TECHNICAL FIELD
[0001] This disclosure relates to a high strength steel plate for sour-resistant line pipes
that is used in the field of sour-resistant line pipes and that is excellent in the
uniformity of material homogeneity, in particular HIC characteristics, in the steel
plate, and to a high strength steel pipe using the same.
BACKGROUND
[0002] In general, a line pipe is manufactured by forming a steel plate manufactured by
a plate mill or a hot rolling mill into a steel pipe by UOE forming, press bend forming,
roll forming, or the like.
[0003] The line pipe used to transport crude oil and natural gas containing hydrogen sulfide
is required to have so-called sour resistance such as resistance to hydrogen-induced
cracking (HIC resistance) and resistance to sulfide stress corrosion cracking (SSCC
resistance), in addition to strength, toughness, weldability, and so on. Above all,
in HIC, hydrogen ions caused by corrosion reaction adsorb on the steel surface, penetrate
into the steel as atomic hydrogen, diffuse and accumulate around non-metallic inclusions
such as MnS in the steel and the hard second phase structure, and become molecular
hydrogen, thereby causing cracking due to its internal pressure.
[0004] Several methods have been proposed to prevent such HIC. JPH5-271766A (PTL 1) and
JPH7-173536A (PTL 2) propose methods for suppressing central segregation in a high
strength steel plate by keeping the C and Mn contents low, while performing morphological
control of sulfide inclusions by keeping the S content low and adding Ca, and supplementing
the decrease in strength associated therewith by adding Cr, Mo, Ni, and the like and
performing accelerated cooling.
[0005] On the other hand, the demand for a steel plate with higher strength and higher toughness
is increasing from the viewpoint of increasing the size of steel structures and reducing
costs. For the purposes of property improvement and alloying element reduction of
steel plates and elimination of heat treatment, high strength steel plates are usually
manufactured by applying a so-called TMCP (Thermo-Mechanical Control Process) technique
combining controlled rolling and controlled cooling.
[0006] In order to increase the strength of the steel material by using TMCP technique,
it is effective to increase the cooling rate at the time of controlled cooling. However,
when the control cooling is performed at a high cooling rate, the surface layer of
the steel plate is rapidly cooled, and the hardness of the surface layer becomes higher
than that of the inside of the steel plate, and the hardness distribution in the plate
thickness direction becomes uneven. Therefore, it is a problem in terms of ensuring
the material homogeneity in the steel plate.
[0007] To solve the above problems, for example,
JP2002-327212A (PTL 3) and
JP3711896 B (PTL 4) describe methods for producing a steel plate for line pipes in which a steel
plate surface after subjection to accelerated cooling is heated to a higher temperature
than the interior using a high-frequency induction heating device such that the hardness
is reduced at the surface layer.
[0008] On the other hand, when the scale thickness on the steel plate surface is uneven,
the cooling rate is also uneven at the underlying steel plate during cooling, causing
a problem of local variation in the cooling stop temperature in the steel plate. As
a result, unevenness in scale thickness causes variation in the steel plate material
property in the plate width direction. On the other hand, JPH9-57327A (PTL 5) and
JP3796133B (PTL 6) describe methods for improving the shape of a steel plate by performing descaling
immediately before cooling to suppress cooling unevenness caused by scale thickness
unevenness.
CITATION LIST
Patent Literature
SUMMARY
(Technical Problem)
[0010] However, although the techniques of PTLs 1 to 4 focus on central segregation area,
none of these documents consider the uniformity of the HIC resistance in the plate
width direction. Variation in central segregation in the plate width direction in
a slab result in variation in the HIC resistance in the plate width direction of the
rolled steel plate.
[0011] Further, according to the present inventors' study, it turned out that there is still
a room for improvement in high strength steel plates obtained by the methods described
in PTLs 5 and 6 in terms of uniformity of the HIC resistance in the plate width direction.
The reason can be considered as follows. The methods of PTLs 5 and 6 apply descaling
to reduce the surface characteristics defects due to the scale indentation during
hot leveling and to reduce the variation in the cooling stop temperature of the steel
plate to improve the steel plate shape. However, no consideration is given to the
cooling conditions for obtaining a uniform material property.
[0012] Thus, conventionally, when combining low-cost chemical compositions and controlled
cooling at a high cooling rate, it was impossible to manufacture a high strength steel
plate that has both of proper material homogeneity in the steel plate and proper HIC
resistance.
[0013] It would thus be helpful to provide a high strength steel plate for sour-resistant
line pipes that is excellent in HIC resistance in which variation in the HIC resistance
in the plate width direction is suppressed, and a high strength steel pipe using the
same.
(Solution to Problem)
[0014] To solve the above problems, the present inventors made intensive studies on the
chemical compositions and microstructures of steel materials and the manufacturing
methods of a high strength steel plate having a strength of X65 grade in accordance
with the API standard in order to prevent HIC generation from the central segregation
area, suppress the variation in the HIC resistance in the plate width direction, and
improve the material homogeneity in the steel plate. As a result, it was discovered
that it is possible to suppress the variation in central segregation in the plate
width direction of a steel plate by a combined use of secondary cooling of a cast
steel (slab) under particular conditions and controlled cooling after hot rolling
under particular conditions, and the present disclosure was completed based on this
discovery.
[0015] We thus provide:
- [1] A high strength steel plate for sour-resistant line pipes comprising: a chemical
composition containing (consisting of), by mass%, C: 0.02 % to 0.08 %, Si: 0.01 %
to 0.50 %, Mn: 0.50 % to 1.80 %, P: 0.001 % to 0.015 %, S: 0.0002 % to 0.0015 %, Al:
0.01 % to 0.08 %, and Ca: 0.0005 % to 0.005 %, with the balance being Fe and inevitable
impurities, wherein in a cross-section perpendicular to a rolling direction of the
steel plate, the number of Mn-concentrated spots that are approximated to an elliptical
shape having a major axis length of more than 1.5 mm, in a measuring region located
±5 mm from a plate thickness center toward a plate thickness direction, is 3 or less
per 100 mm in length in a plate width direction, HIC resistance is 10 % or less in
terms of CAR at a W/4 position, a W/2 position, and a 3W/4 position from one end in
the plate width direction of the steel plate, where W denotes a plate width, variation
in the HIC resistance in the plate width direction in terms of 3σ is 5 % or less when
σ denotes a standard deviation of CARs, and a tensile strength is 520 MPa or more.
- [2] The high strength steel plate for sour-resistant line pipes according to the foregoing
[1], wherein the chemical composition further contains, by mass%, at least one selected
from the group consisting of Cu: 0.50 % or less, Ni: 0.50 % or less, Cr: 0.50 % or
less, and Mo: 0.50 % or less.
- [3] The high strength steel plate for sour-resistant line pipes according to the foregoing
[1] or [2], wherein the chemical composition further contains, by mass%, at least
one selected from the group consisting of Nb: 0.005 % to 0.1 %, V: 0.005 % to 0.1
%, and Ti: 0.005 % to 0.1 %.
- [4] A high strength steel pipe using the high strength steel plate for sour-resistant
line pipes as recited in any one of the foregoing [1] to [3].
(Advantageous Effect of Invention)
[0016] The high strength steel plate for sour-resistant line pipes disclosed herein has
excellent HIC resistance in which variation in the HIC resistance in the plate width
direction is suppressed. Accordingly, the high strength steel pipe disclosed herein
using this high strength steel plate has excellent HIC resistance in which variation
in the HIC resistance in the pipe circumferential direction is suppressed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In the accompanying drawings:
FIG. 1 is a schematic view illustrating a C cross-section of a steel plate for explanation
of the positions of EPMA analyzing regions in an example;
FIG. 2 is a schematic view illustrating a C cross-section of a steel plate for explanation
of the portions for HIC test piece sampling in an example; and
FIGS. 3A and 3B are diagrams for explaining secondary cooling of cast steel in continuous
casting for producing a high strength steel plate according to the present embodiment,
where FIG. 3A is a schematic diagram illustrating an injection range and a water flux
density distribution of coolant when the coolant is injected from one two-fluid spray
nozzle, and FIG. 3B is a schematic diagram illustrating an injection range and a water
flux density distribution of coolant and a lap margin of the injection range when
the coolant is injected from two two-fluid spray nozzles.
DETAILED DESCRIPTION
[0018] Hereinafter, the high strength steel plate for sour-resistant line pipes according
to the present disclosure will be described in detail.
[Chemical composition]
[0019] First, the chemical composition of the high strength steel plate disclosed herein
and the reasons for limitation thereof will be described. Hereinbelow, all units shown
by % are mass%.
C: 0.02 % to 0.08 %
[0020] C contributes effectively to the improvement of strength. However, when the content
is less than 0.02 %, sufficient strength can not be secured. On the other hand, when
the content is more than 0.08 %, the hardness of the surface layer is increased during
accelerated cooling, and the HIC resistance deteriorates. The toughness also decreases.
Therefore, the C content is set in a range of 0.02 % to 0.08 %.
Si: 0.01 % to 0.50 %
[0021] Si is added for deoxidation. However, when the content is less than 0.01 %, the deoxidizing
effect is insufficient. On the other hand, when the content is more than 0.50 %, the
toughness and weldability deteriorate. Therefore, the Si content is set in a range
of 0.01 % to 0.50 %.
Mn :0.50 % to 1.80 %
[0022] Mn contributes effectively to the improvement of strength and toughness. However,
if the content is less than 0.50 %, the addition effect is poor, while if it exceeds
1.80 %, the hardness of the surface layer is increased during accelerated cooling,
and the HIC resistance deteriorates. The weldability also decreases. Therefore, the
Mn content is set in a range of 0.50 % to 1.80 %.
P: 0.001 % to 0.015 %
[0023] P is an inevitable impurity element that degrades the weldability and increases the
hardness of the central segregation area, causing deterioration in HIC resistance.
This tendency becomes more pronounced when the content exceeds 0.015 %. Therefore,
the upper limit is set at 0.015 %. The content is preferably 0.008 % or less. Although
a lower P content is preferable, the P content is set to 0.001 % or more from the
viewpoint of refining cost.
S: 0.0002 % to 0.0015 %
[0024] S is an inevitable impurity element that forms MnS inclusions in the steel and degrades
the HIC resistance, and hence a lower S content is preferable. However, up to 0.0015
% is acceptable. Although a lower S content is preferable, the S content is set to
0.0002 % or more from the viewpoint of refining cost.
Al: 0.01 % to 0.08 %
[0025] Al is added as a deoxidizing agent. However, an Al content below 0.01 % provides
no addition effect, while an Al content beyond 0.08 % lowers the cleanliness of the
steel and deteriorates the toughness. Therefore, the Al content is in a range of 0.01
% to 0.08 %.
Ca: 0.0005 % to 0.005 %
[0026] Ca is an element effective for improving HIC resistance through morphological control
of sulfide inclusions. If the content is less than 0.0005 %, however, the addition
effect is not sufficient. On the other hand, if the content exceeds 0.005 %, not only
the addition effect saturates, but also the HIC resistance is deteriorated due to
the reduction in the cleanliness of the steel. Therefore, the Ca content is in a range
of 0.0005 % to 0.005 %.
[0027] The basic components according to the present disclosure have been described above.
Optionally, however, the chemical composition according to the present disclosure
may also contain at least one selected from the group consisting of Cu, Ni, Cr, and
Mo in the following ranges to further improve the strength and toughness of the steel
plate.
Cu: 0.50 % or less
[0028] Cu is an element effective for improving the toughness and increasing the strength.
To obtain this effect, the Cu content is preferably 0.05 % or more, yet if the content
is too large, the weldability deteriorates. Therefore, when Cu is added, the Cu content
is up to 0.50 %.
Ni: 0.50 % or less
[0029] Ni is an element effective for improving the toughness and increasing the strength.
To obtain this effect, the Ni content is preferably 0.05 % or more, yet excessive
addition of Ni is not only economically disadvantageous but also deteriorates the
toughness of the heat-affected zone. Therefore, when Ni is added, the Ni content is
up to 0.50 %.
Cr: 0.50 % or less
[0030] Cr, like Mn, is an effective element for obtaining a sufficient strength even at
low C content. To obtain this effect, the Cr content is preferably 0.05 % or more,
yet if the content is too large, the weldability deteriorates. Therefore, when Cr
is added, the Cr content is up to 0.50 %.
Mo: 0.50 % or less
[0031] Mo is an element effective for improving the toughness and increasing the strength.
To obtain this effect, the Mo content is preferably 0.05 % or more, yet if the content
is too large, the weldability deteriorates. Therefore, when Mo is added, the Mo content
is up to 0.50 %.
[0032] The chemical composition according to the present disclosure may further optionally
contain one or more selected from the group consisting of Nb, V, and Ti in the following
ranges.
[0033] At least one selected from the group consisting of Nb: 0.005 % to 0.1 %, V: 0.005
% to 0.1 %, Ti: 0.005 % to 0.1 % All of Nb, V, and Ti are elements that can be optionally
added to enhance the strength and toughness of the steel plate. If the content of
each added element is less than 0.005 %, the addition effect is poor, while if it
exceeds 0.1 %, the toughness of the welded portion deteriorates. Therefore, the content
of each added element is preferably in a range of 0.005 % to 0.1 %.
[0034] The balance other than the above-described elements is Fe and inevitable impurities.
However, there is no intention in this expression of precluding the inclusion of other
trace elements, without impairing the action or effect of the present disclosure.
[Mn-concentrated spots]
[0035] In the high strength steel plate for sour-resistant line pipes disclosed herein,
it is important that in a cross-section perpendicular to a rolling direction (plate
length direction) of the steel plate, the number of Mn-concentrated spots that are
approximated to an elliptical shape having a major axis length of more than 1.5 mm,
in a measuring region located ±5 mm from a plate thickness center toward a plate thickness
direction, is 3 or less per 100 mm in length in a plate width direction.
[0036] As used herein, a "Mn-concentrated spot" refers to a site in which the Mn concentration
is higher than the addition amount of Mn (the Mn content in the steel plate) due to
segregation. This site is specifically identified as a site in which the Mn concentration
is 1.60 % or more when the Mn content in the steel plate is 1.50 % or less, and as
a site in which the Mn concentration is at least 0.10 % higher than the Mn content
in the steel plate when the Mn content in the steel plate is more than 1.50 % and
1.80 % or less.
[0037] According to the present inventors' studies, it was revealed that HIC cracking is
likely to occur from the positions of those Mn-concentrated spots having a major axis
length of more than 1.5 mm among the Mn-concentrated spots specified as described
above, and that HIC cracking occurs when the number of Mn-concentrated spots having
a major axis length of more than 1.5 mm exceeds 3 per 100 mm in length in the plate
width direction. Therefore, in the present disclosure, the number of Mn-concentrated
spots having a major axis length of more than 1.5 mm is 3 or less per 100 mm in length
in the plate width direction.
[0038] In the present disclosure, "the number of Mn-concentrated spots having a major axis
length of more than 1.5 mm per 100 mm in length in the plate width direction" is measured
as follows. First, a sample for analysis is cut out from a steel plate and polished
for preparation. This setup is carried out such that the surface of the sample becomes
a cross-section perpendicular to the plate length direction of the steel plate (a
C cross-section). Then, as illustrated in FIG. 1, in the C cross section, Mn concentration
mapping is performed using an electron probe microanalyzer (EPMA) for three regions
centering on each of the three points at the plate thickness center (t/2 position;
t is the plate thickness) of the steel plate and ranging ±5 mm in the plate thickness
direction (i.e., 10 mm thick) and ±200 mm in the plate width direction (i.e., 400
mm wide), at a W/4 position, a W/2 position, and a 3W/4 position from one end in the
plate width direction of the steel plate, where W denotes the plate width (hereinafter,
simply referred to as "W/4 position", "W/2 position", and "3W/4 position", respectively).
Note that the three regions may be one overlapping area depending on the plate width
of the steel plate. The mapping is performed using an electronic probe with a accelerating
voltage of 25 kV and a diameter of 0.15 mm. In each EPMA analyzing region (10 mm thick
and 400 mm wide), the number of Mn-concentrated spots having a major axis length of
more than 1.5 mm is counted and converted to the number per 100 mm in length in the
plate width direction.
[0039] It is preferable that the steel microstructure of the high strength steel plate for
sour-resistant line pipes disclosed herein is bainite microstructure in order to have
a tensile strength as high as 520 MPa or more. In this case, the bainite microstructure
includes a microstructure called bainitic ferrite or granular ferrite which contributes
to transformation strengthening. These microstructures appear through transformation
during or after accelerated cooling. If different microstructures such as ferrite,
martensite, pearlite, martensite austenite constituent, retained austenite, and the
like are mixed in the bainite microstructure, a decrease in strength, a deterioration
in toughness, a rise in surface hardness, and the like occur. Therefore, it is preferable
that microstructures other than the bainite phase have smaller proportions. However,
when the volume fraction of such microstructures other than the bainitic phase is
sufficiently low, their effects are negligible, and up to a certain amount is acceptable.
Specifically, in the present disclosure, if the total of the steel microstructures
other than bainite (such as ferrite, martensite, pearlite, martensite austenite constituent,
and retained austenite) is less than 5 % by volume fraction, there is no adverse effect,
and this is acceptable.
[Uniformity of the HIC resistance in the plate width direction]
[0040] In the high strength steel plate for sour-resistant line pipes disclosed herein,
it is important that the HIC resistance at a W/4 position, a W/2 position, and a 3W/4
position is 10 % or less in terms of CAR, and that the variation in the HIC resistance
in the plate width direction in terms of 3σ is 5% or less when σ denotes a standard
deviation of CARs. This means that the high strength steel plate has excellent HIC
resistance in which variation in the HIC resistance in the plate width direction is
suppressed. The HIC resistance at a W/4 position, a W/2 position, and a 3W/4 position
is preferably 5 % or less in terms of CAR.
[0041] In this disclosure, the "HIC resistance at a W/4 position, a W/2 position, and a
3W/4 position" is evaluated as follows. As illustrated in FIG. 2, in a C-section of
the steel plate, centering on the plate thickness center at a W/4 position, a W/2
position, and a 3W/4 position (total of three points) in the plate width direction,
test pieces of 20 mm thick and 20 mm wide are collected. From each of the three test
pieces thus obtained, three samples are collected, and a total of nine samples are
subjected to hydrogen-induced cracking (HIC) resistance examination. This examination
is conducted in the Method A environment according to NACE TM0284, and the crack area
ratio (CAR) is determined as a hydrogen-induced cracking criterion. In the high strength
steel plate for sour-resistant line pipes disclosed herein, all nine CARs thus obtained
are 10 % or less, and preferably 5 % or less.
[0042] Further, in this disclosure, the "variation in the HIC resistance in the plate width
direction" is evaluated in terms of 3σ when the standard deviation of nine CARs described
above is calculated as σ.
[Tensile strength]
[0043] The high strength steel plate disclosed herein is a steel plate for steel pipes having
a strength of X60 grade or higher in API 5L, and thus has a tensile strength of 520
MPa or more.
[Manufacturing method]
[0044] Hereinafter, the method and conditions for manufacturing the above-described high
strength steel plate for sour-resistant line pipes will be described concretely. The
manufacturing method disclosed herein comprises: subjecting steel having the above
chemical composition to continuous casting to prepare a cast steel (slab); heating
the slab; then hot rolling the slab to obtain a steel plate; and then subjecting the
steel plate to controlled cooling. At this time, by performing secondary cooling in
the continuous casting under particular conditions, and by performing the slab heating
and controlled cooling under particular conditions, it is possible to manufacture
a high strength steel plate for sour-resistant line pipes that has excellent HIC resistance
in which variation in the HIC resistance in the plate width direction is suppressed.
[Secondary cooling of a slab during continuous casting]
[0045] As illustrated in FIGS. 3A and 3B, the following secondary cooling method is used.
Coolant is sprayed on a cast steel 20 in a mist form from a plurality of two-fluid
spray nozzles 10A and 10B to cool the cast steel 20 while feeding the cast steel 20
in its longitudinal direction. The plurality of two-fluid spray nozzles 10A and 10B
are arranged at predetermined intervals in the width direction of the cast steel 20.
Regarding the two-fluid spray nozzles 10 (10A and 10B), the positions on the cast
steel at which a water flux density is 50 % of the water flux density immediately
below the two-fluid spray nozzles 10 are located away by a distance S (mm) from both
ends of each spraying range of the coolant in the width direction of the cast steel
20. The overlapping margin between the spraying ranges of the coolant sprayed from
the two-fluid spray nozzles 10A and 10B adjacent to each other is set in a range of
1.6 S to 2.4 S.
[0046] FIGS. 3A and 3B schematically illustrate the injection ranges and the water flux
density distributions of the coolant injected from two-fluid spray nozzle(s). FIG.
3A illustrates a distance S from both ends of the injection range at which a ratio
of a water flux density at that position to a water flux density immediately below
the two-fluid spray nozzle 10 is 50 %, and FIG. 3B illustrates the overlapping margin
between the injection ranges of the coolant injected from the two two-fluid spray
nozzles 10A and 10B.
[0047] The distance S from both ends of the injection range of the coolant injected from
the two-fluid spray nozzle 10 can be obtained as follows. First, a water flux density
distribution in the width direction of the cast steel of the coolant injected from
the two-fluid spray nozzle 10 is measured. The water flux density distribution can
be measured by placing the two-fluid spray nozzle 10 above a group of measures finely
divided in the width direction of the cast steel 1 and weighing the coolant injected
from the two-fluid spray nozzle 10 for each measuring apparatus.
[0048] The reason for setting the overlapping margin in a range of 1.6 S to 2.4 S is as
follows. That is, in the case of the cast steel being subjected to secondary cooling
with a plurality of two-fluid spray nozzles, even if the two-fluid spray nozzles are
arranged such that the water flux density of the coolant injected from each two-fluid
spray nozzle is uniform in the width direction of the cast steel, the collision pressure
is low at both ends of each injection range of the coolant, resulting in low ability
of cooling cast steel. Thus, it is impossible to cool the cast steel uniformly in
the width direction. However, if the overlapping margin is adjusted in the range of
1.6 S to 2.4 S, it is possible to uniformly cool the cast steel in the width direction,
considering the collision pressure distribution in addition to the water flux density
distribution in the width direction of the cast steel. That is, according to this
method, it is possible to cool the cast steel without lowering the cooling ability
in a region over which the injection ranges of the coolant from the adjacent two-fluid
spray nozzles 10A and 10B overlap, and to suppress the surface temperature deviation
in the width direction of the cast steel, enabling substantially uniform cooling.
Accordingly, it is possible to prepare a slab with suppressed variation in the central
segregation in the width direction.
[0049] Although FIG. 3B illustrates an example using two two-fluid spray nozzles 10A and
10B, in the case of performing secondary cooling of the cast steel with three or more
two-fluid spray nozzles, the overlapping margin of the injection ranges of the coolant
may be set as described above for those adjacent to each other among three or more
two-fluid spray nozzles.
[0050] Further, the two-fluid spray nozzle include, but is not limited to, for example,
a mist nozzle provided with a feed pipe for coolant and air, a mixing pipe, and a
nozzle tip.
[Slab heating temperature]
[0051] Slab heating temperature: 1000 °C to 1300 °C
If the slab heating temperature is lower than 1000 °C, carbides do not solute sufficiently
and the necessary strength can not be obtained. On the other hand, if the slab heating
temperature exceeds 1300 °C, the toughness is deteriorated. Therefore, the slab heating
temperature is set to 1000 °C to 1300 °C. This temperature is the temperature in the
heating furnace, and the slab is heated to this temperature to the center.
[Rolling finish temperature]
[0052] In a hot rolling step, in order to obtain high toughness for base metal, a lower
rolling finish temperature is preferable, yet on the other hand, the rolling efficiency
is lowered. Thus, the rolling finish temperature in terms of a temperature of the
surface of the steel plate needs to be set in consideration of the required toughness
for base metal and rolling efficiency. From the viewpoint of improving the strength
and the HIC resistance, it is preferable to set the rolling finish temperature at
or above the Ar
3 transformation temperature in terms of a temperature of the surface of the steel
plate. As used herein, the Ar
3 transformation temperature means the ferrite transformation start temperature during
cooling, and can be determined, for example, from the components of steel according
to the following equation. Further, in order to obtain high toughness for base metal,
it is desirable to set the rolling reduction ratio in a temperature range of 950 °C
or lower, which corresponds to the austenite non-recrystallization temperature range,
to 60 % or more. The temperature of the surface of the steel plate can be measured
by a radiation thermometer or the like.

where [%X] indicates the content by mass% of the element X in steel.
[Cooling start temperature in the controlled cooling]
[0053] Cooling start temperature: (Ar
3 - 10°C) or higher in terms of a temperature of the surface of the steel plate
[0054] If the temperature of the surface of the steel plate is low at the start of cooling,
ferrite forms in a large amount before controlled cooling, in particular, when the
temperature drop from the Ar
3 transformation temperature exceeds 10 °C, ferrite forms in a volume fraction of more
than 5 %, causing a significant reduction in the strength and a deterioration in the
HIC resistance. Therefore, the temperature of the surface of the steel plate at the
start of cooling is set to (Ar
3 - 10 °C) or higher.
[Cooling rate of the controlled cooling]
[0055] Average cooling rate in a temperature range from 750 °C to 550 °C in terms of an
average temperature of the steel plate: 15 °C/s or higher
[0056] If the average cooling rate in a temperature range from 750 °C to 550 °C in terms
of an average temperature of the steel plate is lower than 15 °C/s, a bainite microstructure
can not be obtained, causing deterioration in the strength and HIC resistance. Therefore,
the cooling rate in terms of an average temperature of the steel plate is set to 15
°C/s or higher. From the viewpoint of variation in the strength and hardness of the
steel plate, the steel plate average cooling rate is preferably 20 °C/s or higher.
The upper limit of the average cooling rate is not particularly limited, yet is preferably
80 °C/s or lower such that excessive low-temperature transformation products will
not be generated.
[Cooling stop temperature]
[0057] Cooling stop temperature: 250 °C to 550 °C in terms of an average temperature of
the steel plate
[0058] After the completion of rolling, a bainite phase is generated by performing controlled
cooling to quench the steel plate to a temperature range of 250 °C to 550 °C which
is the temperature range of bainite transformation. When the cooling stop temperature
exceeds 550 °C, bainite transformation is incomplete and sufficient strength can not
be obtained. In addition, if the cooling stop temperature is lower than 250 °C, the
hardness markedly increases in the surface layer. The cooling stop temperature is
preferably 350 °C to 500 °C.
[0059] Although an average temperature of the steel plate can not be directly measured physically,
a temperature distribution in a cross section in the plate thickness direction can
be determined in real time, for example, by difference calculation using a process
computer on the basis of the surface temperature at the start of cooling measured
with a radiation thermometer and the target surface temperature at the end of cooling.
The average value of temperatures in the plate thickness direction in the temperature
distribution is referred to as the "average temperature of the steel plate" in this
description.
[High strength steel pipe]
[0060] By forming the high strength steel plate disclosed herein into a tubular shape by
press bend forming, roll forming, UOE forming, or the like, and then welding the butting
portions, a high strength steel pipe for sour-resistant line pipes (such as a UOE
steel pipe, an electric-resistance welded steel pipe, and a spiral steel pipe) that
has excellent material homogeneity in the steel plate and that is suitable for transporting
crude oil and natural gas can be manufactured.
[0061] For example, an UOE steel pipe is manufactured by milling and beveling the edges
of a steel plate, forming the steel plate into a steel pipe shape by C press, U-ing
press, and O-ing press, then seam welding the butting portions by inner surface welding
and outer surface welding, and optionally subjecting it to an expansion process. Any
welding method may be applied as long as sufficient joint strength and joint toughness
are guaranteed, yet it is preferable to use submerged arc welding from the viewpoint
of excellent weld quality and manufacturing efficiency.
EXAMPLES
[0062] Steels having the chemical compositions listed in Table 1 (Steel Sample IDs A to
M) were prepared and subjected to continuous casting to obtain slabs with a slab width
of 1600 mm. Secondary cooling was performed with the overlapping margin of the injection
ranges of the coolant injected in a mist form from the three two-fluid spray nozzles
arranged at predetermined intervals in the width direction being set as listed in
Table 2. Note that a distance S from both ends of the injection range of the coolant
in the width direction of the cast steel 20 to the position where the ratio of a water
flux density at that position to a water flux density immediately below the two-fluid
spray nozzles is 50 % was fixed to 70 mm.
[0063] Each slab thus obtained was heated to the temperature as listed in Table 2, and then
hot rolled with the rolling finish temperature and the rolling reduction ratio as
listed in the table, to thereby obtain a steel plate with the plate thickness as listed
in the table. Then, each steel plate was subjected to controlled cooling using a water-cooling
type controlled-cooling device under the conditions listed in Table 2.
Table 1
Steel sample ID |
Chemical composition (mass%) |
Ar3 Temperature (°C) |
C |
Si |
Mn |
P |
S |
Al |
Ca |
Cu |
Ni |
Cr |
Mo |
Nb |
V |
Ti |
A |
0.064 |
0.32 |
1.41 |
0.004 |
0.0004 |
0.024 |
0.0022 |
|
|
|
|
0.010 |
|
|
777 |
B |
0.075 |
0.20 |
1.52 |
0.003 |
0.0005 |
0.032 |
0.0030 |
|
|
|
|
|
|
|
765 |
C |
0.044 |
0.21 |
1.28 |
0.005 |
0.0005 |
0.020 |
0.0017 |
0.23 |
0.11 |
|
0.19 |
0.025 |
|
|
768 |
D |
0.049 |
0.14 |
1.33 |
0.004 |
0.0004 |
0.019 |
0.0021 |
|
|
0.22 |
0.10 |
0.035 |
|
|
777 |
E |
0.046 |
0.24 |
1.23 |
0.006 |
0.0006 |
0.022 |
0.0015 |
|
|
0.20 |
0.14 |
0.021 |
|
0.015 |
783 |
F |
0.053 |
0.25 |
1.27 |
0.004 |
0.0008 |
0.025 |
0.0023 |
|
|
0.35 |
|
0.035 |
0.035 |
|
787 |
G |
0.041 |
0.28 |
1.32 |
0.003 |
0.0005 |
0.021 |
0.0011 |
|
|
0.25 |
0.11 |
0.029 |
|
0.011 |
779 |
H |
0.048 |
0.30 |
1.25 |
0.003 |
0.0004 |
0.020 |
0.0014 |
0.15 |
0.16 |
0.30 |
0.18 |
0.031 |
|
0.008 |
764 |
I |
0.086 |
0.17 |
1.33 |
0.005 |
0.0006 |
0.021 |
0.0021 |
|
0.26 |
|
0.15 |
0.022 |
|
0.010 |
751 |
J |
0.034 |
0.22 |
1.88 |
0.006 |
0.0008 |
0.025 |
0.0014 |
0.12 |
0.25 |
|
|
|
|
|
733 |
K |
0.046 |
0.20 |
1.28 |
0.018 |
0.0004 |
0.023 |
0.0020 |
|
|
0.23 |
0.12 |
0.015 |
|
|
780 |
L |
0.054 |
0.15 |
1.31 |
0.006 |
0.0026 |
0.022 |
0.0016 |
|
0.22 |
0.11 |
0.10 |
0.027 |
0.044 |
0.010 |
767 |
M |
0.055 |
0.19 |
1.44 |
0.017 |
0.0005 |
0.022 |
0.0026 |
|
|
|
|
|
|
|
778 |
Note 1: Underlined if outside the scope of the disclosure. |
Table 2
No. |
Steel sample ID |
Plate thickness |
Overlapping margin for secondary cooling of slab |
Heating temp. |
Rolling finish temperature |
Rolling reduction ratio |
Cooling start temp. |
Cooling start temp. - Ar3 |
Cooling rate (steel plate average) |
Cooling stop temp. |
Category |
|
(mm) |
|
(°C) |
(°C) |
(%) |
(°C) |
(°C) |
(°C/s) |
(°C) |
1 |
A |
34 |
2.0S |
1150 |
880 |
70 |
820 |
43 |
37 |
480 |
Example |
2 |
B |
16 |
2.0S |
1130 |
910 |
75 |
830 |
65 |
54 |
520 |
3 |
C |
25 |
2.1S |
1080 |
880 |
75 |
810 |
42 |
33 |
510 |
4 |
D |
15 |
1.9S |
1080 |
870 |
75 |
810 |
33 |
45 |
440 |
5 |
E |
20 |
2.2S |
1080 |
850 |
80 |
790 |
7 |
31 |
450 |
6 |
F |
34 |
2.4S |
1080 |
840 |
75 |
810 |
23 |
29 |
500 |
7 |
G |
34 |
2.0S |
1080 |
870 |
70 |
830 |
51 |
43 |
390 |
8 |
G |
34 |
2.0S |
1110 |
830 |
75 |
770 |
-9 |
23 |
460 |
9 |
G |
20 |
2.0S |
1110 |
800 |
75 |
780 |
1 |
34 |
470 |
10 |
G |
20 |
2.0S |
1100 |
850 |
75 |
810 |
31 |
31 |
440 |
11 |
H |
34 |
1.8S |
1080 |
860 |
75 |
810 |
46 |
37 |
350 |
12 |
H |
25 |
1.6S |
1150 |
850 |
75 |
820 |
56 |
47 |
500 |
13 |
H |
38 |
2.3S |
1080 |
850 |
75 |
800 |
36 |
32 |
480 |
14 |
G |
34 |
2.2S |
970 |
850 |
75 |
810 |
31 |
31 |
480 |
Comparative example |
15 |
G |
34 |
2.0S |
1080 |
780 |
75 |
740 |
-39 |
25 |
420 |
16 |
G |
34 |
1.9S |
1080 |
830 |
75 |
810 |
31 |
5 |
500 |
17 |
G |
34 |
2.3S |
1080 |
850 |
75 |
800 |
21 |
37 |
180 |
18 |
G |
20 |
2.0S |
1080 |
850 |
75 |
830 |
51 |
13 |
450 |
19 |
G |
20 |
1.5S |
1100 |
850 |
75 |
820 |
41 |
35 |
430 |
20 |
G |
34 |
2.5S |
1130 |
850 |
75 |
810 |
31 |
32 |
450 |
21 |
H |
34 |
2.6S |
1080 |
850 |
75 |
810 |
46 |
38 |
460 |
22 |
B |
16 |
1.4S |
1140 |
910 |
75 |
830 |
65 |
52 |
500 |
23 |
I |
34 |
2.0S |
1080 |
840 |
75 |
800 |
49 |
37 |
430 |
24 |
J |
34 |
2.0S |
1080 |
820 |
75 |
780 |
47 |
27 |
520 |
25 |
K |
34 |
2.0S |
1080 |
860 |
75 |
820 |
40 |
33 |
470 |
26 |
L |
34 |
2.0S |
1080 |
850 |
75 |
810 |
43 |
32 |
450 |
27 |
M |
16 |
2.0S |
1130 |
890 |
75 |
840 |
62 |
42 |
520 |
Note 1: Underlined if outside the scope of the disclosure. |
[Identification of microstructure]
[0064] The microstructure of each obtained steel plate was observed with an optical microscope
and a scanning electron microscope. The microstructures at the plate thickness center
(i.e., t/2 position) of the steel plate are listed in Table 3.
[Evaluation of tensile property]
[0065] From each obtained steel plate, a full-thickness test piece (as prescribed in API-5L
specification) in the transverse direction (direction orthogonal to the rolling direction)
was taken and subjected to tensile test as a tensile test piece to measure the yield
stress (0.5% proof stress) and the tensile strength. The target ranges were a yield
stress of 450 MPa or more and a tensile strength of 520 MPa or more. The results are
listed in Table 3.
[Evaluation of variation in the HIC resistance in the plate width direction]
[0066] Three samples were respectively collected from a W/4 position, a W/2 position, and
a 3W/4 position in the manner described above, and CARs were measured. The maximum
value of the nine measured values thus obtained is presented in the column of "HIC
resistance" in Table 3. Table 3 also lists 3σ when the standard deviation of nine
CARs is calculated as σ. The target range was 10 % or less for the maximum value and
5 % or less for 3σ.
[Measurement of Mn-concentrated spots]
[0067] The number of Mn-concentrated spots having a major axis length of more than 1.5 mm
was counted per 100 mm in length in the plate width direction in the manner described
above. The target range was 3 or less. The results are listed in Table 3.
[DWTT test]
[0068] From each obtained steel plate, a DWTT test piece conforming to the API-5L was taken
and tested at test temperatures of 0 °C to -80 °C to determine a transition temperature
at which the SA value (Shear Area: percent ductile fracture) was 85 %. The target
range for transition temperature was -50 °C or lower. The results are listed in Table
3.
Table 3
No. |
Steel sample ID |
Plate thickness |
Microstructure |
Yield strength |
Tensile strength |
HIC resistance |
Variation in HIC resistance, 3σ |
Mn-concentrated spots |
DWTT 85 % SATT |
Category |
(mm) |
(t/2 position) |
(MPa) |
(MPa) |
(%) |
(%) |
(pcs.) |
(°C) |
1 |
A |
34 |
B |
460 |
575 |
1 |
0.3 |
1 |
-50 |
Example |
2 |
B |
16 |
B |
477 |
589 |
2 |
1.2 |
2 |
-50 |
3 |
C |
25 |
B |
480 |
624 |
0 |
0 |
1 |
-60 |
4 |
D |
15 |
B |
485 |
622 |
0 |
0 |
0 |
-65 |
5 |
E |
20 |
B |
462 |
581 |
0 |
0 |
0 |
-55 |
6 |
F |
34 |
B |
458 |
578 |
3 |
0.7 |
2 |
-50 |
7 |
G |
34 |
B |
504 |
637 |
2 |
0.4 |
1 |
-50 |
8 |
G |
34 |
B |
466 |
574 |
0 |
0 |
2 |
-55 |
9 |
G |
20 |
B |
506 |
621 |
0 |
0 |
0 |
-60 |
10 |
G |
20 |
B |
511 |
628 |
0 |
0 |
0 |
-65 |
11 |
H |
34 |
B |
498 |
629 |
1 |
0.2 |
2 |
-65 |
12 |
H |
25 |
B |
522 |
639 |
2 |
0.5 |
2 |
-60 |
13 |
H |
38 |
B |
531 |
634 |
4 |
1 |
3 |
-60 |
14 |
G |
34 |
B |
415 |
505 |
4 |
2 |
2 |
-60 |
Comparative example |
15 |
G |
34 |
F+B |
420 |
510 |
12 |
8 |
5 |
-65 |
16 |
G |
34 |
F+P |
410 |
513 |
15 |
7 |
6 |
-70 |
17 |
G |
34 |
B+M |
541 |
654 |
14 |
6 |
5 |
-30 |
18 |
G |
20 |
F+P |
430 |
511 |
12 |
6 |
4 |
-50 |
19 |
G |
20 |
B |
482 |
632 |
22 |
7 |
8 |
-60 |
20 |
G |
34 |
B |
476 |
639 |
18 |
8 |
8 |
-60 |
21 |
H |
34 |
B |
489 |
644 |
27 |
8 |
12 |
-35 |
22 |
B |
16 |
B |
468 |
597 |
8 |
6 |
4 |
-55 |
23 |
I |
34 |
B |
510 |
647 |
22 |
8 |
6 |
-30 |
24 |
J |
34 |
B |
516 |
650 |
16 |
6 |
6 |
-65 |
25 |
K |
34 |
B |
501 |
614 |
14 |
7 |
5 |
-60 |
26 |
L |
34 |
B |
483 |
620 |
12 |
8 |
6 |
-60 |
27 |
M |
16 |
B |
503 |
616 |
13 |
7 |
5 |
-60 |
Note 1: Underlined if outside the scope of the disclosure.
Note 2: For nicrostructure, B denotes bainite, F denotes ferrite, M denotes martensite,
and P denotes pearlite. |
[0069] For Nos. 1 to 13, which are our examples, the chemical compositions were within the
scope of the present disclosure and the manufacturing conditions were within the range
suitable for obtaining steel plates according to the present disclosure. All of our
samples had a yield stress of 450 MPa or more, a tensile strength of 520 MPa or more,
a 85 % SATT of -50 °C or lower in the DWTT test, and small variation in the HIC resistance
in the plate width direction, any of which properties were considered good.
[0070] In contrast, for Nos. 14 to 22, which are comparative examples, although the chemical
compositions were within the scope of the present disclosure, the manufacturing conditions
were outside the scope of the preferred conditions for obtaining steel plates according
to the present disclosure. For No. 14, the slab heating temperature was low, the homogenization
of the microstructure and the solid solution state of carbides were insufficient,
and the strength was low.
For No. 15, since ferrite generated excessively due to the low cooling start temperature,
the strength was low and the HIC resistance was inferior.
For Nos. 16 and 18, since pearlite excessively generated as a microstructure in the
mid-thickness part due to the controlled cooling condition outside the suitable range,
the strength was low and the HIC resistance was inferior.
For No. 17, since hard phases such as martensite and martensite austenite constituent
(MA) were formed due to the low cooling stop temperature, the DWTT property and the
HIC resistance were inferior.
For Nos. 19 to 22, since the secondary cooling conditions of the slabs were outside
the suitable range, Mn concentration in the central segregation area was high, variation
in the HIC resistance in the plate width direction was large, and the HIC resistance
was inferior.
For Nos. 23 to 27, since the chemical compositions were outside the scope of the present
disclosure, Mn concentration in the central segregation area was high, variation in
the HIC resistance in the plate width direction was large, and the HIC resistance
was inferior.
INDUSTRIAL APPLICABILITY
[0071] The high strength steel plates for sour-resistant line pipes according to the present
disclosure have excellent HIC resistance in which variation in the HIC resistance
in the plate width direction is suppressed. Therefore, steel pipes (such as electric-resistance
welded steel pipes, spiral steel pipes, and UOE steel pipes) manufactured by cold-forming
the disclosed steel plate can be suitably used for transportation of crude oil and
natural gas that contain hydrogen sulfides where sour resistance is required.
REFERENCE SIGNS LIST
[0072]
10, 10A, 10B two-fluid spray nozzle
20 cast steel