[0001] The present invention relates to a process for producing an extra-high-tensile and
high-toughness steel having a yield strength of 1080 MPa or more that has a high strength
despite a low carbon content and is excellent in stress corrosion resistance in a
stress corrosive environment, such as sea water and salt water.
[0002] In recent years, geophysical exploration on an earth scale, such as search and drilling
for energy resources and occurrence of earthquake, has led to a growing interest in
ocean development in deep sea and activated the construction and installation of various
containers for deep-sea use and the development of research ships for deep-sea use.
[0003] When various containers are used in a deep-sea environment, since a very high pressure
is applied thereto, it is required for materials for these containers to have a high
degree of toughness and strength from the viewpoint of structure.
[0004] In order to cope with the demand for safe, reliable, high-strength and high-toughness
materials, the development of a Ni-containing low alloy steel and an improvement in
the quality thereof have been effected in the art. For example, proposals have been
made on many production processes, such as a process for producing a high-strength
and high-toughness steel comprising Ni-Cr-Mo-V with C + 1/8Mo + V > 0.26 and Cr ≦
0.8 Mo as disclosed in Japanese Unexamined Patent Publication (Kokai) No. 56-9358,
a process for producing a Ni-Cr-Mo-V-based extra high tensile steel as disclosed in
Japanese Unexamined Patent Publication (Kokai) No. 57-188655, which enables a high
strength and a high toughness to be provided in a wide cooling rate range in a quenching
treatment, and a process for a Ni-containing steel product, wherein very low P and
very low S treatments are effected for the purpose of ensuring a high toughness. Although
these processes are effective for increasing strength or toughness, there is a possibility
that the reliability of the steel products produced by the above processes is poor
in the environment contemplated in the present invention. Specifically, since the
containers used in deep sea are exposed to sea water, the steel products should have
a satisfactory resistance to corrosion in sea water, that is, a high resistance to
stress corrosion cracking in sea water.
[0005] Examples of extra high tensile steel products having a high reliability underwater
include a Ni-Cr-Mo-V-based high-toughness and extra-high-tensile steel proposed in
Japanese Examined Patent Publication (Kokoku) No. 64-11105, characterized by comprising
a Ni-containing steel having lowered N and O contents and capable of satisfying a
requirement of Al (%) x N (%) x 10⁴ < 1.5, which high-toughness and extra-high-tensile
steel has a significant effect. In this steel, however, the stress corrosion cracking
resistance at the welding heat affected zone in sea water is inferior to that in the
air as compared with the base material, which requires further study regarding improvement
in safety and reliability. On the other hand, Japanese Examined Patent Publication
(Kokoku) No. 1-51526 proposes a process for producing an extra high tensile steel
having an excellent stress corrosion cracking resistance, which comprises subjecting
a Ni-Mo-Nb-based steel having a Ni content of 5 to 8% to direct quenching-and-tempering.
The strength of the steel product, however, is lower than that contemplated in the
present invention. In the production of a thick high tensile steel by the direct quenching-and-tempering
process, close control is necessary from the viewpoint of the homogeneity and anisotropy
of the quality in the direction of the plate thickness. Further, there is a possibility
that the stability of the quality is deteriorated in the widthwise direction and longitudinal
direction within the steel plate.
[0006] Thus, the conventional extra high tensile steel products have lower stress corrosion
cracking resistance particularly at the welding-heat affected zone in sea water than
in the air and are produced by processes that are disadvantageous in the homogeneity
of the quality in the thicknesswise direction of the thick steel plate and the stability
of the quality within the steel plate. That is, a further improvement in both the
steel products and production processes has been desired in the art.
[0007] An object of the present invention is to improve the homogeneity of the quality of
a thick steel product through an alleviation in the problem of the prior art, i.e.,
a problem of the stress corrosion cracking resistance, particularly a deterioration
in the stress corrosion cracking resistance at the welding heat affected zone in sea
water, together with an increase in the tensile strength. The subject matter of the
present invention is as follows.
[0008] A process for producing an extra high tensile steel having an excellent stress corrosion
cracking resistance, comprises the steps of: heating a slab comprising, in terms of
% by weight, 0.04 to 0.09% of C, 0.01 to 0.10% of Si, 0.05 to 0.65% of Mn, 8.0 to
11.0% of Ni, 0.5 to 1.5% of Mo, 0.2 to 1.5% of Cr, 0.02 to 0.20% of V and 0.01 to
0.08% of Al with the balance consisting of iron and unavoidable impurities or a slab
comprising the above-described ingredients and further comprising at least one member
selected from the group consisting of 0.2 to 1.5% of Cu, 0.005 to 0.10% of Nb and
0.005 to 0.03% of Ti as strength improving elements and 0.0005 to 0.005% of Ca and
0.0005 to 0.0100% of REM (Rare earth metal) as elements having a capability of regulating
the form of inclusions to a temperature between 1000°C and 1250°C, hot-rolling the
slab at a temperature of Ar' point (the term "Ar' point" being used because, in the
steel of the present invention, ferrite is not formed from the austenitic state even
at the Ar3 transformation point and there occurs γ → γ') or above, air-cooling the
rolled plate, reheating the rolled plate at a rate of 120°C/min or less to a temperature
region of from (A
c3 point - 40°C) to (A
c3 point + 40°C), quenching the reheated plate and subsequently tempering the quenched
plate at a temperature of the A
c1 point or below.
Fig. 1 is a diagram showing the relationship between the Mn content and the stress
corrosion cracking resistance of a steel product;
Fig. 2 is a diagram showing the relationship between the temperature rise rate during
reheating and the yield strength;
Fig. 3 is a schematic view of a metallic microstructure in connection with a reheating
temperature region, wherein (A) is a metallic microstructure for a reheating temperature
region of (Ac3 point - 40°C) or below, (B) is a metallic microstructure for a reheating temperature
region falling within the scope of the present invention and (C) is a metallic microstructure
for a reheating temperature region of (Ac3 point + 40°C) or above;
Fig. 4 is a diagram showing the relationship between the yield strength and the KlSCC value of the base material of an example of the present invention; and
Fig. 5 is a diagram showing a notch position for the evaluation of KlSCC value in the welding-heat affected zone in an example of the present invention;
[0009] The present inventors have conducted various studies on steel ingredients and production
process, particularly on hot rolling, reheating, quenching and tempering with a view
to stably producing a Ni-containing low alloy steel having a good resistance to stress
corrosion cracking, particularly stress corrosion cracking at the welding-heat affected
zone, in sea water or salt water and, at the same time, a high tensile strength and
a high toughness and, as a result, have found that, when Mo, V and Nb are added to
a Ni-containing steel having lowered C, Si and Mn contents and the Ni-containing steel
is hot-rolled to sufficiently dissolve these elements in a solid solution form and
reheated and quenched with controlled temperature rise rate and heating temperature
range, the Mo, V and Nb dissolved in a solid solution form are precipitated during
heating to form non-diffusion type reverse transformed γ grains comprising a group
of acicular austenites having a high dislocation density, which enables a reinforcing
mechanism inherent in the Ni-containing steel to be exhibited to attain an increase
in the strength.
[0010] At the outset, the reason for the limitation of ingredients of the steel according
to the present invention will now be described.
[0011] C is an element useful for improving the quenchability and easily increasing the
strength. On the other hand, it has the greatest effect on an improvement in the stress
corrosion cracking resistance of the welding-heat affected zone of the extra high
tensile steel. When the content exceeds 0.09%, a significant lowering in the stress
corrosion cracking resistance of the welding-heat affected zone occurs. On the other
hand, when it is lower than 0.04%, the strength is unsatisfactory For this reason,
the C content is limited to 0.04 to 0.09%.
[0012] Si is useful for improving the strength. It is also indispensable for steel making.
Si is contained in an amount of 0.01% at the smallest. In the case of a high Ni-containing
steel contemplated in the present invention, when the Si content exceeds 0.10%, the
temper brittleness becomes so great that the low-temperature toughness is lowered.
For this reason, the Si content is limited to 0.01 to 0.10%.
[0013] Mn is necessary for improving the quenchability and hot workability. However, when
the Mn content is less than 0.05%, the improvement effect cannot be attained. On the
other hand, in the case of the Ni-containing steel contemplated in the present invention,
the addition of Mn increases the susceptibility to temper brittleness and deteriorates
the stress corrosion cracking resistance of the welding-heat affected zone, so that
the Mn content should be 0.65% or less. Fig. 1 shows the toughness and the results
of a stress corrosion cracking test (K
lSCC test) in artificial sea water for steel plates produced by subjecting a slab having
a composition of 0.06% C - 9.9% Ni - 1.0% Mo - 0.1% V with the amount of addition
of Mn being varied from 0.15 to 1.05% to hot rolling and air cooling, reheating the
cooled plate to 770°C, quenching the reheated plate and tempering the quenched plate
at 540°C. It is apparent that the low-temperature toughness and the stress corrosion
cracking resistance are improved with lowering the Mn content. For this reason, the
Mn content is limited to 0.05 to 0.65%.
[0014] Ni is useful for enhancing the stacking fault energy, increasing the cross slip,
facilitating the occurrence of stress relaxation, increasing the impact absorption
energy and improving the low-temperature toughness.
[0015] Further, Ni exhibits the best effect when it is present together with Mo, V and other
elements contained in the steel of the present invention. Specifically, when the steel
is reheated to a temperature region of from (A
c3 point - 40°C) to (A
c3 point + 40°C), a grain mixture of diffusion type reverse transformed γ grains comprising
a massive austenite formed by dissolution of carbides with non-diffusion type reverse
transformed γ grains comprising a group of acicular austenites not involving the dissolution
of carbides is formed, and the non-diffusion type reverse transformed γ grains have
a higher dislocation density than the diffusion type reverse transformed γ grains
and very effectively contributes to an increase in the strength. Specifically, Ni
serves to delay the dissolution of carbides of Mo, V and other elements, which enables
the group of acicular austenites to be stably maintained up to a high temperature.
For this reason, Ni should be added in an amount of 8.0% or more for the purpose of
ensuring the strength by taking advantage of stabilization of the non-diffusion type
reverse transformed γ grains at a high temperature. On the other hand, when the amount
of addition of Ni exceeds 11.0%, austenite is precipitated during tempering, which
deteriorates the strength and toughness. For this reason, the Ni content is limited
to 8.0 to 11.0%.
[0016] Mo is an element useful for the precipitation hardening by tempering and the inhibition
of temper brittleness and, at the same time, important to the present invention as
with Ni. Specifically, since a fine carbide composed mainly of Mo precipitated in
the course of heating in the step of reheating and quenching remains as an undissolved
carbide up to a high temperature, the group of acicular austenites having a high dislocation
density can be maintained at a high temperature, so that Mo is necessary for ensuring
the strength. However, when the Mo content is less than 0.5%, the dissolution of the
Mo carbide occurs in the reheating and quenching, which causes the non-diffusion type
transformed γ grains to be rapidly attacked by the diffusion type reverse transformed
γ grains, so that a contemplated strength cannot be obtained. On the other hand, when
the Mo content exceeds 1.5%, the effect of improving the strength is saturated, so
that the amount of coarse alloy carbides is increased to lower the toughness. For
this reason, the Mo content is limited to 0.5 to 1.5%.
[0017] Cr serves to improve the quenchability and is useful for ensuring the strength. The
Cr content should be 0.2% at the lowest. When it exceeds 1.5%, the increase in the
strength is saturated and the toughness is lowered. For this reason, the Cr content
is limited to 0.2 to 1.5%.
[0018] V is useful for forming a carbonitride in the tempering that is precipitation-hardened
to ensure the strength. Further, as with Mo, V is finely precipitated during heating
in the reheating and quenching to increase the stability of non-diffusion type reverse
transformed γ grains comprising a group of acicular austenites, which is useful for
ensuring the strength. When the V content is less than 0.02%, no contemplated strength
cannot be attained, while when it exceeds 0.20%, the toughness is lowered. For this
reason, the V content is limited to 0.02 to 0.20%.
[0019] Al is necessary for deoxidation and, at the same time, combines with N to form a
nitride, AlN, that has the effect of refining the structure. However, when the Al
content is less than 0.01%, this effect is small. On the other hand, when it exceeds
0.08%, the amount of inclusions comprising alumina becomes so large that the toughness
is inhibited. For this reason, the Al content is limited to 0.01 to 0.08%.
[0020] In one embodiment of the present invention, at least one member selected from (Cu,
Nb, Ti) and (Ca, REM) is added besides the above-described ingredients. Cu, Nb and
Ti exhibit an equalizing action, that is, serve to improve the strength of the steel.
Further, Nb and Ti are useful also for the refinement of austenite grains. In order
to ensure a desired effect, it is necessary for the lower limits of Cu, Nb and Ti
to be 0.2%, 0.005% and 0.005%, respectively. However, when the Cu, Nb and Ti contents
exceed 1.5%, 0.10% and 0.03%, respectively, not only the low-temperature toughness
is lowered but also the susceptibility to stress corrosion cracking is enhanced. For
this reason, the Cu, Nb and Ti contents are limited to the above-described respective
ranges.
[0021] Ca and REM (Rare earth metal) have the effect of spheroidizing nonmetallic inclusions
and are useful for improving both the toughness and anisotropy. For this purpose,
the Ca and REM should be present in an amount of 0.0005% at the smallest. However,
when the Ca and REM contents exceed 0.005% and 0.0100%, respectively, the toughness
is lowered due to an increase in the amount of inclusions. For this reason, the Ca
and REM contents are limited to 0.0005 to 0.005% and 0.0005 to 0.0100%, respectively.
[0022] The steel of the present invention contains, besides the above-described ingredients,
P, S, N, O and other elements as unavoidable impurities that are detrimental to the
toughness and stress corrosion cracking resistance characteristic of the steel of
the present invention and, therefore, the amount of these unavoidable impurities is
as small as possible. The contents of P, S, N and O are preferably regulated to 0.005%
or less, 0.003% or less, 0.0050% and 0.0030%, respectively.
[0023] The production process which is another subject matter of the present invention will
now be described.
[0024] Even when the steel comprises the above-described composition, the production process
should be proper for attaining the strength, toughness and stress corrosion cracking
resistance contemplated in the present invention. Accordingly, in the process of the
present invention, the rolling, cooling and reheating-quenching-tempering conditions
were limited for the following reasons.
[0025] At the outset, a slab comprising the above-described ingredients is heated to 1000
to 1250°C. In the heating, in order to attain, besides the refinement of heated austenite
grains, utilization of the strengthening by taking advantage of the above-described
non-diffusion type reverse transformed γ and fine precipitation in the reheating-quenching-tempering
after the hot rolling, the slab should be heated to 1000°C or above to sufficiently
dissolve Mo, Cr, V, Nb, etc., in a solid solution form. In this case, when the temperature
is below 1000°C, the dissolution of these elements in a solid solution form is unsatisfactory
and the alloy carbide (M₆C) remaining undissolved is coarsened, which makes it impossible
to expect sufficient precipitation hardening in the tempering and, at the same time,
is causative of a lowering in the toughness. On the other hand, when the temperature
exceeds 1250°C, although alloy carbides of Mo, Cr, V, Nb, etc., are sufficiently dissolved
in a solid solution form, in the Ni-containing steel contemplated in the present invention,
the amount of the oxide on the surface of the slab is increased, which finally results
in the occurrence of a surface flaw after the rolling. Further, heated austenite grains
are coarsened, and it becomes difficult to refine the austenite grains in the subsequent
rolling, which is causative of a lowering in the toughness. For these reasons, the
heating temperature of the slab is limited to 1000 to 1250°C.
[0026] The heated slab is then hot-rolled at a temperature of the Ar' transformation point
and air-cooled. In the steel of the present invention, since the Ar' point is as low
as 400°C, the above requirement can be met by simply subjecting the heated slab to
conventional hot rolling. Further, since the steel of the present invention has a
composition having a sufficiently high quenchability, air cooling alone suffices for
the formation of a martensitic single phase structure including a sufficiently large
amount of dislocation. It is noted that, since non-diffusion type reverse transformed
γ grains contributing to strengthening are the same as the γ grains after the hot
rolling, if it is necessary to ensure a higher low-temperature toughness, although
a lowering in the roll finishing temperature is preferred according to need for the
purpose of refining the γ grains by rolling-recrystallization, there is no limitation
on the method.
[0027] The steel plate after hot rolling and air cooling is then reheated to a temperature
range of from (A
c3 point - 40°C) to (A
c3 point + 40°C) and quenched. In the step of heat treatment, wherein reheating is effected
with the martensite structure used as a precursor structure, when the steel is heated
to an α-γ dual phase coexisting temperature region, diffusion type reverse transformed
γ grains comprising an ordinary massive austenite are formed from old austenite grain
boundaries while a group of acicular austenites are formed from the intragranular
martensite. They coexist together with carbides and ferrite. Since the acicular austenite
is produced by non-diffusion type (martensitic) reverse transformation, it has a large
amount of dislocation that contributes to an increase in the strength. Further, the
heating of the steel plate to a temperature range of from (A
c3 point - 40°C) to (A
c3 point + 40°C) causes the group of acicular austenites to increase their area to form
non-diffusion type reverse transformed γ grains that are stably maintained up to a
high temperature and become fine austenite grains comprising a mixture thereof with
diffusion type reverse transformed γ grains. When quenching is effected from this
temperature region, a martensitic structure, into which further dislocation has been
introduced, is formed, so that it becomes possible to produce an extra high tensile
steel.
[0028] When the steel plate is heated to a temperature of (A
c3 point + 40°C), the non-diffusion type reverse transformed γ grains contributing to
strengthening after quenching are converted to ordinary diffusion type reverse transformed
γ grains, which gives rise to a lowering in the strength of the steel plate. Therefore,
the reheating temperature for quenching should be in the range of from (A
c3 point - 40°C) to (A
c3 point + 40°C) and is preferably A
c3 point ± 20°C from the viewpoint of stabilizing the non-diffusion type reverse transformed
γ grains. The above-described change in the austenite grains (γ grains) is shown in
Fig. 3. Fig. 3 (B) is a schematic view of a grain mixture of non-diffusion type reverse
transformed γ grains with diffusion type reverse transformed γ grains, which grain
mixture has been formed by a treatment in a reheating temperature region for quenching
of from (A
c3 point - 40°C) to (A
c3 point + 40°C) specified in the present invention. Fig. 3 (A) is a diagram showing
the results for a reheating temperature region of (A
c3 point - 40°C) or below, and Fig. 3 (C) is a diagram showing the results for a reheating
temperature region of (A
c3 point + 40°C) or above.
[0029] A temperature rise rate of 120°C/min or less during the reheating is also one of
the characteristic features of the present invention. Fig. 2 shows the results of
a yield strength test on a steel plate produced by subjecting a slab having a composition
of 0.06% C - 9.9% Ni - 1.0% Mo - 0.1% V to heating at 1150°C, rolling and air cooling,
reheating the steel plate to 790°C with varied temperature rise rate, quenching the
steel plate and temperature the quenched steel plate at 540°C. It is apparent that
the strength is improved with lowering the temperature rise rate. It is reported that
the non-diffusion type reverse transformed γ is generally formed by rapid heating.
However, it has been found that, the steel having a high Ni content according to the
present invention, the non-diffusion type reverse transformed γ is formed without
rapid heating and, as opposed to the conventional common knowledge, a temperature
rise rate of 120°C/min or less is advantageous from the viewpoint of increasing the
strength. Detailed studies on this point have revealed that carbides and nitrides
of Mo, Cr, V, Nb, etc., precipitated during gradual heating increase the stability
of the once formed non-diffusion type reverse transformed γ, so that the area ratio
of the non-diffusion type reverse transformed γ grains contributing to strengthening
is increased.
[0030] The steel plate after the reheating and quenching is then tempered at a temperature
of an Ac₁ point or below. In this case, when the temperature exceeds the Ac₁ point,
the strength and toughness are lowered due to the formation of unstable austenite.
For this reason, the tempering temperature is limited to Ac₁ point or below for the
purpose of sufficiently precipitation-strengthening through fine precipitation of
Mo, Cr, V, Nb, etc., to provide a high strength and a high toughness.
[0031] The steel provided by the above-described production process has a high strength
and a high toughness despite a low carbon content and an remarkably improved stress
corrosion cracking resistance, particularly at the welding-heat affected zone.
EXAMPLES
[0032] Steels having compositions specified in Table 1 were produced by the melt process
to provide slabs that were then used to produce steel plates having a thickness of
20 to 80 mm under production conditions according to the process of the present invention
or comparative process specified in Table 2.
[0033] The mechanical properties of these base materials and the K
lSCC value (limiting fracture toughness value relative to stress corrosion cracking resistance)
of the base material portion and welding-heat affected zone were examined. The welding
was effected at a heat input of 25 kJ/cm by TIG welding.
[0034] The mechanical properties of base materials produced by using plates having chemical
compositions specified in Table 1 and production conditions specified in Table 2 and
the results of K
lSCC test for the base material portion and welding-heat affected zone using test pieces
specified in ASTM E 399 in artificial sea water of 3.5% NaCl are given in Table 3.
In the evaluation method, a precracked test piece was used under a service environmental
condition (in this case, sea water), and the tip of the notch is brought to a severe
condition (stress load) to facilitate the occurrence of a delayed fracture. The stress
corrosion cracking resistance is evaluated by effecting a constant load test under
this environment at a K value (a coefficient of stress necessary for preventing the
occurrence of cracking at the tip of the notch) on various levels to determine a limit
of K
lSCC value that does not cause a fracture at a certain K value or less. With respect to
the evaluation of the K
lSCC property of the welding-heat affected zone, a notch is provided at the center of
HAZ as shown in Fig. 5.
[0036] In the examples of the present invention (1-A to 15-O wherein steels falling within
the scope of the present invention is used in combination with the process of the
present invention), the base materials had good mechanical properties, i.e., a high
strength and a high toughness, and with respect to the stress corrosion cracking resistance
as well, both the base material and welding heat affected zone had a sufficiently
high K
lSCC value.
[0037] On the other hand, with respect to comparative examples wherein the process falling
within the scope of the present invention is used in combination with comparative
steels (P to V) outside the chemical composition range specified in the present invention,
in 16-P and 17-Q, since the Mo and V content are low, non-diffusion type reverse transformed
γ grains are not formed and the precipitation strengthening is also small, so that
the strength is unsatisfactory. In 18-R, since the Ni content is low, non-diffusion
type reverse transformed γ grains are not formed, so that the strength is unsatisfactory.
In 19-S and 20-T, since the Mn content and both C and Mn contents are high, the toughness
and the K
lSCC value of the base material and the welding-heat affected zone are low. In 21-U, since
the C and Ni contents are high, the K
lSCC value of the base material and the welding-heat affected zone are low. In 22-V, since
the C content is high, the K
lSCC value of the welding-heat affected zone is low.
[0038] With respect to comparative examples wherein steels falling within the scope of the
present invention are used in combination with comparative processes (23 to 29) outside
the scope of the present invention, in 23-D and 28-J, since the temperature rise rate
in the reheating for quenching is high, the non-diffusion type reverse transformed
γ grains become unstable, which increases the amount of the diffusion type reverse
transformed γ grains, so that the strength becomes unstable. In 24-D, since the reheating
temperature for quenching is so low that a large amount of ferrite is present between
the group of acicular γ grains, which gives rise to a lowering in the strength and
toughness. In 25-B and 27-F, since the slab heating temperature is so low that not
only coarse undissolved precipitates of carbides are present but also the precipitation
strengthening is small, so that the strength and toughness are unsatisfactory. In
26-B and 29-L, since the reheating temperature for quenching is high, the diffusion
type reverse transformed γ grains are formed, so that the strength is unsatisfactory.
Further, in this case, the K
lSCC value of the base material is somewhat lowered. Fig. 4 is a graph showing the K
lSCC values of the steel of the present invention, comparative steel and conventional
materials. From this drawing, it is apparent that the K
lSCC value of the steel of the present invention is on a level significantly improved
over those of the conventional materials.
[0039] As described above, the composition range and process according to the present invention
have enabled an extra high tensile steel having a yield strength of 1080 MPa or more
and excellent in low-temperature toughness and stress corrosion cracking resistance
at the welding-heat affected zone to be stably produced and supplied, so that it has
become possible to significantly improve the reliability of containers and equipment
used in a deep-sea environment.