Technical Field
[0001] The present disclosure relates to steel material.
Background Art
[0002] In recent years, demand has urgently increased for improvement of the material properties
of various steel materials, such as thick steel plates to be used for large structures
such as offshore structures built in ice-bound seas, or bridges, and in addition to
the improvement of corrosion resistance, there is high demand for the improvement
of low-temperature toughness and fatigue characteristics.
[0003] Conventionally, an Sn-alloyed steel has been proposed in order to improve corrosion
resistance in a seawater environment.
[0004] For example, Japanese Patent Application Laid-Open (
JP-A) No. 2010-064110,
JP-A No. 2012-057236, and
JP-A No. 2012-255184 disclose steel materials in which corrosion resistance in an environment containing
chloride ions (Cl
- ions) is improved by the inclusion of Sn in amounts of from 0.005 to 0.3 mass%, from
0.02 to 0.40 mass%, and from 0.01 to 0.50 mass%, respectively.
[0005] Further,
JP-A No. 2012-144799 discloses a steel material for an offshore structure containing Sn in amount of from
0.03 to 0.5 mass%, and composed of ferrite and a hard second phase.
[0006] Further, Japanese Patent No.
5839151 discloses a technique for improving the corrosion resistance of steel by regulating
the Sn concentration ratio between a soft structure and a hard structure by dividing
water cooling into two stages.
SUMMARY OF INVENTION
Technical Problem
[0007] As described above, in order to improve corrosion resistance in a seawater environment
or the like, an Sn-alloyed steel has been proposed. However, in addition to improvement
of corrosion resistance by the addition of Sn, further improvement of mechanical properties,
especially toughness and fatigue characteristics, is required.
[0008] For example, with respect to the inventions of
JP-A Nos. 2010-064110,
2012-057236, and
2012-255184, which disclose improvement of corrosion resistance by the addition of Sn, there
remains room for further improvement in terms of toughness and fatigue characteristics,
and a technique that satisfies all of the demands regarding corrosion resistance,
toughness, and fatigue characteristics is still required.
[0009] In the invention described in
JP-A No. 2012-144799, while both corrosion resistance and low-temperature toughness can be improved, there
remains room for further improvement with respect to fatigue characteristics.
[0010] Further, according to Japanese Patent No.
5839151, the corrosion resistance of steel is improved by regulating the Sn concentration
ratio between the soft structure and the hard structure by dividing water cooling
into two stages; however, there remains room for further improvement with respect
to low-temperature toughness and fatigue characteristics.
[0011] An object of the present disclosure is to provide a steel material which has excellent
corrosion resistance as well as low-temperature toughness and fatigue characteristics.
Solution to Problem
[0012] The present disclosure was made to achieve the above object with a steel material
which essentials were as follows.
- (1) A steel material includes, in terms of percentage by mass:
from 0.01 to 0.20% of C,
from 0.01 to 1.00% of Si,
from 0.05 to 3.00% of Mn,
from 0 to 0.050% of P,
from 0 to 0.0100% of S,
from 0.05 to 0.25% of Sn,
from 0 to 0.100% of Al,
from 0.0005 to 0.0100% of N,
from 0.0001 to 0.0100% of O,
from 0 to 0.050% of Ti,
from 0 to 0.050% of Nb,
from 0 to 0.050% of V,
from 0 to 0.050% of W,
from 0 to 0.050% of Mo,
from 0 to 0.10% of Cu,
from 0 to 0.05% of Ni,
from 0 to 0.10% of Cr,
from 0 to 0.05% of Sb,
from 0 to 0.0010% of B,
from 0 to 0.0100% of Ca,
from 0 to 0.0100% of Mg,
from 0 to 0.0100% of REM, and
a balance consisting of Fe and impurities,
in which the Sn ratio of the Sn concentration, a, at a crystal grain boundary to the
Sn concentration, b, inside a crystal grain, expressed by a/b, is 1.2 or less.
- (2) The steel material according to (1) above in a form of steel plate with a plate
thickness of from 6 to 100 mm.
Advantageous Effects of Invention
[0013] According to the present disclosure, it is possible to obtain a steel material with
excellent corrosion resistance, low-temperature toughness, and fatigue characteristics.
DESCRIPTION OF EMBODIMENTS
[0014] A steel material according to the present embodiments will be described in detail.
[0015] A numerical range expressed by "from x to y" or "between x and y" includes herein
the values of x and y in the range as the minimum and maximum values, respectively.
[0016] A steel material according to the embodiment, comprising in terms of percentage by
mass, from 0.01 to 0.20% of C, from 0.01 to 1.00% of Si, from 0.05 to 3.00% of Mn,
from 0 to 0.050% of P, from 0 to 0.0100% of S, from 0.05 to 0.25% of Sn, from 0 to
0.100% of Al, from 0.0005 to 0.0100% of N, from 0.0001 to 0.0100% of O, from 0 to
0.050% of Ti, from 0 to 0.050% of Nb, from 0 to 0.050% of V, from 0 to 0.050% of W,
from 0 to 0.050% of Mo, from 0 to 0.10% of Cu, from 0 to 0.05% of Ni, from 0 to 0.10%
of Cr, from 0 to 0.05% of Sb, from 0 to 0.0010% of B, from 0 to 0.0100% of Ca, from
0 to 0.0100% of Mg, from 0 to 0.0100% of REM, and a balance consisting of Fe and impurities,
in which the Sn ratio of the Sn concentration, a, at a crystal grain boundary to the
Sn concentration, b, inside a crystal grain, expressed by a/b, is 1.2 or less.
[0017] When a steel material of the embodiment has the above composition, it can be a steel
material excellent in corrosion resistance and also in low-temperature toughness and
fatigue characteristics. Although the reason therefor is not very clear, it is presumed
as follows.
[0018] The present inventors prepared various steel plates with different Sn contents, and
investigated the relationship between corrosion resistance and toughness. As a result,
it has been found that as the Sn content increases, the corrosion resistance improves,
but the absorbed energy (low temperature toughness) at 0°C in the Charpy impact test
may deteriorate in some cases. For example, when the threshold of corrosion resistance
in a SAE J 2334 test is set at 0.6 mm or less, and the threshold of absorbed energy
at 0°C is set at 150 J or more, it has been found that not both can be easily satisfied
stably.
[0019] Therefore, further investigations on corrosion resistance and absorbed energy were
conducted, and as a result the composition of steel material, with which excellent
absorbed energy could be obtained even at high Sn content, was found.
[0020] Further, detailed investigation on the steel material with improved absorbed energy
was conducted, and as a result it was found that the ratio between the Sn at the crystal
grain boundary and the Sn inside the crystal grain strongly influences the low-temperature
toughness of a steel. Also, it was found that the ratio between the Sn at the crystal
grain boundary and the Sn inside the crystal grain also influences the fatigue characteristic
of a steel. Furthermore, it was found that the same influences the corrosion resistance.
[0021] The inventors further studied diligently about a steel material excellent in all
of corrosion resistance, low-temperature toughness, and fatigue characteristics, and
as a result, the following findings were obtained.
[0022] Since the melting point of Sn is low, when Sn is added to a steel material, Sn diffuses
within a crystal grain during cooling after rolling and reheating, and segregates
at the crystal grain boundary. Then, when Sn segregation at the crystal grain boundary
occurs, the toughness of the steel decreases markedly.
[0023] In this regard, when segregation of Sn at a crystal grain boundary of Sn in a steel
material is suppressed, in particular, when the Sn ratio of the Sn concentration [a]
at a crystal grain boundary to the Sn concentration [b] inside a crystal grain, expressed
by [a/b] (hereinafter also simply referred to as "the ratio between the Sn at the
crystal grain boundary and the Sn inside the crystal grain") is 1.2 or less, it has
been found that the low-temperature toughness and the fatigue characteristics are
improved, while maintaining excellent corrosion resistance.
[0024] There is no particular restriction on the means for regulating the ratio between
the Sn at the crystal grain boundary and the Sn inside the crystal grain to 1.2 or
less, and for example, when an Sn-containing steel is produced under appropriate conditions,
it is possible to suppress segregation of Sn at a grain boundary. Specifically, a
steel after the finish rolling is slowly cooled first, then held at a predetermined
temperature for a certain period of time allowing recuperation. Thereafter by conducting
strong-cooling to a temperature of 550°C or less, segregation of Sn at a grain boundary
can be suppressed, and the Sn ratio can be regulated within the above range.
[0025] This embodiment was devised based on the above findings. Each requirement of the
embodiment will be described in detail below.
(A) Chemical Composition
[0026] The reasons for defining the respective elements are as follows. In the following
description, "%" for a content means "mass%".
C: 0.01 to 0.20%
[0027] C is an element for improving the strength of a steel material. However, when the
C content is excessive, the weldability is remarkably deteriorated. Further, as the
C content increases, the formation amount of cementite that acts as a cathode to promote
corrosion in a low pH environment increases, and the corrosion resistance of a steel
material decreases. Therefore, the C content is defined in a range of from 0.01 to
0.20%. The C content is preferably 0.02% or more, and more preferably 0.03% or more.
The lower limit of the C content may be 0.05%, 0.07%, or 0.09%. Further, the C content
is preferably 0.18% or less, and more preferably 0.16% or less. The upper limit of
the C content may be 0.15%, or 0.13%.
Si: 0.01 to 1.00%
[0028] Si is an element necessary for deoxidation. In order to obtain a sufficient deoxidation
effect, it is necessary to contain it 0.01% or more. On the other hand, when the Si
content is excessive, the toughness of a steel material, especially when welding is
performed, the toughness of a base metal and a weld heat affected zone is impaired.
Therefore, the Si content is defined in a range of from 0.01 to 1.00%. The Si content
is preferably 0.03% or more, and more preferably 0.05% or more. The lower limit of
the Si content may be 0.10%, 0.15%, or 0.20%. Also, the Si content is preferably 0.80%
or less, and more preferably 0.60% or less. The upper limit of the Si content may
be 0.50%, 0.40%, or 0.30%.
Mn: 0.05 to 3.00%
[0029] Mn is an element having an action of increasing the strength of a steel material
at low cost. However, when the Mn content is excessive, the Mn segregation increases,
and the toughness deteriorates. Therefore, the Mn content is defined in a range of
from 0.05 to 3.00%. The Mn content is preferably 0.50% or more, and more preferably
0.80% or more. Further, the Mn content is preferably 2.50% or less, and more preferably
2.00% or less.
P: 0 to 0.050%
[0030] P is an element existing as an impurity in a steel material. P is an element that
lowers acid resistance of a steel material, and lowers the corrosion resistance of
a steel material in a chloride corrosion environment where the pH at a corrosion interface
decreases. P also deteriorates the weldability and toughness of a steel material.
Therefore, the P content is limited to 0.050% or less. The P content is preferably
0.040% or less, and more preferably 0.030% or less. For improving the toughness, the
upper limit of the P content may be 0.020%, 0.015%, or 0.010%. Although it is not
easy to completely remove P, it is not necessary to exclude it, and the lower limit
of the P content is 0%. Since the desulfurization cost for dephosphorization to ultra-low
concentration is high, the lower limit of the P content may be 0.0005%, 0.001%, or
0.003%.
S: 0 to 0.0100%
[0031] S is an element existing as an impurity in a steel material. S forms MnS as a starting
point of corrosion in a steel material. When the S content exceeds 0.0100%, the decrease
in corrosion resistance of a steel material becomes conspicuous. Therefore, the S
content is limited to 0.0100% or less. The S content is preferably 0.0080% or less,
more preferably 0.0060% or less, and even more preferably 0.0040% or less. Although
it is not easy to remove S completely, it is not necessary to exclude it, and the
lower limit of the S content is 0%. Since the refining cost for desulphurization to
ultra-low concentration is high, the lower limit of the S content may be 0.0005%,
or 0.0010%.
Sn: 0.05 to 0.25%
[0032] Since Sn significantly suppresses an anode dissolution reaction of a steel material
in a low pH chloride environment, it greatly improves corrosion resistance of a steel
material in a chloride corrosion environment. However, when the Sn content becomes
excessive, not only the above effect is saturated, but also the toughness of a steel
material, and especially when welding is performed, the toughness of a base material,
and a high-heat-input welded joint deteriorates. Therefore, the Sn content is defined
in a range of from 0.05 to 0.25%. The Sn content is preferably 0.07% or more, more
preferably 0.09% or more, and further preferably 0.10% or more. Further, the Sn content
is preferably 0.20% or less, more preferably 0.18% or less, and further preferably
0.016% or less.
Al: 0 to 0.100%
[0033] Al is an element effective for deoxidizing a steel material. Since Si is contained
in a steel material in this embodiment, deoxidation is performed by Si. Therefore,
a deoxidation treatment with Al is not absolutely necessary, and the lower limit of
the Al content is 0%. However, deoxidation with Al may be performed in addition to
the same with Si.
Meanwhile, when the Al content exceeds 0.100%, the corrosion resistance of a steel
material in a low pH environment is lowered, so that the corrosion resistance of the
steel material in a chloride corrosion environment is lowered. Further, when the Al
content exceeds 0.100%, a nitride becomes coarse and the toughness of a steel material
decreases. Therefore, the Al content is defined in a range of from 0 to 0.100%. In
order to obtain the deoxidation effect with Al, the Al content is preferably 0.005%
or more, more preferably 0.010% or more, further preferably 0.015% or more, still
further preferably 0.020% or more, and particularly preferably 0.025% or more. Further,
the Al content is preferably 0.060% or less, and more preferably 0.045% or less.
N: 0.0005 to 0.0100%
[0034] N dissolves in the form of ammonia and has an effect of improving the corrosion resistance
of a steel plate in a saline environment by suppressing the pH decrease due to the
hydrolysis of Fe
3+ in an environment where the amount of air borne salt particle is high. On the other
hand, when the N content is excessive, not only the effect is saturated, but also
the toughness of a steel plate is deteriorated. Therefore, the N content is regulated
in a range of from 0.0005 to 0.0100%. Since it is not easy to lower the lower limit
of N below 0.0005%, and it is also costly, the lower limit is set at 0.0005%. The
lower limit of the N content may be set at 0.0010% or 0.0020%, according to need.
When the content of N exceeds 0.0100%, there arises a risk that coarse AlN is formed
and the toughness is apt to decrease, so the upper limit is set at 0.0100%. In order
to further increase the toughness, the upper limit of the N content may be set at
0.0080% or 0.0060%.
O: 0.0001 to 0.0100%
[0035] When a steel material contains a trace amount of O (oxygen), the toughness of the
same is improved, and especially when welding is applied, the toughness of a welded
joint is improved. Meanwhile, O forms an oxide, such as SnO and SnO
2. Therefore, when the O content becomes excessive, when the O content becomes excessive,
the Sn concentration in the steel cannot be sufficiently secured. In addition, since
the above oxide acts as a starting point of corrosion, the corrosion resistance of
a steel material decreases. Therefore, the O content is regulated in a range of from
0.0001 to 0.0100%. The content of O is preferably 0.0002% or more, and more preferably
0.0003% or more. The lower limit of the O content may be 0.0005%, 0.0010%, 0.0015%,
or 0.0019%. Also, the O content is preferably 0.0090% or less, and more preferably
0.0080% or less. The upper limit of the O content may be 0.0060%, 0.0040%, or 0.0030%.
Ti: 0 to 0.050%
Nb: 0 to 0.050%
V: 0 to 0.050%
[0036] All of Ti, Nb, and V are elements which form precipitates to enhance the strength
of a steel material, and may be contained according to need. It is not prerequisite
to contain the elements, and the lower limits of their contents are all 0%. On the
other hand, when Ti, Nb, or V are excessively contained, the toughness is apt to decrease.
Therefore, each content should be 0.050% or less. Each content is preferably 0.0030%
or less, and more preferably 0.020% or less. In order to obtain the above effect,
one or more kinds selected from Ti, Nb, and V may be contained at 0.001% or more.
W: 0 to 0.050%
Mo: 0 to 0.050%
[0037] When the content of W or Mo exceeds 0.050%, the corrosion resistance decreases. Therefore,
the contents of W and Mo should be respectively 0.050% or less. It is preferable that
both the contents are 0.040% or less. The upper limit of each of the W content and
the Mo content may be 0.030%, 0.020%, 0.010%, or 0.005%. In order to improve the corrosion
resistance, it is preferable that the W content and the Mo content are as small as
possible, and the lower limits of their contents are 0%. However, in order to improve
such properties as strength or toughness (especially low-temperature toughness), W
and Mo may be contained, and the lower limits of their contents may be 0.010%, or
0.020%.
Cu: 0 to 0.10%
[0038] It is generally believed that Cu is an element that improves the corrosion resistance
of a steel material. However, the present inventors have found that the corrosion
resistance of a steel material decreases in a corrosive environment containing a chloride
as assumed in this embodiment, when it contains Cu. The Cu content is preferably as
low as possible, and the lower limit of the Cu content should be 0%. Meanwhile, considering
possibility of contamination as an impurity, the Cu content is set at 0.10% or less.
For the sake of enhancement of the corrosion resistance, the Cu content is preferably
0.07% or less, more preferably 0.05% or less, further preferably 0.03% or less, and
still further preferably 0.02% or less. The Cu content is particularly preferably
0.01% or less.
Ni: 0 to 0.05%
[0039] It is generally believed that Ni improves, similarly to Cu, the corrosion resistance
of a steel material. However, the present inventors have found that the corrosion
resistance of a steel material decreases in a corrosive environment containing a chloride
as assumed in this embodiment, when it contains Ni. The Ni content is preferably as
low as possible, and the lower limit of the Ni content should be 0%. Meanwhile, even
when it is mixed in as an impurity, so long as the Ni content is 0.05% or less, the
corrosion resistance decrease is only slight. Therefore, the Ni content is set at
0.05% or less. For the sake of enhancement of the corrosion resistance, the Ni content
is preferably 0.03% or less, more preferably 0.02% or less, and further preferably
0.01% or less.
Cr: 0 to 0.10%
[0040] It is generally believed that Cr is an element that improves corrosion resistance
of steel material. However, the present inventors have found that the corrosion resistance
of a steel material is deteriorated in a corrosive environment containing a chloride
as assumed in this embodiment, when it contains Cr. The Cr content is preferably as
low as possible, and the lower limit of the Cr content should be 0%. Meanwhile, considering
possibility of contamination as an impurity, the Cr content is set at 0.10% or less.
For the sake of enhancement of the corrosion resistance, the Cr content is preferably
0.07% or less, more preferably less than 0.05%, further preferably 0.03% or less,
and still further preferably 0.02% or less. The Cr content is particularly preferably
0.01% or less.
Sb: 0 to 0.05%
[0041] Since Sb is an element that improves the acid resistance, Sb may be contained as
necessary. It is not indispensable to contain Sb, and the lower limit of its content
is 0%. Incidentally, even when Sb is contained in an amount exceeding 0.05%, not only
the effect is saturated, but also the toughness and the like of the steel material
are deteriorated. Therefore, the Sb content is set at 0.05% or less. The upper limit
of the Sb content may be 0.04% or less, or 0.03% or less. In order to obtain the above
effect, the Sb content is preferably 0.005% or more, more preferably 0.010% or more,
and further preferably 0.015% or more. When it is not necessary to obtain the above
effect, the upper limit of the Sb content may be 0.015%, 0.010%, or 0.005% according
to need.
B: 0 to 0.0010%
[0042] B is an element for increasing the strength of a steel material by addition of a
trace amount thereof, so it may be added optionally. It is not indispensable to contain
B, and the lower limit of its content is 0%. When B is added in an amount exceeding
0.0010%, the toughness may be deteriorated, so the B content is set at 0.0010% or
less. In order to obtain the above effect, the B content is preferably 0.0003% or
more, and more preferably 0.0005% or more. When it is not necessary to obtain the
above effect, the upper limit of the B content may be 0.0005%, or 0.0003%, according
to need.
Ca: 0 to 0.0100%
[0043] Ca is present in the form of an oxide in a steel material, and has an action of suppressing
decrease in pH at the interface in a corrosion reaction zone to prevent corrosion,
and therefore Ca may be included if necessary. It is not indispensable to contain
Ca, and the lower limit of its content is 0%. When the Ca content exceeds 0.0100%,
the above effect is saturated. Accordingly, the Ca content is set at 0.0100% or less.
The Ca content is preferably 0.0050% or less, and more preferably 0.0040% or less.
In order to obtain the above effect, the Ca content is preferably 0.0002% or more,
and more preferably 0.0005% or more. When it is not necessary to obtain the above
effect, the upper limit of the Ca content may be 0.0030%, 0.0005%, or 0.0002% or less,
according to need.
Mg: 0 to 0.0100%
[0044] Similar to Ca, Mg has an action of suppressing decrease in pH at the interface in
a corrosion reaction zone to prevent corrosion of a steel material, and therefore
Mg may be included according to need. It is not indispensable to contain Mg, and the
lower limit of its content is 0%. When the Mg content exceeds 0.0100%, the above effect
is saturated. Therefore, the Mg content is set at 0.0100% or less. The Mg content
is preferably 0.0050% or less, and more preferably 0.0040% or less. In order to obtain
the above effect, the Mg content is preferably 0.0002% or more, and more preferably
0.0005% or more. When it is not necessary to obtain the above effect, the upper limit
of the Mg content may be set at 0.0030%, 0.0005%, or 0.0002%, according to need.
REM: 0 to 0.0100%
[0045] Since REM (rare earth element) is an element that improves the weldability of a steel
material, it may be included as necessary. It is not indispensable to contain REM,
and the lower limit of its content is 0%. When the REM content exceeds 0.0100%, the
above effect is saturated. Therefore, the REM content should be 0.0100% or less. The
REM content is preferably 0.0050% or less, and more preferably 0.0040% or less. In
order to obtain the above effect, the REM content is preferably 0.0002% or more, and
more preferably 0.0005% or more. When it is not necessary to obtain the above effect,
the upper limit of the Mg content may be set at 0.0030%, 0.0005%, or 0.0002%, according
to need.
[0046] In this regard, REM is a collective term of 17 elements including 15 elements of
lanthanoid, as well as Y and Sc. One or more of these 17 elements may be included
in a steel material, and the REM content means the sum of the contents of such elements.
[0047] The balance of the chemical composition of a steel material of the embodiment is
Fe and impurities.
[0048] In this regard, "impurity" means a component which is mixed in when a steel material
is produced industrially due to various factors related to the raw material, such
as ore, and scrap, or a production process, and which is tolerable so long as the
embodiment is not adversely affected.
(B) Sn Ratio
The Sn ratio of the Sn concentration [a] at a crystal grain boundary to the Sn concentration
[b] inside a crystal grain, expressed by [a/b]: 1.2 or less
[0049] As described above, the Sn ratio between the crystal grain boundary and the crystal
grain inside affects the low-temperature toughness, the fatigue characteristics and
the corrosion resistance of a steel. When Sn is segregated at the crystal grain boundary
and the Sn ratio between the crystal grain boundary and the crystal grain inside exceeds
1.2, the improvement effect on the low-temperature toughness and the fatigue characteristics
cannot be expected. Therefore, the Sn ratio between the crystal grain boundary and
the crystal grain inside is set at 1.2 or less. The Sn ratio is preferably 1.1 or
less, and more preferably 1.05 or less. Although the lower limit of the Sn ratio need
not be particularly determined, the lower limit may be set at 0.7, 0.8, 0.9, or 1.0.
[0050] There is no precipitate of Sn in a steel material of the embodiment, and the extraction
residue is 0%. That is, all of Sn is dissolved as a solid solution in a steel material.
[0051] An Sn ratio between the crystal grain boundary and the crystal grain inside of the
embodiment may be determined by the following method. Firstly, a cylindrical specimen
having a diameter of 3 mm and a length of 10 mm is prepared from a steel material
at a position of 1/4 t (t represents plate thickness or wall thickness). Then, the
specimen was subjected to an ultra-high vacuum impact fracture mechanism attached
to an Auger spectroscopic analyzer (Model 670i, manufactured by ULVAC-PHI, Inc.),
and the fracture surface, which is formed by fracture in vacuum (1.0E
-9 Torr or less) in an atmosphere at the liquid nitrogen temperature (-150°C), is observed.
The fracture surface is mostly occupied by cleavage fracture surfaces having a river
pattern, and dimple fracture surfaces, and sparse intergranular fractured surfaces
are also recognized. The crystal grain boundary and the crystal grain inside of the
fracture surface are discriminated by a macro-fractographic method, and Auger spectra
are measured at 10 positions in each crystal grain boundary and crystal grain inside.
To verify the discrimination between the crystal grain boundary and the crystal grain
inside, the fracture surface examined by the macro-fractographic method is analyzed
by Auger spectroscopy with respect to C, which is apt to segregate at a crystal grain
boundary, to confirm discrimination between the crystal grain boundary and the crystal
grain inside. The Sn ratio is calculated by measuring the ratio of the concentrations
(atom%) of Sn between the crystal grain boundary and the crystal grain inside. In
this regard, the relative sensitivity coefficient is calibrated with Au.
(C) Dimensions
[0052] There is no particular restriction on the dimensions such as the thickness of a steel
material of the embodiment. However, the effect of improving the corrosion resistance,
the low-temperature toughness, and the fatigue resistance is more remarkably obtained
when a steel material is used in a form of a steel plate having a thickness of from
6 to 100 mm. The thickness (plate thickness) of a steel plate is preferably from 10
to 40 mm. A steel material may be a steel pipe or a section steel, and its thickness
or wall thickness may be from about 3 to 50 mm.
(D) Production Method
[0053] A steel material according to the embodiment can be produced using, for example,
the production method described below.
[0054] Namely a method of producing a steel material including:
a step of preparing a slab whose chemical composition is the same as the above composition,
a heating step of heating the slab from 1000 to 1150°C,
a rough rolling step of applying rough rolling to the slab,
a finish rolling step of applying finish rolling to the slab having undergone rough
rolling such that the finishing temperature of the surface becomes from 900 to 750°C
while keeping the rolling reduction rate from 950°C at 50% or higher,
a first accelerated cooling step of performing accelerated cooling of the finish-rolled
slab (steel material) at a cooling rate of from 5 to 10°C/s until the surface temperature
reaches 630°C or less,
a recuperation step of suspending accelerated cooling of the slab (steel material)
after the first accelerated cooling step and allowing cooling in the air for 30 to
120 sec (suspension of accelerated cooling and cooling in the air is hereinafter referred
to as "holding"), and further allowing recuperation by the heat from the inside of
the slab (steel material) until the surface temperature reaches a range of from 650
to 700°C
a second accelerated cooling step of performing accelerated cooling of the slab (steel
material) after the recuperation step at a cooling rate of from 10 to 60°C/s until
the surface temperature reaches 550°C or less, and
an air cooling step of performing cooling in the air after the second accelerated
cooling step.
[0055] The heating temperature in the heating step is from 1000 to 1150°C. When the temperature
is within the above range, the austenite grain size at the time of heating can be
kept small, so that grain refining of the rolled structure can be achieved. When the
heating temperature is 1150°C or lower, coarsening of austenite grains is suppressed
and coarsening of the structure after cooling transformation is also suppressed, so
that excellent low-temperature toughness can be achieved. On the other hand, when
the heating temperature is 1000°C or higher, the alloy elements are sufficiently solutionized,
so that the deterioration of the internal quality of the steel is suppressed, and
the finishing temperature in rolling is not excessively lowered, so that the enhancement
of low-temperature toughness can be expected.
[0056] Further, when the finishing temperature at the surface in the rolling step is 900°C
or lower, the growth of recrystallized austenite grains is suppressed, and grain refining
thereof is promoted. Further, when the finishing temperature is 750°C or higher, the
ferrite structure becomes less susceptible to processing, so that the low-temperature
toughness is improved. Consequently, the finishing temperature is set from 900 to
750°C.
[0057] Furthermore, when the rolling reduction rate from 950°C is 50% or more, partial recrystallization
of austenite hardly occurs, so that a duplex grain structure is suppressed to enhance
the low-temperature toughness. Consequently, the rolling reduction rate from 950°C
is set at 50% or more.
[0058] Regarding cooling after rolling, water cooling is carried out under the following
conditions.
<Slow Cooling After Completion of Rolling (First Accelerated Cooling Step)>
[0059] After finish rolling, accelerated cooling is immediately performed at a cooling rate
of from 5 to 10°C/s until the surface temperature of a steel material becomes 630°C
or lower. With the cooling rate within the above range, grain boundary segregation
of Sn can be suppressed. When the cooling rate is 5°C/s or more, Sn diffusion is suppressed.
When it is 10°C/s or less, the Sn ratio between the crystal grain boundary and the
crystal grain inside is reduced, although the reason therefor is not very clear. As
a result, in both cases, the low-temperature toughness and the fatigue characteristics
are improved.
<Recuperation by Holding before Accelerated Cooling (Recuperation Step)>
[0060] After slow cooling, the accelerated cooling is suspended allowing cooling in the
air (holding) for recuperation until the surface temperature of the cooled steel material
rises again due to the internal temperature of the steel material and the surface
temperature is equalized in a temperature range of from 650 to 700°C. The holding
time (this time is the accelerated cooling suspension time corresponding to the recuperation
time) is 30 to 120 sec. Owing to the recuperation step, it is possible to segregate
elements that are apt to segregate, such as S, P, and C, into the crystal grain boundary,
and to suppress diffusion of Sn. When the holding time is 30 sec or more, uniform
recuperation deep into the inside of a steel material becomes possible. When the holding
time is 120 seconds or less, elevation of the surface temperature of a steel material
up to a temperature range exceeding 700°C may be suppressed more easily so that diffusion
of Sn may be reduced to suppress segregation.
<Accelerated Cooling (Second Accelerated Cooling Step)>
[0061] Thereafter, cooling is resumed at a cooling rate of from 10 to 60°C/s until the surface
temperature reaches 550°C or less. By accelerated cooling under the above conditions,
it is possible to suppress segregation of Sn at the crystal grain boundary, and to
refine the steel structure. When the cooling rate is 10°C/s or more, diffusion of
Sn is suppressed, and segregation at the grain boundary is suppressed. Meanwhile,
when the cooling rate is 60°C/s or less, an increase in the strength of a steel material
plate is suppressed, and the fatigue resistance is improved.
[0062] After the second accelerated cooling step, cooling in the air is performed.
[0063] In a case where a steel material of the embodiment is used for a large structure,
such as a bridge and an offshore structure, the tensile strength should preferably
be in a range of from 400 to 650 MPa. The tensile strength may be also from 480 to
580 MPa.
EXAMPLES
[0064] The present disclosure will be described more specifically below by way of Examples,
provided that the present disclosure is not limited to the Examples.
[0065] A steel having the chemical composition shown in Table 1 was melted in a furnace
and then cast in to a slab with a thickness of 300 mm. The slab was heated, subjected
to rough rolling and finish rolling, and then quickly cooled to a steel plate having
a plate thickness of 20 mm. The production conditions are shown in Table 2.
[Table 1]
Steel grade |
Chemical composition (mass%, balance: Fe and impurities) |
C |
Si |
Mn |
P |
S |
Sn |
Al |
N |
O |
Ti |
Nb |
A |
0.13 |
0.33 |
1.41 |
0.010 |
0.0030 |
0.18 |
0.033 |
0.0041 |
0.0050 |
|
|
B |
0.12 |
0.31 |
1.33 |
0.001 |
0.0010 |
0.12 |
0.020 |
0.0028 |
0.0010 |
|
|
c |
0.10 |
0.31 |
1.30 |
0.003 |
0.0100 |
0.11 |
0.040 |
0.0038 |
0.0030 |
|
|
D |
0.14 |
0.36 |
1.22 |
0.010 |
0.0080 |
0.09 |
0.027 |
0.0024 |
0.0030 |
|
|
E |
0.11 |
0.34 |
1.13 |
0.050 |
0.0050 |
0.20 |
0.036 |
0.0033 |
0.0050 |
|
|
F |
0.12 |
0.38 |
1.62 |
0.005 |
0.0010 |
0.17 |
0.023 |
0.0020 |
0.0002 |
0.011 |
0.024 |
G |
0.13 |
0.31 |
1.13 |
0.003 |
0.0060 |
0.09 |
0.023 |
0.0036 |
0.0080 |
|
|
H |
0.08 |
0.21 |
1.90 |
0.010 |
0.0005 |
0.12 |
0.025 |
0.0045 |
0.0050 |
|
|
I |
0.08 |
0.28 |
1.02 |
0.005 |
0.0030 |
0.19 |
0.031 |
0.0034 |
0.0050 |
|
0.016 |
J |
0.12 |
0.21 |
1.94 |
0.001 |
0.0010 |
0.05 |
0.023 |
0.0026 |
0.0030 |
0.015 |
0.008 |
K |
0.08 |
0.21 |
1.02 |
0.003 |
0.0030 |
0.05 |
0.020 |
0.0030 |
0.0020 |
|
|
L |
0.13 |
0.31 |
1.13 |
0.005 |
0.0010 |
0.12 |
0.020 |
0.0030 |
0.0030 |
|
|
M |
0.08 |
0.28 |
1.02 |
0.050 |
0.0050 |
0.19 |
0.031 |
0.0034 |
0.0050 |
|
|
N |
0.10 |
0.25 |
1.13 |
0.003 |
0.0050 |
0.12 |
0.030 |
0.0020 |
0.0030 |
|
|
O |
0.13 |
0.32 |
1.25 |
0.005 |
0.0050 |
- |
0.030 |
0.0036 |
0.0030 |
|
|
P |
0.10 |
0.22 |
1.17 |
0.010 |
0.0030 |
0.02 |
0.030 |
0.0040 |
0.0030 |
|
|
Q |
0.14 |
0.25 |
1.61 |
0.005 |
0.0080 |
0.30 |
0.028 |
0.0034 |
0.0050 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
V |
W |
Mo |
Cu |
Ni |
Cr |
Sb |
B |
Ca |
Mg |
REM |
A |
|
|
0.030 |
|
0.01 |
|
|
|
|
|
|
B |
|
|
|
|
|
|
|
|
|
|
|
C |
|
|
|
|
0.01 |
|
|
|
|
|
|
D |
|
|
|
|
|
|
|
|
|
|
|
E |
|
|
0.020 |
|
|
|
|
|
|
|
|
F |
|
0.011 |
|
0.07 |
0.03 |
|
|
0.0003 |
|
|
|
G |
0.009 |
|
|
|
|
|
|
|
0.0004 |
|
|
H |
|
|
0.010 |
|
|
|
|
0.0002 |
|
0.0033 |
|
I |
|
|
|
|
|
0.01 |
|
|
|
|
0.0019 |
J |
0.007 |
|
|
0.03 |
|
|
0.01 |
|
|
|
|
K |
|
|
|
0.12 |
|
|
|
|
|
|
|
L |
|
|
0.070 |
|
0.02 |
|
|
|
|
|
|
M |
|
|
|
|
0.07 |
|
|
|
|
|
|
N |
|
|
|
|
|
1.10 |
|
|
|
|
|
O |
|
|
0.030 |
|
0.03 |
|
|
|
|
|
|
P |
|
|
0.010 |
|
|
|
|
|
|
|
|
Q |
|
|
|
|
0.01 |
|
|
|
|
|
|
[Table 2]
Test No. |
Steel grade |
Rolling step |
1st accelerated cooling step |
Recuperation step |
2nd accelerated cooling step |
Heating temperature (°C) |
Finishing temperature (°C) |
Reduction rate at 950°C or higher (%) |
Slow cooling rate (°C/s) |
Cooling completion temperature (°C) |
Holding time (s) |
Holding time completion temperature (°C) |
Accelerated cooling rate (°C/s) |
Cooling completion temperature (°C) |
1 |
A |
1150 |
850 |
52 |
7 |
600 |
60 |
680 |
30 |
500 |
2 |
B |
1150 |
800 |
55 |
6 |
580 |
30 |
650 |
10 |
520 |
3 |
C |
1120 |
750 |
55 |
7 |
620 |
30 |
650 |
40 |
450 |
4 |
D |
1150 |
840 |
50 |
7 |
600 |
60 |
660 |
50 |
400 |
5 |
E |
1120 |
890 |
52 |
6 |
630 |
90 |
700 |
20 |
520 |
6 |
F |
1150 |
900 |
55 |
5 |
580 |
120 |
700 |
20 |
500 |
7 |
G |
1000 |
810 |
58 |
10 |
600 |
60 |
650 |
20 |
550 |
8 |
H |
1150 |
880 |
55 |
6 |
600 |
60 |
690 |
40 |
500 |
9 |
I |
1150 |
750 |
55 |
7 |
620 |
30 |
660 |
20 |
520 |
10 |
J |
1120 |
860 |
50 |
5 |
630 |
30 |
670 |
30 |
480 |
11 |
K |
1150 |
860 |
52 |
6 |
600 |
60 |
660 |
30 |
450 |
12 |
L |
1120 |
860 |
55 |
5 |
600 |
30 |
660 |
20 |
400 |
13 |
M |
1150 |
890 |
50 |
7 |
580 |
60 |
700 |
40 |
520 |
14 |
N |
1150 |
890 |
55 |
6 |
620 |
90 |
700 |
30 |
500 |
15 |
O |
1120 |
890 |
55 |
6 |
620 |
60 |
700 |
30 |
520 |
16 |
P |
1120 |
850 |
55 |
5 |
600 |
60 |
680 |
30 |
500 |
17 |
Q |
1120 |
850 |
52 |
5 |
580 |
60 |
650 |
30 |
520 |
18 |
A |
1150 |
850 |
50 |
2 |
650 |
90 |
680 |
30 |
500 |
19 |
A |
1150 |
850 |
50 |
30 |
520 |
30 |
600 |
30 |
520 |
20 |
A |
1150 |
850 |
50 |
6 |
600 |
120 |
720 |
30 |
520 |
21 |
A |
1150 |
850 |
55 |
6 |
620 |
0 |
- |
30 |
500 |
22 |
A |
1150 |
850 |
50 |
10 |
600 |
30 |
650 |
8 |
560 |
23 |
A |
1150 |
850 |
50 |
6 |
620 |
30 |
650 |
65 |
380 |
[0066] Subsequently, a cylindrical specimen having a diameter of 3 mm and a length of 10
mm was cut out from each steel plate, and subjected to an ultra-high vacuum impact
fracture mechanism attached to an Auger spectroscopic analyzer (Model 670i, manufactured
by Ulvac Inc.), and the fracture surface, which was formed by fracture in vacuum (1.0E-9
Torr or less) in an atmosphere at the liquid nitrogen temperature (-150°C), was observed.
The fracture surface was mostly occupied by cleavage fracture surfaces having a river
pattern, and dimple fracture surfaces, and sparse intergranular fractured surfaces
were also recognized. The crystal grain boundary and the crystal grain inside of the
fracture surface were discriminated by a macro-fractographic method, and Auger spectra
were measured at 10 positions in each crystal grain boundary and crystal grain inside.
To verify the discrimination between the crystal grain boundary and the crystal grain
inside, the fracture surface examined by the macro-fractographic method was analyzed
by Auger spectroscopy with respect to C, which was apt to segregate at a crystal grain
boundary, to confirm discrimination between the crystal grain boundary and the crystal
grain inside. The Sn ratio was calculated by measuring the ratio of the concentrations
(atom%) of Sn between the crystal grain boundary and the crystal grain inside. In
this regard, the relative sensitivity coefficient was calibrated with Au.
[0067] Further, a corrosion resistance test, a toughness test, and a fatigue test were conducted
for each steel plate.
<Corrosion Resistance Test>
[0068] A specimen having a length of 60 mm, a width of 100 mm, and a thickness of 3 mm was
cut out from each steel plate, and subjected to the SAE J 2334 test. In doing so,
two specimens were taken from each steel plate, and on one of them, an anticorrosion
coating was formed in advance. The SAE J 2334 test will be described below.
[0069] The SAE J 2334 test is an accelerated deterioration test in which a cycle of humid
stage and dry stage (humid → salt application → dry; 24 hours in total) is repeated
to simulate a severely corrosive environment where the amount of air borne salt particle
exceeds 1 mdd. The SAE J 2334 test was conducted repeating a cycle under the following
conditions. The corrosion form under the following conditions is similar to the corrosion
form of an atmospheric exposure test.
(Test Conditions)
[0070]
Humid stage: 50°C, 100% RH, 6 hours,
Salt application stage: Immersion in the aqueous solution with 0.5 mass% of NaCl,
0.1 mass% of CaCl2, and 0.075 mass% of NaHCO3 for 0.25 hours,
Dry stage: 60°C, 50% RH, 17.75 hours.
[0071] In addition, a shotblasting treatment was applied to the surface of each specimen.
With respect to some specimens, after the shotblasting treatment, an anticorrosion
primary coating, an under coating, an intermediate coating, and an over coating were
applied one on another to form an anticorrosion coating having a total thickness of
250 µm.
[0072] As the anticorrosion primary coating, an inorganic zinc rich paint ("SHINTO-ZINC
#2000" produced by SHINTO PAINT CO., LTD.) was coated to a thickness of 75 µm, and
as a mist coating an epoxy resin paint ("NEO-GOSE #2300 MC" produced by SHINTO PAINT
CO., LTD.) was applied. As the under coating, an epoxy resin coating ("NEO-GOSE #2300
PS" produced by Shinto Paint Co., Ltd.) was spray-coated to a film thickness of 120
µm. In addition, as the intermediate coating, an intermediate paint for a fluorine
resin paint ("SHINTO-FLON #100 intermediate paint" produced by SHINTO PAINT CO., LTD.)
was coated to a thickness of 30 µm. Further, as the over coating, a fluorine resin
coating ("SHINTO-FLON #100" produced by SHINTO PAINT CO., LTD.) was spray-coated to
a film thickness of 25 µm.
[0073] For each specimen having the anticorrosion coating, a cross scratch was formed on
the anticorrosion coating to expose part of the steel material. With respect to each
of the specimens on which an anticorrosion coating was not formed, rust was formed
uniformly over the entire specimen surface after the test, and therefore its corrosion
amount was determined. The "corrosion amount" was determined as the average plate
thickness decrement of the specimen when a surface rust layer on the surface was removed.
Specifically, the plate thickness decrement was calculated using the weight change
of the specimen before and after the test, and the surface area of the specimen, and
used as the corrosion amount.
[0074] The criteria for pass or fail at a corrosion resistance test were as follows. A SAE
J 2334 test was conducted for 120 cycles using a specimen on which an anticorrosion
coating was not formed, and one in which the corrosion amount was 0.60 mm or less
was judged for passed. Further, a SAE J2334 test was conducted for 200 cycles using
a specimen on which an anticorrosion coating was formed, and one in which the detached
area at a scratched zone was 20% or less, and the maximum corrosion depth was 0.40
mm or less was judged as pass.
<Low-temperature Toughness Test>
[0075] The low-temperature toughness was evaluated on an impact test specimen taken from
a central part in the plate thickness direction of the plate and in the direction
perpendicular to the rolling direction, by determining the absorbed energy (vE
0) at 0°C using a V-notch specimen according to JIS Z 2242. A specimen with an absorbed
energy of 150 J or more was judged as pass.
<Fatigue Test>
[0076] In a fatigue test, the stress amplitude was changed as a test parameter, and the
relationship between the stress amplitude and the fatigue fracture life was represented
by a S-N diagram, and a fatigue limit was derived therefrom. In the fatigue test,
a No. 2 specimen specified in JIS Z 2275 was used, and the load ratio (the value obtained
by dividing the minimum load by the maximum load) was set at 0.1. In this regard,
the fatigue fracture life was defined as the time point at which the displacement
(the displacement of the cylinder of an actuator that applied the load to a specimen)
at the maximum load increased by 1 mm as compared with the start of the test. When
the fatigue fracture life was 5.5x10
5 cycles or more, the fatigue resistance was judged as pass.
[0077] The results are summarized in Table 3.
[Table 3]
Test No. |
Steel grade |
Sn ratio between grain boundary and grain inside |
SAE J2334 test without a coating 120CY |
SAE J2334 test with a coating 200CY |
Absorbed energy (J) |
Fatigue characteristics (×105) |
|
Corrosion amount (mm) |
Detached area (%) |
Maximum corrosion depth (mm) |
1 |
A |
1.1 |
0.50 |
20 |
0.38 |
150 |
6.2 |
Example of present disclosure |
2 |
B |
1.1 |
0.40 |
15 |
0.35 |
155 |
6.0 |
3 |
C |
1.1 |
0.50 |
20 |
0.35 |
162 |
6.2 |
4 |
D |
1.2 |
0.60 |
20 |
0.30 |
150 |
6.5 |
5 |
E |
1.1 |
0.50 |
20 |
0.38 |
158 |
6.0 |
6 |
F |
1.1 |
0.50 |
20 |
0.38 |
155 |
6.7 |
7 |
G |
1.2 |
0.60 |
20 |
0.35 |
150 |
6.0 |
8 |
H |
1.0 |
0.40 |
15 |
0.35 |
155 |
6.8 |
9 |
I |
1.1 |
0.60 |
15 |
0.30 |
162 |
6.0 |
10 |
J |
1.2 |
0.50 |
20 |
0.35 |
155 |
6.5 |
11 |
K |
1.1 |
0.70 |
50 |
0.45 |
140 |
5.5 |
Comparative Example |
12 |
L |
1.0 |
0.80 |
45 |
0.50 |
150 |
6.5 |
13 |
M |
1.1 |
1.10 |
55 |
1.20 |
155 |
6.0 |
14 |
N |
1.1 |
1.50 |
60 |
1.60 |
165 |
6.0 |
15 |
O |
- |
1.50 |
50 |
1.10 |
165 |
6.0 |
16 |
P |
0.7 |
1.15 |
20 |
0.30 |
145 |
5.5 |
17 |
Q |
1.3 |
0.40 |
25 |
0.30 |
143 |
5.8 |
18 |
A |
1.7 |
0.70 |
35 |
0.45 |
146 |
3.9 |
19 |
A |
1.8 |
0.70 |
30 |
0.40 |
145 |
5.8 |
20 |
A |
1.5 |
0.80 |
30 |
0.42 |
148 |
3.7 |
21 |
A |
1.6 |
0.70 |
25 |
0.45 |
146 |
4.3 |
22 |
A |
1.6 |
0.70 |
20 |
0.42 |
145 |
5.5 |
23 |
A |
1.5 |
0.70 |
30 |
0.45 |
143 |
4.5 |
[0078] Test Nos. 1 to 10 are Examples of the present disclosure which satisfy all the requirements
of the present disclosure. As obvious from Table 3, in the SAE J 2334 test, the corrosion
amount of the specimen without a coating was 0.60 mm or less, and in the scratched
zone of the specimen with a coating the detached area was 20% or less, and the maximum
corrosion depth was 0.40 mm or less. In the toughness test, the Charpy absorbed energy
at 0°C was 150 J or more. Further, in the fatigue test, the fatigue fracture life
was 5.5 × 10
5 cycles or more.
[0079] In contrast thereto, in Test Nos. 15 and 16, which were Comparative Examples, the
Sn content in the steel material was less than the defined lower limit value, and
consequently the corrosion resistance was inferior. Further, in Test No. 17, in which
the Sn content in the steel material exceeded the defined upper limit value, the Sn
ratio between the crystal grain boundary and the crystal grain inside exceeded 1.2,
and as a result the low-temperature toughness and the fatigue resistance were inferior.
[0080] Further, in Test Nos. 18 to 23, the Sn ratio between the crystal grain boundary and
the crystal grain inside exceeded 1.2, and as a result the corrosion resistance slightly
decreased, and the low-temperature toughness and the fatigue resistance were also
inferior.
[0081] Further, in Test Nos. 11 to 14, which were Comparative Examples, the content of Mo,
Cu, Ni, or Cr in the steel material exceeded the defined upper limit value, and as
a result the corrosion resistance was inferior.
INDUSTRIAL APPLICABILITY
[0082] According to the present disclosure, it becomes possible to obtain a steel material
excellent in corrosion resistance, low-temperature toughness, and fatigue characteristics.
Therefore, a steel material according to the present disclosure is suitable for use
as a material for a large structure, such as an offshore structure used in a cold
district, and a bridge.