[Technical Field]
[0001] The present invention relates to a hot-rolled steel sheet having hydrogen induced
cracking resistance (hereinafter, called HIC resistance) and a strength of X52 or
more in accordance with API (American Petroleum Institute) standards which can preferably
be used as a material for an electric resistance welded steel pipe. The electric resistant
welded steel pipe is used as a line pipe for transporting energy resources such as
crude oil and a natural gas. The present invention also relates to a method for manufacturing
the steel sheet.
[Background Art]
[0002] Although UOE steel pipes have been mainly used for linepipes to date from the viewpoint
of transport efficiency because UOE steel pipes can be manufactured to have a large
diameter and a large thickness, high strength electric resistance welded steel pipes,
which are manufactured with a high productivity from less expensive material, hot-rolled
steel sheets, in a coil shape (hot-rolled steel strips), are being increasingly used
instead of UOE steel pipes nowadays. Electric resistance welded steel pipes have an
advantage in that they are superior to UOE steel pipes in terms of variation in wall
thickness and roundness in addition to cost. On the other hand, since the pipe production
method for electric resistance welded steel pipes involves cold roll forming, it is
characteristic that, when pipe production is performed, plastic strain given to the
cold-rolled steel pipes is significantly large compared to that given to UOE steel
pipes.
[0003] Nowadays, in exploitation of crude oil and natural gas, there is an increasing tendency
for oil fields and gas fields to be developed in the polar areas or in deeper regions
due to an increase in the demand for energy and due to the progress of drilling technology.
Linepipes which are used at such places are required to have so-called sour resistance
such as HIC resistance and sulfate stress corrosion cracking resistance (SSC) in addition
to strength, toughness and weldability. In the case of linepipes, which are not subjected
to stress after having been laid, HIC resistance is particularly important.
[0004] HIC is a phenomenon in which hydrogen ions, which have been generated by a corrosion
reaction, increase internal pressure by becoming hydrogen atoms at the surface of
a steel sheet, by entering the steel, and by accumulating around inclusions such as
MnS, around carbides having a large grain diameter such as NbC, and around a second
hard phase so as to cause the steel material to eventually crack. In addition, in
the case where a steel material is given plastic strain, since many dislocations are
formed around the inclusions, the carbides, and the second hard phase mentioned above,
hydrogen atoms are more likely to accumulate, which results in HIC being more likely
to occur.
[0005] To date, various solutions have been proposed in order to solve the problem of HIC
described above.
[0006] Patent Literature 1 discloses a method for improving HIC resistance in which inclusions,
which become the origins of HIC, are rendered harmless by controlling the total contents
of chemical elements which combine respectively with S (sulfur), O (oxygen), and N
(nitrogen) to form inclusions to be 0.01% or less or by controlling the maximum diameter
of inclusions to be 5 µm or less, and in which the hardness of a center segregation
part is controlled to be Hv 330 or less.
[0007] Patent Literature 2 discloses a method for decreasing the area ratio of HIC by decreasing
the size of TiN grains, which become the origin of HIC. Specifically, the size of
Al-Ca-based sulfides in molten steel is decreased by controlling a weight ratio CaO/Al
2O
3 to be 1.2 to 1.5 as a result of controlling the contents of Al and Ca in order to
control the grain diameter of Al-Ti-Ca-based compound inclusions, which are formed
using the sulfides as nuclei, to be 30 µm or less.
[0008] In addition, Patent Literature 3 discloses a method in which the formation of carbonitrides
of Nb and Ti, which become the origins of HIC, is less likely to occur by controlling
Nb concentration to be 0.06% or less and Ti concentration to be 0.025% or less in
a region located at a distance in the thickness direction of 5% of the thickness from
the central part in the thickness direction.
[0009] Patent Literature 4 discloses a method for manufacturing a high strength linepipe
excellent in terms of HIC resistance in which HIC resistance is improved by decreasing
the degree of center segregation as a result of decreasing Mn content in steel and
in which Cr and Mo, which are comparatively less likely to undergo center segregation,
are utilized.
[Citation List]
[Patent Literature]
[0010]
[PTL 1] Japanese Unexamined Patent Application Publication No. 2006-63351
[PTL 2] Japanese Patent No. 4363403 (International Publication No. WO2005/075694)
[PTL 3] Japanese Unexamined Patent Application Publication No. 2011-63840
[PTL 4] Japanese Patent No. 2647302 (Japanese Unexamined Patent Application Publication No. 5-271766)
[Summary of Invention]
[Technical Problem]
[0011] However, in the case of the technique according to Patent Literature 1, since the
hardness of a center segregation part is still high, there is a problem in that sufficient
HIC resistance cannot be achieved in the case of an electric resistance welded steel
pipe, which is given large plasticity when forming is performed, even if it is possible
to render inclusions, which become the origins, harmless.
[0012] In addition, in the case of the techniques according to Patent Literature 2 and Patent
Literature 3, since no specific measure is taken in order to control the hardness
of a center segregation part, there is still a problem in that a large HIC occurs
in the case of an electric resistance welded steel pipe even if it is possible to
render inclusions, which become the origins, harmless.
[0013] In addition, in the case of the technique according to Patent Literature 4, since
there is an increase in the hardness of a center segregation part as a result of the
formation of a second hard phase such as martensite being promoted by the excessive
addition of Cr and Mo, there is a problem in that it is necessary to further decrease
the hardness of a center segregation part in the case of an electric resistance welded
steel pipe, which is given a large plasticity when forming is performed.
[0014] The present invention has been completed in view of the problems described above,
and an object of the present invention is to provide an electric resistance welded
steel pipe for a high strength linepipe excellent in terms of HIC resistance which
can preferably be used for an electric resistance welded steel linepipe and with which,
for example, a crack length ratio (herein after, called CLR) is 15% or less when HIC
occurs after the linepipe is given 10% of plastic strain.
[0015] Here, "excellent in terms of HIC resistance" refers to a case where a crack length
ratio (CLR) is 15% or less after a steel sheet has been immersed in a NACE solution
(NACE TM-0284 solution A: 5%NaCl + 0.5%CH
3OOH, 1 atmosphere of saturated H
2S, and pH = 3.0 to 4.0) for 96 hours.
[Solution to Problem]
[0016] The present invention has been completed in order to decrease the hardness of a center
segregation part and in order to achieve desired strength on the basis of the knowledge
which has been obtained by conducting many experiments regarding the relationship
between the hardness of a center segregation part and steel chemical composition and
the relationship of constituent microstructures to HIC performance and manufacturing
conditions.
[0017] First, the relationship between the HIC performance of a product and the hardness
of a center segregation part was investigated. As a result, it was found that it is
possible to achieve a crack length rate (CLR) of 15% or less in the case where the
Vickers hardness of a center segregation part is HV 230 or less. The finding, that
is, the fact that the hardness of a center segregation part is controlled in order
to improve HIC resistance, is conventionally known as described in Patent Literature
1.
[0018] However, from the results of further collecting the data of products, since it was
found that there is a case where a CLR is more than 15% even if the highest hardness
of a center segregation part is controlled to be Hv 230 or less, the reason for that
was investigated from the viewpoint of material uniformity. Fig. 1 illustrates the
relationship between the hardness ratio of a center segregation part to a non-segregation
part (the Vickers hardness of a center segregation part/the Vickers hardness of a
non-segregation part) and a crack length ratio (CLR). As Fig. 1 indicates, it was
found that a CLR is 15% or less in the case where the hardness ratio is 1.20 or less.
[0019] This is thought to be because, in the case where hardness distribution in the thickness
direction is not uniform, since strain is concentrated at the interface between a
portion having a high hardness in a center segregation part and the other portion
when a steel sheet is given large plastic strain, the interface becomes the trap site
of hydrogen atoms.
[0020] Subsequently, by investigating the chemical composition of steel, with which a hardness
ratio of a center segregation part to a non-segregation part being less than 1.20
is achieved, an SP value (= Mn + Mo + 11.3 x C + 0.29 × (Cu + Ni) + 0.60 x Cr + 0.88
x V) was derived by incorporating the segregation coefficients of constituent chemical
elements in continuously cast slab, which had been calculated using a unique computation
simulation, into the carbon equivalent equation (CEQ = C + Mn / 6 + (Cr + Mo + V)
/ 5 + (Cu + Ni) / 15). Fig. 2 illustrates the relationship between the hardness ratio
of a center segregation part to a non-segregation part and an SP value. From the results,
it was found that it is necessary to control an SP value to be 1.90 or less in order
to control the hardness ratio of a center segregation part to a non-segregation part
to be less than 1.20.
[0021] The present invention has been completed on the basis of the knowledge described
above and further investigations, and the subject matter of the present invention
is as follows.
[0022] [1] A hot-rolled steel sheet for a high strength linepipe excellent in terms of HIC
resistance, the steel sheet having a chemical composition containing, by mass%, C:
0.02% or more and 0.06% or less, Si: 0.05% or more and 0.25% or less, Mn: 0.60% or
more and 1.10% or less, P: 0.008% or less, S: 0.0010% or less, Nb: 0.010% or more
and 0.060% or less, Ti: 0.001% or more and 0.020% or less, Mo: 0.05% or less, Cr:
0.05% or more and 0.50% or less, Al: 0.01% or more and 0.08% or less, Ca: 0.0005%
or more and 0.0050% or less, O: 0.005% or less, one or more selected from among Cu:
0.50% or less, Ni: 0.50% or less, and V: 0.10% or less, and the balance being Fe and
inevitable impurities, and a metallic structure composed of bainitic-ferrite, in which
expression (1) below is satisfied, and in which the ratio of the hardness of a center
segregation part to the hardness of a non-segregation part is less than 1.20.

where SP is derived from SP = Mn + Mo + 11.3 × C + 0.29 × (Cu + Ni) + 0.60 × Cr +
0.88 × V, and where atomic symbols in the equation respectively represent the contents
(mass%) of the corresponding chemical elements.
[0023] [2] The hot-rolled steel sheet for a high strength linepipe excellent in terms of
HIC resistance according to item [1], the steel sheet having the chemical composition,
in which expression (2) below is satisfied.

where EC is expressed by EC = [Ca]eff / (1.25 × S), where [Ca]eff is derived from
Ca - (0.18 + 130 × Ca) × O, and where atomic symbols Ca, S, and O in the equations
respectively represent the contents (mass%) of the corresponding chemical elements.
[0024] [3] The hot-rolled steel sheet for a high strength linepipe excellent in terms of
HIC resistance according to item [1] or [2], the steel sheet having the chemical composition,
in which the ratio of the hardness of a center segregation part to the hardness of
a non-segregation part is less than 1.20.
[0025] [4] A method for manufacturing a hot-rolled steel sheet for a high strength linepipe
excellent in terms of HIC resistance, the method including heating a steel slab having
the chemical composition according to item [1] or [2] at a temperature of 1100°C or
higher and 1300°C or lower, performing rough rolling, thereafter performing finish
rolling under condition that cumulative rolling reduction ratio is 20% or more in
a temperature range of 930°C or lower, performing accelerated cooling on the hot-rolled
steel sheet to a temperature of 380°C or higher and 600°C or lower at an average cooling
rate of 5°C/sec. or more and 100°C/sec. or less in terms of the temperature of the
central part in the thickness direction, and coiling the cooled steel sheet into a
coil shape.
[Advantageous Effects of Invention]
[0026] According to the present invention, by strictly controlling the hardness of a center
segregation part through optimization of the steel microstructure, it is possible
to manufacture a hot-rolled steel sheet for an electric resistance welded steel linepipe
that has an improved HIC resistance after formation of the electric resistance welded
steel pipe, which has been subjected to large plastic strain and that can be used
without any problem under a harsh environment equivalent to a NACE solution. In addition,
the hot-rolled steel sheet manufactured using the present invention can also be used
for a spiral steel pipe for a linepipe.
[Brief Description of Drawings]
[0027]
[Fig. 1] Fig. 1 is a diagram illustrating the relationship between (the hardness of
a center segregation part / the hardness of a non-segregation part) and a crack length
ratio (CLR).
[Fig. 2] Fig. 2 is a diagram illustrating the relationship between an SP value and
(the hardness of a center segregation part / the hardness of a non-segregation part).
[Fig. 3] Fig. 3 is a diagram illustrating the positions where the hardness of a center
segregation part and the hardness of a non-segregation part were determined.
[Description of Embodiments]
[0028] The reasons for the limitations on the constituent elements of the present invention
will be described hereafter.
1. Regarding chemical composition
[0029] First, the reasons for the limitations on the chemical composition of the steel according
to the present invention will be described. Here, % used when describing the chemical
composition always represents mass%.
C: 0.02% or more and 0.06% or less
[0030] C is a chemical element which significantly contributes to an increase in the strength
of steel, and such an effect is realized in the case where the C content is 0.02%
or more, but, in the case where the C content is more than 0.06%, since a second phase
such as a pearlite microstructure is likely to be formed, there is a deterioration
in HIC resistance. Therefore, the C content is set to be in a range of 0.02% or more
and 0.06% or less, or preferably in a range of 0.03% or more and 0.05% or less.
Si: 0.05% or more and 0.25% or less
[0031] Si is a chemical element which is added for solute strengthening and added in order
to decrease scale-off quantity when hot rolling is performed, and such an effect is
realized in the case where the Si content is 0.05% or more, but, in the case where
the Si content is more than 0.25%, since red scale excessively grows, cooling ununiformity
occurs when hot rolling is performed, which results in a deterioration in the uniformity
of aesthetic appearance and material properties. Therefore, the Si content is set
to be in a range of 0.05% or more and 0.25% or less, or preferably 0.10% or more and
0.25% or less. In addition, since there is a deterioration in toughness in an electric
resistance weld zone as a result of forming of MnSi-based oxides when electric resistance
welding is performed, it is preferable that Si be added so that the ratio Mn/Si be
4.0 or more and 12 or less.
Mn: 0.60% or more and 1.10% or less
[0032] Mn is a chemical element which contributes to an improvement in strength and toughness
as a result of decreasing the grain diameter of a steel microstructure, and such an
effect is realized in the case where the Mn content is 0.60% or more. On the other
hand, in the case where the Mn content is increased, since a fine martensite microstructure
is more likely to be formed in center segregation part, and since MnS, which becomes
the origin of HIC, is more likely to be formed, it is necessary that the Mn content
be controlled to be 1.10% or less. Therefore, the Mn content is set to be in a range
of 0.60% or more and 1.10% or less, or preferably in a range of 0.75% or more and
1.05% or less.
P: 0.008% or less
[0033] Since P is a chemical element which is contained as an inevitable impurity, and since
P deteriorates HIC resistance as a result of significantly increasing the hardness
of a center segregation part, it is preferable that the P content be as small as possible,
however, a P content of 0.008% or less is acceptable. Moreover, since there is an
increase in cost due to an increase in refining time in order to markedly decrease
the P content, it is preferable that the P content be 0.002% or more.
S: 0.0010% or less
[0034] Since S is, like P, a chemical element which is inevitably contained in steel, and
since S forms MnS in steel, it is preferable that the S content be as small as possible,
however, a S content of 0.0010% or less is acceptable, or preferably 0.0006% or less.
Nb: 0.010% or more and 0.060% or less
[0035] Nb is a chemical element which contributes to an increase in the strength of steel
as a result of precipitating in the form of fine Nb carbonitrides in a coiling process
when hot-rolled steel sheet is manufactured. Also, Nb is a chemical element which
contributes to an improvement in the toughness of a weld zone as a result of inhibiting
the growth of austenite grains when electric resistance welding is performed. Such
effects are realized in the case where the Nb content is 0.010% or more. On the other
hand, in the case where the Nb content is more than 0.060%, Nb carbonitrides having
a large grain diameter, which become the origins of HIC, are more likely to be formed.
Therefore, the Nb content is set to be in a range of 0.010% or more and 0.060% or
less, or preferably in a range of 0.030% or more and 0.060% or less.
Ti: 0.001% or more and 0.020% or less
[0036] Ti is a chemical element which is added in order to render N, which significantly
deteriorates the toughness of steel, harmless by fixing N in the form of TiN. Such
an effect is realized in the case where the Ti content is more than 0.001%. On the
other hand, in the case where the Ti content is more than 0.020%, since there is an
increase in the amount of Ti carbonitrides which precipitate along the cleavage plane
of Fe, there is a deterioration in the toughness of steel. Therefore, the Ti content
is set to be in a range of 0.001% or more and 0.020% or less, or preferably in a range
of 0.005% or more and 0.015% or less.
Mo: 0.05% or less
[0037] Mo is a chemical element which is significantly effective for improving the toughness
and strength of steel by improving hardenability, but, since Mo forms a martensite
microstructure as a result of being concentrated in a center segregation part, there
is a deterioration in HIC resistance. Therefore, it is preferable that the Mo content
be as small as possible, however, a Mo content of 0.05% or less is acceptable. It
is more preferable that the Mo content be 0.01% or less.
Cr: 0.05% or more and 0.50% or less
[0038] Cr is a chemical element which is effective for improving the toughness and strength
of steel by improving hardenability, and such an effect is realized in the case where
the Cr is added 0.05% or more, but, in the case where the Cr is added more than 0.50%,
there is a significant deterioration in the toughness of a weld zone as a result of
forming Cr oxides when electric resistance welding is performed. In order to inhibit
such a deterioration, the Cr content is set to be in a range of 0.05% or more and
0.50% or less, or preferably in a range of 0.05% or more and 0.30% or less.
Al: 0.01% or more and 0.08% or less
[0039] Although Al is added as a deoxidation agent, there is insufficient deoxidation effect
in the case where the Al content is less than 0.01%, and, on the other hand, there
is a deterioration in HIC resistance and toughness due to an increase in the amount
of Al-based oxides having a large grain diameter which are retained in steel in the
case where the Al content is more than 0.08%. Therefore, the Al content is set to
be in a range of 0.01% or more and 0.08% or less, or preferably in a range of 0.01%
or more and 0.05% or less.
Ca: 0.0005% or more and 0.0050% or less
[0040] Ca is a chemical element which is effective for improving HIC resistance by controlling
the shape of sulfide-based inclusions, and such an effect is realized in the case
where the Ca content is 0.0005% or more. On the other hand, in the case where the
Ca content is more than 0.0050%, such an effect becomes saturated, and, in addition,
there is a deterioration in HIC resistance as a result of forming a large amount of
Ca oxides. Therefore, the Ca content is set to be in a range of 0.0005% or more and
0.0050% or less, or preferably in a range of 0.0010% or more and 0.0030% or less.
O: 0.005% or less
[0041] Since oxygen deteriorates hot workability, corrosion resistance, toughness, and HIC
resistance as a result of forming various oxides, it is preferable that the oxygen
content be as small as possible, however, an oxygen content of 0.005% or less is acceptable,
or preferably 0.0035% or less.
[0042] In the present invention, one or more selected from among Cu, Ni, and V may be further
added in the amounts described below.
Cu: 0.50% or less
[0043] Cu is a chemical element which contributes to an improvement in the toughness and
strength of steel through an improvement in hardenability, and, since Cu is less likely
to be concentrated in a center segregation part than Mn and Mo which have similar
effect, Cu can increase the strength of steel without deteriorating HIC resistance.
Therefore, Cu is added in accordance with the strength grade. Such an effect is realized
in the case where the Cu content is 0.05% or more, but, in the case where the Cu content
is more than 0.50%, the effect becomes saturated and there is an unnecessary increase
in cost. Therefore, the Cu content is 0.50% or less, or preferably 0.40% or less.
Ni: 0.50% or less
[0044] Ni is, like Cu, a chemical element which contributes to an improvement in the toughness
and strength of steel through an improvement in hardenability, and, since Ni is less
likely to be concentrated in a center segregation part than Mn and Mo which have a
similar effect, Ni can increase the strength of steel without deteriorating HIC resistance.
Therefore, Ni is added in accordance with the strength grade. Such an effect is realized
in the case where the Ni content is 0.05% or more, but, in the case where the Ni content
is more than 0.50%, the effect becomes saturated and there is an unnecessary increase
in cost. Therefore, the Ni content is 0.50% or less, or preferably 0.40% or less.
V: 0.10% or less
[0045] V is a chemical element which contributes to an increase in the strength of steel
through solute strengthening and precipitation strengthening in the case where the
V content is 0.005% or more, but, in the case where the V content is more than 0.10%,
since there is an increase in the hardness of a center segregation part, there is
a deterioration in HIC resistance. Therefore, the V content is set to be 0.10% or
less, or preferably 0.080% or less.
SP: 1.90 or less
[0046] In the present invention, an SP value, which is derived from the contents of various
alloy chemical elements, satisfies expression (1) below.

where SP is derived from SP = Mn + Mo + 11.3 × C + 0.29 × (Cu + Ni) + 0.60 × Cr +
0.88 × V, where atomic symbols in the equation respectively represent the contents
(mass%) of the corresponding chemical elements, and where the atomic symbol of a chemical
element which is not added is assigned a value of 0 (zero).
[0047] An SP value was formulated in order to estimate the hardness of a center segregation
part of a hot-rolled steel sheet which is used as a raw material of an electric resistance
welded steel pipe using the contents of various alloy chemical elements, and, since
the chemical elements are markedly concentrated in a center segregation part in the
case where the SP value is more than 1.90, the condition that the hardness ratio of
a center segregation part to a non-segregation part is less than 1.20 is not satisfied.
In addition, since the hardness ratio of a center segregation part to a non-segregation
part decreases with decreasing SP value, it is necessary to control the upper limit
of the SP value to be, for example, 1.75 in the case where it is required that HIC
resistance be further improved in order to achieve a CLR of 5% or less.
EC: 1.2 or more and 4.0 or less
[0048] Moreover, in the present invention, it is preferable that an EC value which is described
below satisfy expression (2) below in order to effectively render sulfide-based inclusions
harmless by adding Ca.

where EC is expressed by EC = [Ca]eff / (1.25 × S), where [Ca]eff is derived from
Ca - (0.18 + 130 × Ca) × O, and where atomic symbols Ca, S, and O in the equations
respectively represent the contents (mass%) of the corresponding chemical elements.
[0049] The EC value indicates whether the content of Ca, which is added in order to control
the shape of sulfide-based inclusions, is sufficient to form CaS, and the Ca content
is insufficient in the case where the EC value is less than 1.2, which results in
MnS, which becomes the origin of HIC, being formed. On the other hand, in the case
where the EC value is more than 4.0, since Ca-based oxides are formed in a large amount,
there is a deterioration in HIC resistance due to a deterioration in the cleaning
level of steel. Therefore, it is preferable that the EC value be in a range of 1.2
or more and 4.0 or less, or more preferably in a range of 1.4 or more and 3.6 or less.
[0050] Here, the remainder of the chemical elements other than constituents described above
consists of Fe and inevitable impurities. However, other trace elements may be added
as long as the effects of the present invention are not decreased.
2. Regarding metallic structure
[0051] Subsequently, the metallic structure of the present invention will be described.
[0052] It is necessary to form a metallic structure composed of a bainitic-ferrite microstructure
in order to achieve not only a high strength of X52 (a YS of more than 380 MPa) or
more in accordance with API standards but also minimum required toughness (a ductile-brittle
transition temperature of -60°C or lower in a Charpy impact test) for a steel pipe
which is used for a linepipe. Since there is a deterioration in yield strength, toughness,
and HIC resistance in the case where different kinds of microstructures such as ferrite,
fine martensite, pearlite, and residual austenite exist in a bainitic-ferrite microstructure,
it is preferable that the area fractions of the microstructures other than a bainitic-ferrite
microstructure be as small as possible. However, in the case where the area fractions
of the microstructures other than a bainitic-ferrite microstructure are markedly small,
since the influences of the microstructures other than a bainitic-ferrite microstructure
are negligible small, the microstructures other than a bainitic-ferrite microstructure
may be included to some extent. Specifically, a microstructure having a total area
fraction of the steel microstructures other than a bainitic-ferrite microstructure
(such as a ferrite microstructure, a fine martensite microstructure, a pearlite microstructure,
and a residual austenite microstructure) of less than 3% may be considered to be a
single bainitic-ferrite microstructure and is included in the present invention.
[0053] The metallic structure described above can be achieved by using steel having the
chemical composition described above and the manufacturing method described below.
3. Regarding the hardness of a center segregation part
[0054] From the results of the investigations regarding the relationship between the results
of the HIC test on an electric resistance welded steel linepipe and the hardness of
a center segregation part of a steel sheet, it was found that there is a case where
the condition that a CLR is 15% or less cannot be satisfied even if the Vickers hardness
of a center segregation part is controlled to be Hv 230 or less. From the results
of the investigations regarding the reason for that conducted from the viewpoint of
material uniformity, it was found that, as Fig. 1 illustrates, the CLR is 15% or less
in the case where the hardness ratio of a center segregation part to a non-segregation
part (the Vickers hardness of a center segregation part/the Vickers hardness of a
non-segregation part) is less than 1.20. Then, from the results of the investigations
regarding a steel chemical composition with which the ratio of the hardness of a center
segregation part to the hardness of a non-segregation part becomes less than 1.20,
it was found that, as Fig. 2 illustrates, the SP value of the steel chemical composition
with which the ratio of the hardness of a center segregation part to the hardness
of a non-segregation part becomes less than 1.20 is 1.90 or less.
[0055] Here, the hardness of a center segregation part and the hardness of a non-segregation
part were, as Fig. 3 illustrates, respectively determined for 15 points each on a
center segregation line and in a portion located at 200 µm from the center segregation
line, and the arithmetic average values of the determined values were derived, where
the center segregation line was exposed by performing etching using a 2%-nital solution
for a duration of 30 seconds or more on a test piece for microstructure observation.
4. Regarding manufacturing conditions
[0056] Subsequently, manufacturing conditions for achieving the steel microstructure described
above will be described.
[0057] A slab heating temperature is set to be 1100°C or higher and 1300°C or lower. In
the case where the temperature is lower than 1100°C, since the temperature is not
high enough for carbides, which are formed in steel when continuous casting is performed,
to completely form solid solutions, the required strength cannot be achieved. On the
other hand, in the case where the temperature is higher than 1300°C, since there is
a marked increase in austenite grain diameter, there is a deterioration in toughness.
Here, this temperature refers to the temperature of the interior of the heating furnace,
and the center of the slab is presumed to be heated to this temperature.
[0058] In finish rolling, it is necessary that finish rolling be performed under the condition
that cumulative rolling reduction ratio is 20% or more at a temperature of 930°C or
lower. In the case where the cumulative rolling reduction ratio is less than 20%,
since there are an insufficient number of nucleation sites of a bainitic-ferrite microstructure,
there is an excessive increase in the grain diameter of the microstructure, which
results in a deterioration in toughness. However, in the case where the cumulative
rolling reduction ratio is more than 80%, since the effect becomes saturated, and
since a very high load is applied to a rolling mill, it is preferable that the upper
limit of the cumulative rolling reduction ratio be 80% or less.
[0059] The average cooling rate for the central part in the thickness direction of a steel
sheet is set to be 5°C/sec. or more and 100°C/sec. or less. In the case where the
cooling rate is less than 5°C/sec, the area fractions of a ferrite microstructure
and/or a pearlite microstructure become 3% or more even if hardenability increasing
chemical elements such as Cu, Ni, and Cr are added. Therefore, it is necessary that
the cooling rate be 5°C/sec. or more. On the other hand, in the case where the cooling
rate is more than 100°C/sec, the area fraction of a martensite microstructure becomes
3% or more. The cooling rate of the central part in the thickness direction of a steel
sheet was calculated by deriving the temperature history of the central part in the
thickness direction of the steel sheet by performing heat-transfer calculation using
the cooling capacity (heat-transfer coefficient) of a run-out, which had been investigated
in advance, and the surface temperature of the steel sheet, which had been determined
using a radiation thermometer on the run-out.
[0060] The cooling stop temperature is set to be in a range of 380°C or higher and 600°C
or lower. In the case where the cooling stop temperature is higher than 600°C, since
the area fraction of a ferrite microstructure and a pearlite microstructure becomes
3% or more, and since there is an increase in the diameter of precipitation strengthening
grains such as Nb carbonitrides, there is a decrease in strength. On the other hand,
in the case where the cooling stop temperature is lower than 380°C, since there is
an improvement in the deformation resistance of a steel sheet, it is difficult to
coil the steel sheet into a coil shape, and there is a decrease in strength due to
precipitation strengthening grains such as Nb carbonitrides not being precipitated.
[EXAMPLE 1]
[0061] By performing hot rolling on steel materials having the chemical compositions given
in Table 1 under the hot rolling conditions and the cooling conditions given in Table
2, and by coiling the hot-rolled steel sheets, hot-rolled steel sheets having the
thicknesses given in Table 2 were obtained. Here, steel grade G through K are comparative
example steels having a chemical composition, SP value or the like which is out of
the range according to the present invention.
[Table 1]
mass% |
Steel Grade |
C |
Si |
Mn |
P |
S |
Nb |
Ti |
Mo |
Al |
Ca |
Cu |
Ni |
Cr |
V |
O |
SP Value*1 |
EC Value*2 |
Note |
A |
0.06 |
0.18 |
0.90 |
0.006 |
0.0004 |
0.045 |
0.012 |
0.01 |
0.045 |
0.0022 |
- |
- |
0.15 |
- |
0.0025 |
1.68 |
2.1 |
Example Steel |
B |
0.04 |
0.13 |
1.05 |
0.007 |
0.0005 |
0.025 |
0.010 |
0.01 |
0.040 |
0.0025 |
- |
- |
0.10 |
- |
0.0017 |
1.57 |
2.6 |
Example Steel |
C |
0.04 |
0.13 |
0.76 |
0.005 |
0.0004 |
0.042 |
0.008 |
0.02 |
0.038 |
0.0028 |
0.37 |
0.34 |
0.10 |
- |
0.0031 |
1.50 |
2.2 |
Example Steel |
D |
0.05 |
0.10 |
0.84 |
0.005 |
0.0004 |
0.035 |
0.009 |
0.01 |
0.033 |
0.0030 |
0.12 |
0.10 |
0.25 |
- |
0.0022 |
1.63 |
3.5 |
Example Steel |
E |
0.03 |
0.16 |
1.00 |
0.005 |
0.0004 |
0.035 |
0.009 |
0 |
0.033 |
0.0030 |
- |
0.09 |
0.30 |
0.080 |
0.0022 |
1.62 |
3.5 |
Example Steel |
F |
0.05 |
0.13 |
1.03 |
0.006 |
0.0004 |
0.044 |
0.008 |
0 |
0.042 |
0.0025 |
0.30 |
0.30 |
0.08 |
0.060 |
0.0025 |
1.87 |
2.5 |
Example Steel |
G |
0.04 |
0.13 |
1.25 |
0.005 |
0.0006 |
0.028 |
0.008 |
0 |
0.045 |
0.0025 |
0.17 |
0.14 |
- |
- |
0.0020 |
1.79 |
2.0 |
Comparative Example Steel |
H |
0.04 |
0.13 |
1.05 |
0.006 |
0.0004 |
0.042 |
0.010 |
0.20 |
0.034 |
0.0021 |
0.15 |
0.15 |
- |
- |
0.0018 |
1.79 |
2.6 |
Comparative Example Steel |
I |
0.06 |
0.13 |
1.00 |
0.008 |
0.0005 |
0.025 |
0.012 |
0 |
0.055 |
0.0023 |
0.40 |
0.42 |
0.08 |
0.045 |
0.0016 |
2.00 |
2.5 |
Comparative Example Steel |
J |
0.06 |
0.13 |
1.10 |
0.004 |
0.0006 |
0.055 |
0.013 |
0.03 |
0.035 |
0.0045 |
- |
- |
- |
0.020 |
0.0015 |
1.83 |
4.5 |
Comparative Example Steel |
K |
0.04 |
0.19 |
1.45 |
0.006 |
0.0009 |
0.034 |
0.009 |
0.17 |
0.040 |
0.0025 |
- |
- |
0.10 |
- |
0.0016 |
2.13 |
1.5 |
Comparative Example Steel |
Annotation: An underlined portion indicates a value out of the range according to
the present invention.
*1 SP=Mn+Mo+11.3xC+0.29x(Cu+Ni)+0.60xCr+0.88xV, where an atomic symbols in the equation
respectively represent the contents (mass%) of the corresponding chemical elements.
*2 EC=[Ca]eff/(1.25xS), where [Ca]eff is derived from Ca-(0.18+130xCa)xO,
and where atomic symbols Ca, S, and O in the equations respectively represent the
contents (mass%) of the corresponding chemical elements. |
[Table 2]
Steel Sheet No. |
Steel Grade |
Thickness (mm) |
Slab Heating Temperature (°C) |
Cumulative Rolling Reduction Ratio in Finish Rolling (%) |
Finishing Delivery Temperature (°C) |
Average Cooling Rate of Central Part in Thickness Direction (°C/sec.) |
Cooling Stop Temperature (°C) |
Note |
1 |
A |
16 |
1250 |
40 |
820 |
25 |
540 |
Example |
2 |
B |
22 |
1200 |
55 |
810 |
80 |
500 |
Example |
3 |
C |
10 |
1200 |
25 |
840 |
50 |
450 |
Example |
4 |
C |
12 |
1200 |
45 |
840 |
20 |
500 |
Example |
5 |
C |
19 |
1200 |
55 |
810 |
10 |
520 |
Example |
6 |
C |
25 |
1200 |
65 |
810 |
25 |
560 |
Example |
7 |
D |
14 |
1200 |
40 |
820 |
60 |
420 |
Example |
8 |
D |
16 |
1200 |
40 |
820 |
55 |
480 |
Example |
9 |
D |
19 |
1200 |
55 |
810 |
30 |
530 |
Example |
10 |
E |
18 |
1150 |
55 |
810 |
10 |
510 |
Example |
11 |
F |
12 |
1200 |
33 |
830 |
15 |
500 |
Example |
12 |
C |
19 |
1350 |
55 |
810 |
20 |
520 |
Comparative Example |
13 |
C |
19 |
1200 |
15 |
810 |
20 |
520 |
Comparative Example |
14 |
C |
19 |
1200 |
55 |
820 |
2 |
520 |
Comparative Example |
15 |
C |
19 |
1200 |
55 |
820 |
20 |
650 |
Comparative Example |
16 |
G |
22 |
1200 |
60 |
810 |
30 |
550 |
Comparative Example |
17 |
H |
19 |
1200 |
55 |
810 |
10 |
540 |
Comparative Example |
18 |
I |
16 |
1150 |
40 |
820 |
15 |
540 |
Comparative Example |
19 |
J |
16 |
1250 |
40 |
820 |
15 |
540 |
Comparative Example |
20 |
K |
20 |
1250 |
55 |
830 |
10 |
540 |
Comparative Example |
Annotation: An underlined portion indicates a value out of the range according to
the present invention. |
[0062] Using test pieces which had been collected from the obtained hot-rolled steel sheet,
and by performing microstructure observation, a tensile test, a Charpy impact test,
hardness determination, and a HIC test, tensile properties, toughness, and HIC resistance
were evaluated.
[0063] By collecting a test piece for microstructure observation from the obtained hot-rolled
steel sheet, by polishing and etching a cross-section in the rolling direction, and
by using an optical microscope (at a magnification of 400 times) and an electron scanning
microscope (at a magnification of 1000 times), photographs were taken for 5 microscopic
fields or more in the central part in the thickness direction of the steel sheet in
order to observe the kinds of microstructures and whether or not steel microstructures
other than a bainitic-ferrite microstructure (such as ferrite, fine martensite, pearlite,
and residual austenite) existed.
[0064] A tensile test piece was collected from the obtained hot-rolled steel sheet so that
the longitudinal direction was at a right angle to the rolling direction (C direction),
and a tensile test was performed at room temperature in accordance with API-5L specification
in order to determine yield strength YS (deformation stress for a nominal strain of
0.5%) and tensile strength TS.
[0065] A v-notched test piece was collected from the central part in the thickness direction
of the obtained hot-rolled steel sheet so that the longitudinal direction was at a
right angle to the rolling direction (C direction), and absorbed energy and a percent
brittle fracture were determined by performing a Charpy impact test at a temperature
range of -140°C to 0°C in accordance with JIS Z 2242 in order to determine a temperature
(fracture transition temperature) at which a percent brittle fracture was 50%. Here,
three test pieces were used for one temperature in order to obtain the arithmetic
averages of the determined absorbed energy and percent brittle fracture.
[0066] The hardness of a center segregation part and the hardness of a non-segregation part
were respectively determined for 15 points each on a segregation line and in a portion
located at 200 µm from the segregation line, and the arithmetic average values of
the determined values were derived, where the segregation line was exposed by performing
etching using a 2%-nital solution for a duration of 30 seconds or more on a test piece
for microstructure observation (Fig. 3). Here, the hardness was determined using a
Vickers hardness meter with a testing force of 0.3 kgf. The hardness ratio was calculated
by dividing the hardness of a segregation part by the hardness of a non-segregation
part.
[0067] Using a HIC test piece having the thickness of the steel sheet, a width of 20 mm,
and a length of 100 mm which was collected from the obtained hot-rolled steel sheet
so that the longitudinal direction was the rolling direction of the steel sheet, a
HIC test was performed using an A solution in accordance with NACE TM 0284 in order
to evaluate HIC resistance. Here, 10 test pieces were used for one coil, and a compressive
strain of 10% in a width direction was applied to the test pieces in advance in order
to simulate plastic strain which is applied to a steel sheet when forming is performed
in a process for manufacturing an electric resistance welded steel pipe. From the
test results, in the case where CLR was 15% or less for all the test pieces for one
coil, the coil was judged as satisfactory (O) in terms of HIC resistance. In the case
where the CLR was more than 15% for one or more of the test pieces for one coil, the
coil was judged as unsatisfactory (x) in terms of HIC resistance.
[0068] The obtained results are given in Table 3.
[Table 3]
Steel Sheet No. |
Steel Grade |
Metallic Structure |
Yield Strength (MPa) |
Tensile Strength (MPa) |
Charpy (vTrs) |
Hardness Ratio |
HIC Resistance |
Note |
1 |
A |
BF |
511 |
585 |
-70 |
1.06 |
○ |
Example |
2 |
B |
BF |
435 |
508 |
-120 |
1.04 |
○ |
Example |
3 |
C |
BF |
490 |
557 |
-100 |
1.01 |
○ |
Example |
4 |
C |
BF |
495 |
563 |
-125 |
1.01 |
○ |
Example |
5 |
C |
BF |
489 |
563 |
-85 |
1.01 |
○ |
Example |
6 |
C |
BF |
482 |
560 |
-95 |
1.01 |
○ |
Example |
7 |
D |
BF |
480 |
546 |
-130 |
1.07 |
○ |
Example |
8 |
D |
BF |
494 |
554 |
-100 |
1.07 |
○ |
Example |
9 |
D |
BF |
497 |
563 |
-95 |
1.07 |
○ |
Example |
10 |
E |
BF |
500 |
567 |
-80 |
1.06 |
○ |
Example |
11 |
F |
BF |
534 |
616 |
-100 |
1.17 |
○ |
Example |
12 |
C |
BF |
488 |
558 |
-40 |
1.02 |
○ |
Comparative Example |
13 |
C |
BF |
516 |
573 |
-50 |
1.01 |
○ |
Comparative Example |
14 |
C |
BF+F+P |
467 |
539 |
-50 |
1.02 |
× |
Comparative Example |
15 |
C |
F+P |
460 |
545 |
-45 |
1.02 |
× |
Comparative Example |
16 |
G |
BF |
472 |
547 |
-100 |
1.16 |
× |
Comparative Example |
17 |
H |
BF |
498 |
573 |
-110 |
1.15 |
× |
Comparative Example |
18 |
I |
BF |
476 |
548 |
-70 |
1.24 |
× |
Comparative Example |
19 |
J |
BF |
505 |
582 |
-60 |
1.17 |
× |
Comparative Example |
20 |
K |
BF |
533 |
600 |
-100 |
1.30 |
× |
Comparative Example |
Annotation: An underlined portion indicates a value out of the range according to
the present invention. |
[0069] The examples of the present inventions were all steel sheets having a high yield
strength YS of 380 MPa or more, minimum required toughness for a linepipe as indicated
by a vTrs of -60°C or lower, and excellent HIC resistance as indicated by a hardness
ratio of less than 1.20. On the other hand, the comparative examples, which were out
of the range according to the present invention, did not achieve the desired properties
for a hot-rolled steel sheet for a high strength electric resistance welded steel
pipe excellent in terms of HIC resistance, because the desired toughness was not achieved,
or because there was a deterioration in HIC resistance.