that are to be within a material temperature range over 900°C or further over 950°C
are especially preferred subjects in the invention.
[0018] According to the invention, there is provided a ferritic stainless steel material
for automobile exhaust gas passage components, which satisfies all the requirements
of high-temperature strength durable to exposure to high temperature of 1000°C, good
thermal fatigue resistance, good workability and good low-temperature toughness. The
material meets the recent tendency in the art toward elevated exhaust gas temperatures
and brings about an broadened latitude in planning exhaust gas passage upstream components.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] In the invention, it is important to increase the high-temperature strength (0.2
% yield strength) of the steel material at a level of 1000°C with keeping high the
high-temperature strength (0.2 % yield strength) thereof at a level of 600°C. It is
extremely effective to make the steel material have high strength both in the two
temperature ranges for keeping high the thermal fatigue resistance thereof. As a result
of various investigations, it is desirable that the 0.2 % yield strength at 600°C
and the 0.2 % yield strength at 1000°C of the steel material are both at least 1.5
times higher than the yield strength at the same temperatures of SUS444 steel. Concretely,
it is desirable that the 0.2 % yield strength at 600°C of the steel material is at
least 200 MPa and the 0.2 % yield strength at 1000°C thereof is at least 15 MPa. It
has been found that the material having such high-temperature strength characteristics
has good high-temperature fatigue resistance satisfactory for practical use when it
receives repeated temperature change between ordinary temperature and 1000°C or so
as automobile exhaust gas passage components.
[0020] In the invention, Cu is used for improving the high-temperature strength of the steel
material in a temperature range including 600°C (range of from about 500 to 800°C).
Specifically, when Cu is added to the steel material, an ε-Cu phase is precipitated
at a temperature of around 600°C, and this finely disperses in the matrix of the material
to thereby express a precipitation-reinforcing phenomenon. In order that the steel
material can keep the high-temperature strength (0.2 % yield strength) in the temperature
range higher by at least about 1.5 times than that of SUS444 steel, it is necessary
to take advantage of Nb and Mo solid solution reinforcement in addition to the precipitation
of the ε-Cu phase. As a result of various investigations, controlling the constitutive
ingredients in order that the content of Nb, Mo and Cu could satisfy the formula (1)
makes it possible to increase the high-temperature range of at most 800°C strength
of the steel material by at least about 1.5 times that of SUS444 steel.

[0021] In a temperature range over 800°C, solid solution of the ε-Cu phase is further promoted,
and the effect of Cu to enhance the high-temperature strength of the steel material
is weakened. In order to increase the high-temperature strength (0.2 % yield strength)
at 1000°C of the steel material by at least about 1.5 times that of SUS444 steel,
it is important to fully take advantage of the solid solution reinforcement with Nb
and Mo. As the solid solution of Cu is also effective for enhancing the high-temperature
strength, it is also utilized. As a result of various investigations, it has been
found that the constitutive ingredients must be controlled so as to satisfy the formula
(2).

[0022] The coefficient of Nb in formula (2) corresponds to the increase in the 0.2 % yield
strength (MPa) at 1000°C per 0.1 % by mass of Nb; and the coefficient of Mo and Cu
each correspond to the increase in the 0.2 % yield strength (MPa) at 1000°C per 1
% by mass of Nb and Cu, respectively.
[0023] However, in order to increase the 0.2 % yield strength of the steel material at high
temperature of 1000°C by at least about 1.5 times that of SUS444 steel, the composition
that satisfies the above formula (2) is not enough. More detailed investigations have
confirmed that, in particular, it is extremely important to make the steel material
have a metal texture in which the Nb and Mo precipitates are reduced as much as possible.
Concretely, after final annealing, the steel material must have a texture condition
in which the total amount of Nb and Mo existing as a precipitation phase therein is
at most 0.2 % by mass.
[0024] Not only for keeping the high-temperature strength of the steel material but also
for keeping well the workability, the low-temperature toughness and the weldability
thereof, it is extremely effective to make the steel material have the above-mentioned
texture condition after final annealing. In case where the amount of Nb or Mo added
is considerably large, the amount of the solid solution Mo or the solid solution Nb
can be sufficiently secured even when the total amount of Nb and Mo existing as a
precipitation phase is more than 0.2 % by mass, and the high-temperature strength
of the steel material at 1000°C could be increased owing to their solid solution reinforcement.
In this case, however, it is difficult to enhance both the low-temperature toughness
and the workability of the steel material.
[0025] "Total amount (% by mass) of Nb and Mo existing as a precipitation phase" can be
determined as follows: The residue of the precipitation phase as extracted out through
constant potential electrolysis in an water-free solvent electrolytic solution (SPEED
method) is analyzed for elementary quantification, and the total mass of Nb and Mo
in the residue is divided by the total mass of the dissolved matrix and the extracted
precipitation phase in electrolysis, and this is expressed as percentage.
[0026] For obtaining the texture condition where the total amount of Nb and Mo existing
as a precipitation phase is at most 0.2 % by mass, the cooling rate from 1050°C to
500°C in the cooling step in the final annealing must be controlled to at least 5°C/sec.
For example, in case where a pipe produced by welding is applied to automobile exhaust
gas passage components, a steel sheet before formed into a pipe, or after formed into
a pipe but before used as the component, may be processed at least once for final
annealing that comprises soaking under heat at 1050 to 1100°C for from 0 to 10 minutes
followed by cooling from 1050°C to 500°C at a cooling rate of at least 5°C/sec. Insofar
as the steel material is processed once to thereby have the texture condition as above
before used as an automobile exhaust gas passage component, any superfluous precipitation
phase of Nb and Mo would not form when the automobile exhaust gas passage component
formed of the steel material is used under heat at a temperature of 1000°C or so,
and practically, therefore, the high-temperature strength and the low-temperature
toughness of the steel material would not worsen.
[0027] The alloying ingredients are described below.
[0028] C and N are generally effective for improving creep strength and other high-temperature
strength properties but degrade oxidation resistant property, workability, low-temperature
toughness and weldability when contained in excess. In the invention, both C and N
are limited to a content of at most 0.03 % by mass.
[0029] Si is effective for improving high-temperature oxidation resistance. However, when
added in excess, it increases hardness and thus degrades workability and low-temperature
toughness. In the invention, the Si content is limited to at most 1 % by mass.
[0030] Mn improves high-temperature oxidation resistance, especially scale peeling resistance.
In order to sufficiently secure high-temperature oxidation resistance on a level of
1000°C, the Mn content must be at least 0.6 % by mass. However, Mn impairs workability
and weldability when added in excess. Further, Mn is an austenite-stabilizing element
that when added in a large amount facilitates martensite phase formation and thus
causes a decline in thermal fatigue resistance and workability. The Mn content is
therefore limited to at most 2 % by mass, preferably at most 1.5 % by mass, more preferably
less than 1.5 % by mass.
[0031] Ni contributes to improvement of low-temperature toughness, but when added too much,
it may lower cold elongation. In the invention, the acceptable Ni content is up to
3 % by mass, but more preferably, the Ni content is at most 0.6 % by mass.
[0032] Cr stabilizes ferrite phase and contributes to improvement of oxidation resistance,
an important property of high-temperature materials. In the invention, the Cr content
is secured to be at least 15 % by mass for sufficiently exhibiting its effect. However,
too much Cr makes the steel material brittle and worsens the workability thereof,
and therefore the Cr content is not more than 25 % by mass.
[0033] Nb is effective for increasing high-temperature strength in a temperature range of
around 600°C or so by solid solution reinforcement, but the invention takes advantage
of the solid solution reinforcing effect of Nb for securing high-temperature strength
in a high temperature range of higher than 900°C. For this, the Nb content must be
at least 0.3 % by mass, and it must satisfy the above-mentioned formula (2). In addition,
as so mentioned in the above, the invention must secure the steel texture condition
where the total amount of Nb and Mo existing as a precipitation phase is at most 0.2
% by mass. In this connection, Nb has a strong affinity for C and N, therefore readily
forming precipitates that may lower high-temperature strength, low-temperature toughness,
workability and other properties. Accordingly, the Nb content is limited to at most
0.7 % by mass.
[0034] Cu is an important element in the invention. Specifically, as so mentioned in the
above, the invention takes advantage of the fine dispersion precipitation phenomenon
of the ε-Cu phase of the steel material to thereby enhance the strength thereof at
around 600°C (from about 500 to 850°C) and to improve the thermal fatigue resistance
thereof. In a high temperature range over 850°C, Cu further plays a role of assisting
the high-temperature strength-enhancing effect of Nb and Mo, based on the solid solution
enhancement with Cu. As a result of various studies, the Cu content must be at least
more than 1 % by mass for satisfactorily attaining these effects. However, too much
Cu worsens workability, low-temperature toughness and weldability, and therefore the
uppermost limit of the Cu content is limited to 2 % by mass.
[0035] Mo, like Nb, is effective for increasing high temperature strength by solid solution
reinforcement. Especially in the invention, the high temperature strength in a high
temperature range over 900°C must be increased, and Mo addition in an amount of at
least 1 % by mass is indispensable. As so mentioned in the above, the invention must
secure the steel texture condition where the total amount of Nb and Mo existing as
a precipitation phase is at most 0.2 % by mass. Excess Mo addition may result in formation
of carbide and Laves phase (Fe
2Mo), thereby impairing high temperature strength and low-temperature toughness. Accordingly,
the Mo content is limited to at most 2.5 % by mass.
[0036] W is an element effective for increasing high temperature strength in a high temperature
range over 900°C, and in the invention, the W content must be at least 1 % by mass.
However, excess W addition impairs workability, and therefore, the W content must
be at most 2.5 % by mass, more preferably at most 2 % by mass.
[0037] Al is used as a deoxidizer in a steel making, and acts for improving high temperature
oxidation resistance. However, too much Al addition has negative influences on surface
properties, workability, weldability and low-temperature toughness. Accordingly, Al
is added within a range of at most 0.15 % by mass.
[0038] V contributes to improvement of high-temperature strength when added in combination
with Nb and Cu. When existing along with Nb, V improves workability, low-temperature
toughness, resistance to grain boundary corrosion susceptibility, and toughness of
weld heat affected zone In order to sufficiently attain all these effects, V is added
in the invention in an amount of at least 0.03 % by mass. However, excessive addition
of V impairs workability and low-temperature toughness. Accordingly, the V content
is limited to at most 0.2 % by mass.
[0039] Ti and Zr are elements effective for improving high-temperature strength; and if
desired, at least one of these may be added. However, excessive addition impairs toughness.
In case where at least one of Ti and Zr is added, the total content thereof must be
less than 1 % by mass.
[0040] B and Co, like Ni, are elements contributing to low-temperature toughness. If desired,
one or two of B and Co may be added. However, excessive addition lowers cold elongation;
and therefore, the B content is at most 0.02 % by mass and the Co content is at most
2 % by mass. More effectively, the B content is from 0.0005 to 0.02 % by mass.
[0041] REM (rare earth element) and Ca are elements that contribute to high-temperature
oxidation resistance. If desired, at least one of these may be added. More effectively,
the total content of REM and Ca is at least 0.001 % by mass. However, excessive addition
thereof may have some negative influences on producibility, and therefore, the total
content of REM and Ca is limited to at most 0.1 % by mass.
[0042] The stainless steel material of the invention may be produced by preparing a stainless
steel having a controlled composition as above according to an ordinary steel melting
method, then working it into a steel sheet having a predetermined thickness according
to an ordinary stainless steel sheet producing method, thereafter welding it into
a pipe, or shaping and further working it. In this process, in the final annealing
step where the steel is heated at 1050 to 1100°C, it is important to cool the steel
from 1050°C to 500°C at a controlled cooling rate of at least 5°C/sec as so mentioned
in the above. Overstepping the cooling condition, the steel could hardly have a texture
condition where the total amount of Nb and Mo existing as a precipitation phase is
at most 0.2 % by mass, and it may be difficult to enhance the high-temperature strength
(0.2 % yield strength) of the steel material at 1000°C stably on a level of at least
about 1.5 times that of SUS444. Under the condition, in addition, the low-temperature
toughness of the steel material may also be lowered.
EXAMPLES
[0043] Ferritic stainless steels shown in Table 1 were produced according to a steel melting
method, and then worked into cold-rolled annealed steel sheets having a thickness
of 2 mm according to a process of hot rolling, annealing of hot-rolled sheets, cold
rolling and final annealing. The final annealing was attained under the condition
as simulated for final annealing of steel materials for exhaust gas passage components.
The final annealing condition was as follows: After heated at 1050°C with soaking
for 1 minute, the steels except some comparative samples (such as No. 21) were cooled
from 1000°C to 500°C at a mean cooling rate of at least 5°C/sec. The cooling rate
was monitored with a thermocouple attached to the surface of each sample. Samples
of the cold-rolled annealed steel sheets thus obtained after the final annealing were
tested and analyzed for various properties of exhaust gas passage components.
Table 1
| Steel No. |
Chemical Ingredients (mass%) |
Left Side of Formula (1) |
Left Side of Formula (2) |
| C |
Si |
Mn |
Ni |
Cr |
Mo |
Nb |
Cu |
W |
Al |
V |
N |
Others |
| Invention Steels |
1 |
0.005 |
0.19 |
0.65 |
0.02 |
17.8 |
1.35 |
0.47 |
1.68 |
1.55 |
0.04 |
0.04 |
0.009 |
|
17.39 |
10.59 |
| 2 |
0.006 |
0.25 |
0.60 |
0.01 |
18.2 |
1.65 |
0.56 |
1.05 |
1.25 |
0.05 |
0.04 |
0.010 |
|
15.22 |
12.23 |
| 3 |
0.007 |
0.16 |
0.79 |
0.02 |
16.5 |
1.55 |
0.56 |
1.06 |
1.59 |
0.01 |
0.05 |
0.012 |
|
14.78 |
12.03 |
| 4 |
0.010 |
0.14 |
0.80 |
0.02 |
24.7 |
1.98 |
0.43 |
1.54 |
1.84 |
0.01 |
0.04 |
0.009 |
|
19.66 |
11.18 |
| 5 |
0.008 |
0.08 |
1.12 |
0.02 |
18.0 |
2.06 |
0.39 |
1.48 |
1.51 |
0.02 |
0.05 |
0.008 |
Ti:0.08 |
19.65 |
10.71 |
| 6 |
0.006 |
0.09 |
1.16 |
0.02 |
20.4 |
2.45 |
0.45 |
1.45 |
1.78 |
0.02 |
0.12 |
0.012 |
Zr:0.09 |
21.49 |
12.38 |
| 7 |
0.007 |
0.12 |
1.25 |
0.01 |
22.5 |
1.36 |
0.65 |
1.39 |
1.97 |
0.03 |
0.04 |
0.016 |
|
15.92 |
13.17 |
| 8 |
0.009 |
0.06 |
1.35 |
0.02 |
20.9 |
2.03 |
0.69 |
1.88 |
1.48 |
0.03 |
0.06 |
0.012 |
REM:0.04,Ca0.01 |
22.26 |
15.35 |
| 9 |
0.010 |
0.06 |
0.77 |
0.03 |
15.9 |
2.05 |
0.45 |
1.79 |
1.66 |
0.04 |
0.05 |
0.008 |
Ti:0.15,Co:0.01 |
21.53 |
11.75 |
| 10 |
0.010 |
0.08 |
0.60 |
0.01 |
18.8 |
2.16 |
0.35 |
1.95 |
1.74 |
0.04 |
0.07 |
0.007 |
B:0.0012 |
22.92 |
10.55 |
| Comparati ve Steels |
21 |
0.006 |
0.06 |
0.75 |
0.02 |
18.5 |
1.22 |
0.55 |
1.40 |
1.88 |
0.03 |
0.07 |
0.011 |
|
15.16 |
11.39 |
| 22 |
0.009 |
0.12 |
0.51 |
0.02 |
16.5 |
0.21 |
0.19 |
1.46 |
2.04 |
0.02 |
0.05 |
0.012 |
Ti:0.15 |
10.04 |
4.00 |
| 23 |
0.005 |
0.24 |
1.12 |
0.01 |
17.2 |
0.88 |
0.22 |
0.68 |
2.16 |
0.01 |
0.04 |
0.009 |
|
8.74 |
5.40 |
| 24 |
0.005 |
0.29 |
1.18 |
0.01 |
18.9 |
1.55 |
0.58 |
2.25 |
2.55 |
0.03 |
0.06 |
0.008 |
|
21.95 |
12.93 |
| 25 |
0.009 |
0.06 |
0.69 |
0.01 |
20.4 |
1.30 |
0.69 |
0.42 |
0.18 |
0.04 |
0.11 |
0.009 |
|
9.85 |
13.16 |
| 26 |
0.007 |
0.12 |
0.48 |
0.02 |
19.2 |
1.45 |
0.41 |
2.08 |
0.00 |
0.01 |
0.06 |
0.012 |
|
20.22 |
10.09 |
| 27 |
0.008 |
0.19 |
0.75 |
0.02 |
2.04 |
2.55 |
0.12 |
1.88 |
0.88 |
0.02 |
0.04 |
0.016 |
|
24.17 |
7.84 |
| 28 |
0.008 |
0.06 |
0.69 |
0.03 |
22.9 |
1.68 |
0.79 |
1.12 |
1.24 |
0.02 |
0.03 |
0.015 |
|
16.07 |
15.77 |
| 29 |
0.008 |
0.08 |
0.56 |
0.02 |
24.8 |
2.30 |
0.71 |
0.78 |
1.84 |
0.02 |
0.05 |
0.008 |
B:0.0015 |
17.03 |
15.64 |
| 30 |
0.007 |
0.15 |
0.84 |
0.01 |
15.9 |
3.58 |
0.55 |
1.69 |
1.05 |
0.02 |
0.05 |
0.009 |
|
28.70 |
16.26 |
| Underlined: Outside the scope of the invention. |
[0044] The samples (after final annealing) were tested and analyzed for the total amount
of Nb and Mo existing as a precipitation phase therein (this is expressed as "amount
of precipitated Nb + precipitated Mo"), and the 0.2 % yield strength at 600°C, the
0.2 % yield strength at 1000°C, the low-temperature toughness and the cold workability
thereof in the manner mentioned below.
[Amount of precipitated Nb + precipitated Mo]
[0045] According to a SPEED method as mentioned above, a sample is tested though constant
potential electrolysis at a potential at which the matrix of the sample dissolves
but the precipitation phase thereof does not dissolve, and the residue of the extracted
precipitation phase is analyzed for elementary determination. The total mass of Nb
and Mo in the residue is divided by the total mass of the dissolved matrix and the
extracted precipitation phase in electrolysis, and this is expressed as percentage
of the amount of precipitated Nb + precipitated Mo. In the SPEED method, used is 10
% acetylacetone + 1 % tetramethylammonium chloride + methyl alcohol solution as a
water-free solvent.
[0.2 % yield strength at 600°C, 1000°C]
[0046] A test piece for tensile strength having a thickness of 2 mm (the pulling direction
of the sample is the same as the rolling direction thereof) is tested for tensile
strength at 600°C and tensile strength at 1000°C according to JIS G0567. Samples of
which the 0.2 % yield strength at 600°C is at least 200 MPa, corresponding to about
at least 1.5 times that of SUS444 steel, are good; and those of which the strength
is lower than it are not good. Samples of which the 0.2 % yield strength at 1000°C
is at least 15 MPa, corresponding to about at least 1.5 times that of SUS444 steel,
are good; and those of which the strength is lower than it are not good.
[Low-temperature toughness]
[0047] A V-notch Charpy impact test piece is cut out of a sample having a thickness of 2
mm (the direction in which the test piece is hit with a hammer is in parallel to the
rolling direction of the sample), and tested in a Charpy impact test at a pitch of
25°C within a range of from -75°C to 25°C according to JIS Z2242, thereby determining
the ductility-toughness transition temperature of the sample. Samples of which the
transition temperature is not higher than -25°C are rated G (good in point of the
low-temperature toughness); and those of which the transition temperature is higher
than -25°C are rated NG (not good in point of the low-temperature toughness).
[Cold workability]
[0048] Three tensile test pieces (JIS 13B) are cut out of a sample having a thickness of
2 mm in such a manner that the pulling direction thereof could be at an angle of 0°,
45° or 90° relative to the rolling direction thereof. According to JIS 2241, these
are tested for tensile strength at break (test times n = 3). The broken pieces are
butt-jointed, and the elongation at break (%) thereof is determined. According to
the following formula (3), the mean elongation EL
A of the sample is computed, and this EL
A indicates the cold elongation of the tested sample.

[0049] In this, EL
L means the elongation at break of the sample at a pulling direction of 0° (mean value
of n = 3); EL
D means the elongation at break at a pulling direction of 45° (mean value of n = 3);
and EL
T means the elongation at break at a pulling direction of 90° (mean value of n = 3).
Samples having EL
A of at least 30 % are rated G (good in point of the cold workability); and those having
EL
A of smaller than 30 % are rated NG (not good in point of the cold workability).
[0050] The results are shown in Table 2. In Table 2, "cooling rate in final annealing" means
the mean cooling rate from 1050°C to 500°C.
Table 2
| Steel No. |
Cooling Rate in Final Annealing (°C/sec) |
Amount of Precipitated Nb + Precipitated Mo (mass%) |
0.2 % Yield Strength at 600°C (MPa) |
0.2 % Yield Strength at 1000°C (MPa) |
Low-Temperature Toughness |
Cold Work ability |
| Invention Steels |
1 |
15.2 |
0.02 |
230 |
15 |
G |
G |
| 2 |
10.4 |
0.20 |
221 |
17 |
G |
G |
| 3 |
8.2 |
0.16 |
220 |
17 |
G |
G |
| 4 |
11.2 |
0.18 |
254 |
16 |
G |
G |
| 5 |
8.6 |
0.05 |
231 |
19 |
G |
G |
| 6 |
10.1 |
0.06 |
249 |
20 |
G |
G |
| 7 |
10.6 |
0.04 |
230 |
22 |
G |
G |
| 8 |
5.6 |
0.05 |
269 |
23 |
G |
G |
| 9 |
11.2 |
0.06 |
248 |
20 |
G |
G |
| 10 |
11.5 |
0.04 |
264 |
21 |
G |
G |
| Comparative Steels |
21 |
4.8 |
0.25 |
204 |
13 |
NG |
NG |
| 22 |
5.8 |
0.02 |
164 |
8 |
G |
G |
| 23 |
10.2 |
0.06 |
176 |
10 |
G |
G |
| 24 |
10.5 |
0.16 |
226 |
16 |
G |
NG |
| 25 |
10.6 |
0.04 |
140 |
17 |
G |
G |
| 26 |
8.2 |
0.04 |
220 |
11 |
G |
G |
| 27 |
8.5 |
0.67 |
230 |
9 |
NG |
G |
| NG |
10.7 |
0.58 |
205 |
19 |
G |
NG |
| 29 |
11.5 |
1.20 |
150 |
17 |
NG |
G |
| 30 |
11.6 |
1.58 |
220 |
20 |
NG |
NG |
| Underlined: Outside the scope of the invention, or unsatisfactory in point of the
properties. |
[0051] The steel materials of the invention examples that satisfy the requirements for the
composition and the amount of precipitated Nb + precipitated Mo all had 0.2 % yield
strength at 600°C and 0.2 % yield strength at 1000°C both higher by at least about
1. 5 times than those of SUS444 steel, as known from Table 2; and accordingly, they
have excellent high-temperature strength in a high temperature range over 850°C, and
have sufficiently good thermal fatigue resistance. In addition, their low-temperature
toughness and cold workability are also good.
[0052] In contrast, No. 21 is not good, though its composition falls within the scope of
the invention. This is because the cooling rate from 1000°C to 500°C in the final
annealing was lower than 5°C/sec, and therefore a large amount of Nb and Mo precipitates
formed during the cooling step thereby giving a texture condition in which the amount
of precipitated Nb + precipitated Mo was too much. This comparative sample was poor
in the high-temperature strength at 1000°C, the low-temperature toughness and the
cold workability. In No. 22, the content of Mo and Nb was small; and in No. 23, the
Cu content was additionally small. Since these do not satisfy the formulas (1) and
(2), their high-temperature strength at 600°C and 1000°C was poor. In No. 24, the
W content was too much, and therefore, this was poor in the cold workability. In No.
25, the Cu content was low and this did not satisfy the formula (1), and the high-temperature
strength at 600°C of this comparative sample was poor. In No. 26, the Cu content was
too much, and this did not satisfy the formula (2). In addition, W was not added to
it, and therefore the high-temperature strength at 1000°C of the comparative sample
was low. In No. 27, the Mo content was too much, and in the texture thereof, the amount
of precipitated Nb + precipitated Mo was too much. Its Nb content was too low, and
this did not satisfy the formula (2). Its high-temperature strength at 1000°C and
its low-temperature toughness were poor. In No. 28, the Nb content was high, and in
the texture thereof, the amount of precipitated Nb + precipitated Mo was too much,
and its cold workability was poor. In No. 29, the content of Mo and Nb was high, and
in the texture thereof, the amount of precipitated Nb + precipitated Mo was too much,
and its low-temperature toughness was poor. In addition, since its Cu content was
small, its high-temperature strength at 600°C was low. In No. 30, the Mo content was
too high, and in the texture of thereof, the amount of precipitated Nb + precipitated
Mo was too much. However, owing to the solid solution of Mo therein, the high-temperature
strength at 1000°C of the comparative sample was high, but the low-temperature toughness
and the cold workability thereof were poor.