CN110462080A - Acid resistance line-pipes high-strength steel sheet and its manufacturing method and the high tensile steel tube for using acid resistance line-pipes high-strength steel sheet - Google Patents
Acid resistance line-pipes high-strength steel sheet and its manufacturing method and the high tensile steel tube for using acid resistance line-pipes high-strength steel sheet Download PDFInfo
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Abstract
The present invention provides that a kind of not only Resistant to HIC is excellent but also resistance to SSCC under harsher corrosive environment also excellent acid resistance line-pipes high-strength steel sheet.Acid resistance line-pipes high-strength steel sheet of the invention is characterized in that, with as follows at being grouped as: containing C:0.02~0.08%, Si:0.01~0.50%, Mn:0.50~1.80%, P:0.001~0.015%, S:0.0002~0.0015%, Al:0.01~0.08% and Ca:0.0005~0.005% in terms of quality %, remainder is made of Fe and inevitable impurity, and the structure of steel of 0.5mm is dislocation density 1.0 × 10 under surface of steel plate14~7.0 × 1014(m‑2) bainite structure, the deviation of the Vickers hardness of 0.5mm is calculated as 30HV when standard deviation is set as σ with 3 σ hereinafter, the tensile strength with 520MPa or more under surface of steel plate.
Description
Technical field
The present invention relates to be suitable for build, marine structure, shipbuilding, building, construction industrial machinery field line pipe
, the acid resistance line-pipes high-strength steel sheet and its manufacturing method that property uniform in material in steel plate is excellent.In addition, the present invention relates to
And a kind of high tensile steel tube using above-mentioned acid resistance line-pipes high-strength steel sheet.
Background technique
Generally, line pipe is by will utilize UOE molding, bent into shape and roller by heavy plate mill or the steel plate of hot-rolling mill manufacture
It rolls into type etc. and is shaped to steel pipe to manufacture.
Wherein, for conveying the line pipe of the crude oil containing hydrogen sulfide, natural gas in addition to needing intensity, toughness, weldability
Deng other than, it is also necessary to which resistance to hydrogen induced cracking (resistance to HIC (Hydrogen Induced Cracking) property), halophile stress are rotten
Lose so-called acid resistance as anti-thread breakage (resistance to SSCC (Sulfide Stress Corrosion Cracking) property).Wherein,
For HIC, the hydrogen ion adsorption generated by corrosion reaction invades steel in the form of the hydrogen of atom shape in steel surface
Inside, and spread, gather around the non-metallic inclusions such as MnS in steel or the 2nd hard phase constitution, become the hydrogen of molecularity,
It is cracked because of its internal pressure, therefore becomes problem in the line pipe relatively low relative to oil well pipe strength grade, to this
It is open that there are many countermeasure technologies.On the other hand, for SSCC, it is known that generally in oil well high-strength seamless steel pipe and weldering
The high rigidity region of socket part generates, and is not considered as problem substantially in the relatively low line pipe of hardness.However, in recent years, crude oil,
Gas extraction environment is more and more harsher, it has been reported that in the environment that hydrogen sulfide sectional pressure is high or pH is low, in the mother of line pipe
Material portion also generates SSCC, it is indicated that is improved under harsher corrosive environment by controlling the hardness of steel pipe internal-surface surface section
The importance of resistance to SSCC.
In general, in the manufacture of line-pipes high-strength steel sheet, using be combined with controlled rolling and control it is cooling, it is so-called
TMCP (Thermo-Mechanical Control Process, controlled rolling and controlled cooling) technology.In order to use the TMCP technology come into
The high intensity of row steel, it is effective for so that cooling velocity when cooling control is become larger.However, being cooled down with high cooling velocity
When control, since steel plate surface section is cooled rapidly, the hardness of surface section is got higher compared with inside steel plate, plate thickness direction
Deviation is distributed in hardness.Therefore, there are problems in the viewpoint for ensuring the property uniform in material in steel plate.
To solve the above-mentioned problems, such as in patent document 1,2 a kind of manufacturing method of steel plate is disclosed, by carrying out
After rolling, surface section terminate the cooling control of the high cooling velocity for making surface re-heat before bainitic transformation, to obtain plate thickness
The small steel plate of the material difference in direction.In addition, disclosing a kind of manufacturing method of line-pipes steel plate in patent document 3,4, lead to
Crossing will accelerate surface of steel plate after cooling to be heated to reduce the hard of surface section than internal high temperature using high-frequency induction heating apparatus
Degree.
On the other hand, in the case where the scale thickness of surface of steel plate is uneven, when cooling, the cooling of the steel plate of its underpart
Speed also generates deviation, and the cooling deviation for stopping temperature of the part in steel plate becomes problem.As a result, can be because of scale thickness
Unevenness and plate width direction generate steel plate material deviation.In contrast, a kind of method is disclosed in patent document 5,6,
The inhomogeneous cooling as caused by scale thickness unevenness is reduced by derusting before cooling, improves plate profile.
Existing technical literature
Patent document
Patent document 1: No. 3951428 bulletins of Japanese Patent No.
Patent document 2: No. 3951429 bulletins of Japanese Patent No.
Patent document 3: Japanese Unexamined Patent Publication 2002-327212 bulletin
Patent document 4: No. 3711896 bulletins of Japanese Patent No.
Patent document 5: Japanese Unexamined Patent Publication 9-57327 bulletin
Patent document 6: No. 3796133 bulletins of Japanese Patent No.
Summary of the invention
However, the research of people etc. according to the present invention, shows that the manufacturing method recorded in by above patent document 1~6 obtains
To high-strength steel sheet in, there are rooms for improvement in terms of the resistance to SSCC under harsher corrosive environment.As its reason,
Think as follows.
In the manufacturing method documented by patent document 1,2, due to the ingredient of steel plate when transformation behavior difference, sometimes no
The effect to homogenize to the sufficient material caused by re-heat.In addition, obtained by the manufacturing method recorded in patent document 1,2
When the tissue on the surface layer of steel plate is heterogeneous structure as 2 phase constitution of ferrite-bainite, in the micro-vickers hardness of underload
In test, it can be pressed into which tissue is tested, and makes hardness number generate relatively large deviation because of pressure head.
Due to accelerating the cooling velocity of the surface section in cooling big in manufacturing method documented by patent document 3,4,
The case where only when heating steel sheet surface in the presence of the hardness for being unable to fully reduction surface section.
On the other hand, in the method documented by patent document 5,6, although when being reduced by derusting because of heat straightening
Surface texture caused by the impression defect of oxide skin is bad, and the cooling deviation for stopping temperature by reducing steel plate improves steel
Plate shape, but do not make any consideration about the cooling condition for obtaining uniform material.This is because if surface of steel plate
Cooling velocity generates deviation, then the hardness of steel plate can be made to generate deviation.That is, surface of steel plate carries out cold if cooling velocity is slow
When but, " film boiling " and bubble that the film of bubble is generated between surface of steel plate and cooling water are forming the preceding due to cooling water of film
" nuclear boiling " that is separated with surface while occurring, the cooling velocity of surface of steel plate can be made to generate deviation.As a result, steel plate table can be made
The hardness in face generates deviation.The point is not considered in technology documented by patent document 5,6.
Therefore, the present invention is in view of the above subject, it is therefore intended that it is excellent but also harsher to provide not only Resistant to HIC together
Resistance to SSCC under corrosive environment also excellent acid resistance line-pipes high-strength steel sheet and its advantageous manufacturing method.In addition,
It is an object of the invention to propose using high tensile steel tube obtained by above-mentioned acid resistance line-pipes high-strength steel sheet.
The inventors of the present invention in order to ensure the resistance to SSCC under harsher corrosive environment, to steel at be grouped as, it is microcosmic
A large amount of experiment and research is repeated in tissue and manufacturing condition.Finally, it is found that: the resistance to SSCC in order to make high tensile steel tube
It further increases, such as only inhibits surface hardness and insufficient previously known, the tissue of the pole surface section by especially making steel plate,
Specifically make the structure of steel dislocation density 1.0 × 10 of 0.5mm under surface of steel plate14~7.0 × 1014(m-2) bainite group
It knits, the ascending amount of hardness can be inhibited in the coating procedure after tubing, as a result, improve the resistance to SSCC of steel pipe.In addition, being
It realizes such structure of steel, needs the cooling velocity of 0.5mm under strict control surface of steel plate, successfully have found its condition.
The present invention is to know to see and complete based on this.
That is, the gist of the invention composition is as follows.
[1] a kind of acid resistance line-pipes high-strength steel sheet, which is characterized in that have as follows at being grouped as: with quality %
Meter contains C:0.02~0.08%, Si:0.01~0.50%, Mn:0.50~1.80%, P:0.001~0.015%, S:
0.0002~0.0015%, Al:0.01~0.08% and Ca:0.0005~0.005%, remainder is by Fe and inevitably
Impurity is constituted,
The structure of steel of 0.5mm is dislocation density 1.0 × 10 under surface of steel plate14~7.0 × 1014(m-2) bainite structure,
Under surface of steel plate the deviation of the Vickers hardness of 0.5mm be calculated as 30HV when standard deviation is set as σ with 3 σ hereinafter,
Tensile strength with 520MPa or more.
[2] the acid resistance line-pipes high-strength steel sheet according to above-mentioned [1], wherein mentioned component is formed with matter
% meter is measured, further containing selected from Cu:0.50% or less, Ni:0.50% or less, Cr:0.50% or less and Mo:0.50% or less
In it is one kind or two or more.
[3] the acid resistance line-pipes high-strength steel sheet according to above-mentioned [1] or [2], wherein mentioned component composition with
Quality % meter, further containing selected from Nb:0.005~0.1%, V:0.005~0.1%, Ti:0.005~0.1%, Zr:
0.0005~0.02%, one kind or two or more in Mg:0.0005~0.02% and REM:0.0005~0.02%.
[4] a kind of manufacturing method of acid resistance line-pipes high-strength steel sheet, which is characterized in that will have as follows into grouping
At steel disc be heated to 1000~1300 DEG C of temperature after, carry out hot rolling and steel plate be made, it is described at being grouped as in terms of quality %
Contain C:0.02~0.08%, Si:0.01~0.50%, Mn:0.50~1.80%, P:0.001~0.015%, S:0.0002
~0.0015%, Al:0.01~0.08% and Ca:0.0005~0.005%, remainder are Fe and inevitable impurity
Thereafter, cooling control is carried out to above-mentioned steel plate with following condition,
Surface of steel plate temperature when cooling beginning: (Ar3- 10 DEG C) more than,
Average cooling rate in terms of the steel billet temperature of 0.5mm under surface of steel plate from 750 DEG C to 550 DEG C: 80 DEG C/s hereinafter,
Average cooling rate in terms of steel plate mean temperature from 750 DEG C to 550 DEG C: 15 DEG C/s or more,
From 550 DEG C to the average cooling rate of temperature when cooling stopping in terms of the steel billet temperature of 0.5mm under surface of steel plate:
150 DEG C/s or more, and
The cooling temperature that stops in terms of steel plate mean temperature: 250~550 DEG C.
[5] manufacturing method of the acid resistance line-pipes high-strength steel sheet according to above-mentioned [4], wherein mentioned component
Composition is in terms of quality %, further containing selected from Cu:0.50% or less, Ni:0.50% or less, Cr:0.50% or less and Mo:
It is one kind or two or more in 0.50% or less.
[6] manufacturing method of the acid resistance line-pipes high-strength steel sheet according to above-mentioned [4] or [5], wherein above-mentioned
At being grouped as in terms of quality %, further containing selected from Nb:0.005~0.1%, V:0.005~0.1%, Ti:0.005~
0.1%, a kind in Zr:0.0005~0.02%, Mg:0.0005~0.02% and REM:0.0005~0.02% or 2 kinds with
On.
[7] a kind of high tensile steel tube is high-strength using acid resistance line-pipes described in any one of above-mentioned [1]~[3]
It spends obtained by steel plate.
Acid resistance line-pipes high-strength steel sheet of the invention and the height using the acid resistance line-pipes high-strength steel sheet
Not only Resistant to HIC is excellent for intensity steel pipe, but also the resistance to SSCC under harsher corrosive environment is also excellent.In addition, according to this
The manufacturing method of the acid resistance line-pipes high-strength steel sheet of invention, it is excellent can to manufacture not only Resistant to HIC, but also harsher
Corrosive environment under resistance to SSCC also excellent acid resistance line-pipes high-strength steel sheet.
Detailed description of the invention
Fig. 1 is the schematic diagram for taking method to be illustrated to the test film for evaluating the resistance to SSCC in embodiment.
Specific embodiment
Hereinafter, the acid resistance line-pipes high-strength steel sheet to the disclosure is specifically described.
[at being grouped as]
Firstly, to the high-strength steel sheet based on the disclosure at being grouped as and its restriction reason is illustrated.Below
The all quality % of unit indicated in explanation by %.
C:0.02~0.08%
C helps to effectively improve intensity, but when content is less than 0.02% is unable to ensure enough intensity, on the other hand,
If it exceeds 0.08%, then when accelerating cooling, since surface section, the hardness in center segregation portion rise, resistance to SSCC and resistance to HIC
Property be deteriorated.In addition, toughness is also deteriorated.Therefore, C amount is limited to 0.02~0.08% range.
Si:0.01~0.50%
Si is to add for deoxidation, but deoxidation effect is insufficient when content is less than 0.01%, on the other hand, if super
0.50% is crossed, then toughness, weldability can be made to be deteriorated, therefore Si amount is limited to 0.01~0.50% range.
Mn:0.50~1.80%
Mn helps to effectively improve intensity, toughness, but its additive effect is insufficient when content is less than 0.50%, another party
Face, if it exceeds 1.80%, then when accelerating cooling, since surface section, the hardness in center segregation portion rise, resistance to SSCC and resistance to
HIC is deteriorated.In addition, weldability is also deteriorated.Therefore, Mn amount is limited to 0.50~1.80% range.
P:0.001~0.015%
P is inevitable impurity element, and the hardness in center segregation portion is made to rise and make while making weldability be deteriorated
Resistant to HIC is deteriorated.If it exceeds 0.015%, then the trend becomes significantly, the upper limit to be defined as 0.015%.Preferably
0.008% or less.The lower content the better, but from the viewpoint of refining cost, make its 0.001% or more.
S:0.0002~0.0015%
S be inevitable impurity element, become MnS field trash in steel and Resistant to HIC made to be deteriorated, thus preferably compared with
It is few, it allows to be 0.0015% or less.The lower content the better, but from the viewpoint of refining cost, make its 0.0002% with
On.
Al:0.01~0.08%
Al is added as deoxidier, does not have additive effect when less than 0.01%, on the other hand, if it exceeds 0.08%,
Then the cleannes of steel reduce, degraded toughness, therefore Al amount is limited to 0.01~0.08% range.
Ca:0.0005~0.005%
Ca is so that Resistant to HIC is improved effective element the form control by sulfide-based field trash, but be less than
Its additive effect is insufficient when 0.0005%.When on the other hand, more than 0.005%, not only effect is saturated, but also because of the cleaning of steel
Degree reduces and Resistant to HIC is made to be deteriorated, therefore Ca amount is limited to 0.0005~0.005% range.
More than, the basis of the disclosure is illustrated, but in order to realize that the intensity, toughness of steel plate further changes
It is kind, the disclosure at be grouped as can arbitrarily contain in following range it is one kind or two or more in Cu, Ni, Cr and Mo.
Cu:0.50% or less
Cu is that improvement to toughness and intensity rise effective element, in order to obtain the effect, preferably comprise 0.05% with
On, if content is excessive, weldability is deteriorated, therefore is used as the upper limit for 0.50% when addition Cu.
Ni:0.50% or less
Ni is that improvement to toughness and intensity rise effective element, in order to obtain the effect, preferably comprise 0.05% with
On, it is not only unfavorable in economy if content is excessive, but also make the degraded toughness of welding heat affected zone, therefore add Ni
When by 0.50% be used as the upper limit.
Cr:0.50% or less
It is same as Mn, even if Cr is pair also to obtain the effective element of enough intensity at low C, the effect in order to obtain,
0.05% or more is preferably comprised, if content is excessive, harden ability is become over, therefore aftermentioned dislocation density is got higher, resistance to
SSCC is deteriorated.In addition, weldability is also deteriorated.Therefore, the upper limit is used as by 0.50% when adding Cr.
Mo:0.50% or less
Mo is the effective element of rising of the improvement and intensity to toughness, and the effect, preferably comprises 0.05% in order to obtain
More than, if content is excessive, harden ability is become over, therefore aftermentioned dislocation density is got higher, and resistance to SSCC is deteriorated.In addition,
Weldability is also deteriorated, and therefore, is used as the upper limit for 0.50% when adding Mo.
The disclosure at being grouped as and further arbitrarily can also contain a kind or 2 in Nb, V and Ti in following range
Kind or more.
Selected from Nb:0.005~0.1%, V:0.005~0.1%, Ti:0.005~0.1%, Zr:0.0005~0.02%,
It is one kind or two or more in Mg:0.0005~0.02% and REM:0.0005~0.02%
Nb, V and Ti are provided to improve the intensity of steel plate and toughness and the element that can arbitrarily add.Each leisure of each element
When content is less than 0.005%, additive effect is insufficient, on the other hand, if it exceeds 0.1%, then the degraded toughness of weld part, because
This, when addition all preferably 0.005~0.1% range.Zr, Mg and REM are to be miniaturize by crystal grain and to improve toughness
Or the element that fracture-resistant can be added arbitrarily is improved by the control of field trash character.Each comfortable content of these elements
When less than 0.0005%, additive effect is insufficient, on the other hand, if it exceeds 0.02%, effect saturation, therefore, when addition
All preferably 0.0005~0.02% range.
The present disclosure discloses it is a kind of for improve use acid resistance line-pipes high-strength steel sheet high tensile steel tube it is resistance to
The technology of SSCC, in addition to acid resistance, it is also necessary to while meeting Resistant to HIC, such as preferably make the CP found out by following formula (1)
Value is 1.00 or less.It should be noted that as long as the element not added substitutes into 0.
+ 2.37 [%Mn]/6+ of CP=4.46 [%C] (1.74 [%Cu]+1.7 [%Ni])/15+ (1.18 [%Cr]+1.95
[%Mo]+1.74 [%V])/5+22.36 [%P] (1)
Wherein, [%X] indicates content (quality %) in the steel of X element.
Here, above-mentioned CP value is the public affairs designed to infer the material in center segregation portion by the content of each alloying element
The CP value of formula, above-mentioned formula (1) is higher, and the constituent concentration in center segregation portion is higher, and the hardness in center segregation portion rises.Therefore, lead to
Crossing makes the CP value 1.00 found out in above-mentioned formula (1) hereinafter, the crackle being able to suppress in HIC test generates.In addition, due to CP
Value is lower, and the hardness in center segregation portion is lower, therefore when requiring higher Resistant to HIC, can make to be limited to 0.95 thereon.
It should be noted that the remainder in addition to above-mentioned element is made of Fe and inevitable impurity.But as long as not
Function and effect of the invention are damaged, even other microelements.For example, N is the element inevitably contained in steel,
If its content be 0.007% or less, preferably 0.006% hereinafter, if can be allowed in the present invention.
[tissue of steel plate]
Next, being illustrated to the structure of steel of the acid resistance line-pipes high-strength steel sheet of the disclosure.It is drawn to realize
The high intensity that intensity is 520MPa or more is stretched, needing structure of steel is bainite structure.In particular, surface section generation martensite,
When the hard phases such as island-like martensite (MA), surface hardness rises, and the deviation of the hardness in steel plate increases and hinders property uniform in material.
In order to inhibit the rising of surface hardness, make the structure of steel bainite structure of surface section.Here, bainite structure, which is included in, helps
Phase transformation is carried out when the acceleration of phase transformation strengthening is cooling or after acceleration is cooling is referred to as bainite ferrite or granular ferritic
Tissue.If different types of tissue such as ferrite, martensite, pearlite, island-like martensite, retained austenite is mixed in bayesian
In body tissue, then the reduction of intensity, the deterioration of toughness, rising of surface hardness etc., therefore the group other than bainite phase can be generated
It is more fewer better to knit point rate.But the volume fraction of the tissue other than bainite phase it is sufficiently low when, their influence can be ignored,
As long as being therefore allowed to for a degree of amount.Specifically, in the disclosure, if the structure of steel other than bainite
Adding up in terms of volume fraction less than 5% for (ferrite, martensite, pearlite, island-like martensite, retained austenite etc.), then do not have
Have a significant impact, therefore can be allowed to.
In addition, there is also various forms corresponding with cooling velocity in bainite structure, but in the disclosure, it is important
Be make steel plate pole surface section tissue, specifically make the structure of steel dislocation density 1.0 × 10 of 0.5mm under surface of steel plate14
~7.0 × 1014(m-2) bainite structure.Since the coating procedure Dislocations density after tubing can reduce, as long as steel
The dislocation density of 0.5mm is 7.0 × 10 under plate surface14(m-2) below, it will be able to by the rising because of the hardness caused by age-hardening
Amount is suppressed to irreducible minimum.On the contrary, if the dislocation density of 0.5mm is more than 7.0 × 10 under surface of steel plate14(m-2), then after tubing
Coating procedure Dislocations density will not reduce, increase significantly hardness, resistance to SSCC made to be deteriorated.Because making
Obtain good resistance to SSCC after pipe and the range of preferred dislocation density is 6.0 × 1014(m-2) below.On the other hand, steel plate
The dislocation density of 0.5mm is less than 1.0 × 10 under surface14(m-2) Shi Buneng is maintained as the intensity of steel plate.In order to ensure X65 etc.
The intensity of grade preferably has 2.0 × 1014(m-2) more than dislocation density.It should be noted that in the high-strength steel sheet of the disclosure,
As long as the dislocation density of the structure of steel of 0.5mm is in above range under surface of steel plate, the depth away from surface of steel plate is the model of 0.5mm
The pole surface section enclosed also has same dislocation density, as a result, the effect that above-mentioned resistance to SSCC is improved can be obtained.
It should be noted that if making the dislocation density 7.0 × 10 of 0.5mm under surface of steel plate14(m-2) hereinafter, then under surface
The HV0.1 of 0.5mm is 230 or less.From the viewpoint of the resistance to SSCC for ensuring steel pipe, it is important that inhibit the surface layer of steel plate hard
Degree, the HV0.1 230 of 0.5mm is hereinafter, can will be under the surface after the coating procedure after tubing under the surface by making steel plate
The HV0.1 of 0.5mm is suppressed to 260 or less, it can be ensured that resistance to SSCC.
In addition, in the high-strength steel sheet of the disclosure, the deviation of the Vickers hardness of 0.5mm is by standard deviation under surface of steel plate
30HV or less is calculated as when being set as σ with 3 σ to be also important.Its reason is: under measurement surface of steel plate when the Vickers hardness of 0.5mm
3 σ be more than 30HV in the case where, due to the hardness deviation on the pole surface layer of steel plate, i.e., pole surface layer exist part high rigidity portion
Position, thus generate using the position as the deterioration of the resistance to SSCC of starting point.It should be noted that preferably existing in advance when finding out standard deviation
100 points or more measure Vickers hardness.
The high-strength steel sheet of the disclosure is the steel for steel pipes plate of the intensity of the X60 grade with API 5L or more, therefore is had
There is the tensile strength of 520MPa or more.
[manufacturing method]
Hereinafter, to for manufacturing above-mentioned acid resistance line-pipes high-strength steel sheet manufacturing method and manufacturing condition have
Body explanation.Is carried out by hot rolling and steel is made after the steel disc formed with mentioned component heating for the manufacturing method of the disclosure
Then plate carries out the cooling control under rated condition to the steel plate.
(slab heating temperature)
Slab heating temperature: 1000~1300 DEG C
When slab heating temperature is less than 1000 DEG C, the solid solution of carbide is insufficient, cannot get required intensity, another party
Face, if it exceeds 1300 DEG C, then degraded toughness, therefore make 1000~1300 DEG C of slab heating temperature.It should be noted that the temperature
For the in-furnace temperature of heating furnace, slab is heated to the temperature until central part.
(rolling terminates temperature)
In hot-rolled process, high base metal tenacity in order to obtain, it is more lower better that rolling terminates temperature, but then, rolling
Efficiency reduces, thus with the rolling of surface of steel plate thermometer end temperature needs to consider required base metal tenacity and rolling efficiency and
Setting.From the viewpoint of improving intensity and Resistant to HIC, so that rolling is terminated temperature and Ar is calculated as with surface of steel plate temperature3Phase
It is more than height.Here, Ar3Transformation temperature refers to the ferrite transformation start temperature in cooling, for example, can according to the ingredient of steel by
Following formula is found out.In addition, high base metal tenacity in order to obtain, preferably makes to be equivalent to the 950 of austenite non-recrystallization temperature region
The reduction ratio of DEG C temperature region below is 60% or more.It should be noted that radiation thermometer can be used in the surface temperature of steel plate
Etc. being measured.
Ar3- 80 [% of (DEG C)=910-310 [%C] -80 [%Mn] -20 [%Cu] -15 [%Cr] -55 [%Ni]
Mo]
Wherein, [%X] indicates content (quality %) in the steel of X element.
(the cooling start temperature of cooling control)
Cooling start temperature: (Ar is calculated as with surface of steel plate temperature3- 10 DEG C) more than
If surface of steel plate temperature when cooling beginning is low, the ferrite generation quantitative change before cooling control is more, especially
If from Ar3The temperature slippage of transformation temperature is more than 10 DEG C, then generates the ferrite that volume fraction is more than 5%, and strength reduction becomes
Greatly, while Resistant to HIC is deteriorated, therefore makes surface of steel plate temperature (Ar when cooling beginning3- 10 DEG C) more than.
(cooling velocity of cooling control)
In order to realize high intensity and reduce the deviation of the hardness in steel plate, improve property uniform in material, it is important that
Control the average cooling rate in the cooling velocity and steel plate of surface section.In particular, the dislocation in order to make 0.5mm under surface of steel plate
Density, i.e. 3 σ need the cooling velocity to 0.5mm under surface of steel plate to control in above range.
Average cooling rate in terms of the steel billet temperature of 0.5mm under surface of steel plate from 750 DEG C to 550 DEG C: 80 DEG C/s or less
If the average cooling rate in terms of the steel billet temperature of 0.5mm under surface of steel plate from 750 DEG C to 550 DEG C is more than 80
DEG C/s, then the dislocation density of 0.5mm can be more than 7.0 × 10 under surface of steel plate14(m-2).As a result, 0.5mm under surface of steel plate
HV0.1 is more than 230, and the HV0.1 of 0.5mm is more than 260 under the surface after coating procedure after tubing, the resistance to SSCC of steel pipe
It is deteriorated.Therefore, make 80 DEG C/s or less of the average cooling rate.Preferably 50 DEG C/s or less.The lower limit of the average cooling rate
Be not particularly limited, but if cooling velocity is too small, then generate ferrite, pearlite and become intensity deficiency, therefore from preventing
From the viewpoint of the situation, preferably 20 DEG C/s or more.
Average cooling rate in terms of steel plate mean temperature from 750 DEG C to 550 DEG C: 15 DEG C/s or more
When average cooling rate in terms of steel plate mean temperature from 750 DEG C to 550 DEG C is less than 15 DEG C/s, it cannot get bainite
Organize and generate the deterioration of strength reduction, Resistant to HIC.Therefore, make the 15 DEG C/s of cooling velocity in terms of steel plate mean temperature with
On.From the viewpoint of from the deviation of armor plate strength and hardness, the average cooling velocity of steel plate is preferably 20 DEG C/s or more.This is average
The upper limit of cooling velocity is not particularly limited, in order to avoid excessively generating low temperature phase change product, preferably 80 DEG C/s or less.
From 550 DEG C to the average cooling rate of temperature when cooling stopping in terms of the steel billet temperature of 0.5mm under surface of steel plate:
150 DEG C/s or more
For the steel billet temperature of 0.5mm is calculated as 550 DEG C of coolings below under with surface of steel plate, it is important that with stabilization
Nuclear boiling state cooling, the rising of water yield density is indispensable.From 550 in terms of the steel billet temperature of 0.5mm under surface of steel plate
When the average cooling rate of temperature when DEG C to cooling stopping is less than 150 DEG C/s, it can not become with the cooling of nuclear boiling state, In
The pole surface section of steel plate generates hardness deviation, and 3 σ of 0.5mm can be more than 30HV under surface of steel plate, as a result, resistance to SSCC is deteriorated.
Therefore, make 150 DEG C/s or more of the average cooling rate.Preferably 170 DEG C/s or more.The upper limit of the average cooling rate does not have
It is particularly limited to, considers from the restriction in equipment, preferably 250 DEG C/s or less.
It should be noted that 0.5mm and steel plate mean temperature can not directly be measured in a manner of physics under surface of steel plate,
But surface when the cooling stopping of the surface temperature and target when can be according to the cooling beginning measured using radiation thermometer
Temperature, such as the Temperature Distribution in plate thickness section is found out by Difference Calculation using process computer in real time.By the temperature
The temperature of 0.5mm is as " steel billet temperature of 0.5mm under surface of steel plate " in this specification under surface of steel plate in distribution, by this
The average value of the temperature in the plate thickness direction in Temperature Distribution is as " the steel plate mean temperature " in this specification.
(cooling to stop temperature)
It is cooling to stop temperature: 250~550 DEG C of steel plate mean temperature In
After rolling, and being quenched to temperature region, i.e. 250~550 DEG C of bainitic transformation in cooling control
Bainite phase.If the cooling temperature that stops is more than 550 DEG C, bainitic transformation is incomplete, cannot get enough intensity.Separately
Outside, when cooling stopping temperature is less than 250 DEG C, the hardness rising of surface section becomes obvious, the dislocation density of 0.5mm under surface of steel plate
Become more than 7.0 × 1014(m-2), therefore resistance to SSCC is deteriorated.In addition, the hardness in center segregation portion is also got higher, Resistant to HIC
It is deteriorated.Therefore, in order to inhibit the deterioration of the property uniform in material in steel plate, the cooling temperature that stops of cooling control is with the average temperature of steel plate
Degree is calculated as 250~550 DEG C.
[high tensile steel tube]
After the high-strength steel sheet of the disclosure is shaped to tubulose using bent into shape, rolling and forming, UOE molding etc.,
Docking section is welded, can manufacture be suitable for conveying crude oil or natural gas, that property uniform in material in steel plate is excellent is resistance to
Acid line-pipes high tensile steel tube (UOE steel pipe, electric-resistance-welded steel pipe, spiral steel pipe etc.).
For example, UOE steel pipe carries out retaining wall on slope by the end to steel plate, is suppressed and formed using C compacting, U compacting, O
After steel pipe shape, seam weld is carried out to docking section using inner surface welding and outer surface welding, further as needed through expansion
Plumber's sequence and manufacture.In addition, as long as welding method can obtain enough strength of joints and joint toughness, so that it may be any
Method, it is preferable to use submerged-arc welding from the viewpoint of excellent welding quality and manufacture efficiency.
Embodiment
It will be become shown in table 1 using continuous casting process and slab be made at the steel (steel grade A~K) being grouped as, be heated to
After temperature shown in table 2, carrying out rolling shown in table 2 terminates the hot rolling of temperature and reduction ratio, and plate shown in table 2 is made
Thick steel plate.Then, cooling control is carried out to steel plate using the cooling controller of water-cooling type under conditions of being shown in table 2.
[determination of tissue]
The microstructure of obtained steel plate is observed using optical microscopy and scanning electron microscope.By steel plate
The tissue in tissue and the plate thickness center of the position of 0.5mm is shown in table 2 under surface.
[measurement of tensile strength]
Complete thick test film with rolling direction direction at right angle is subjected to tension test as tension test sheet, measurement is drawn
Stretch intensity.Show the result in table 2.
[measurement of Vickers hardness]
For with rolling direction section at right angle, according to the 0.5mm under surface of steel plate of JIS Z 2244 position finding
100 points of Vickers hardness (HV0.1), finds out its average value and standard deviation.The value of average value and 3 σ is shown in table 2.Here,
It is measured with HV0.1 to replace usually used HV10, this is because so that impression is become smaller and being measured with HV0.1,
Therefore it can become hardness information, the hardness information more sensitive to microstructure closer to the position on surface.
[dislocation density]
X-ray diffraction sample is taken from the position with average hardness, sample surfaces are ground and remove deoxidation
Change skin, the position of 0.5mm carries out X-ray diffraction measure under surface of steel plate.Dislocation density is used from by X-ray diffraction measure
The method that the strain that half breadth β is found out converts.In the diffracted intensity curve obtained by common X-ray diffraction, by
It is overlapped in both different 2 rays of 1 ray of K α and K α of wavelength, therefore is separated using Rachinger method.The extraction of strain
Use Williamsson-Hall method described below.The expansion of half breadth is influenced by the dimension D and strain stress of crystallite, can be with
Following formula by two factors and in the form of calculated.That is, β=β 1+ β 2=(0.9 λ/(D × cos θ))+2 ε × tan θ.Into
One step deforms the formula, becomes β cos θ/λ=0.9 λ/D+2 ε × sin θ/λ.β cos θ/λ is marked relative to sin θ/λ
It draws, strain stress is calculated by the slope of straight line.It should be noted that it should be noted that calculate used in diffracted ray be (110), (211),
(220).The ε of ρ=14.4 is used by the conversion of strain stress to dislocation density2/b2.It should be noted that θ indicates the θ -2 by X-ray diffraction
θ method and the peak angle calculated, λ indicate the wavelength of the X-ray used in X-ray diffraction.B is the Burgers vector of Fe (α)
(Burgers vector) is in the present embodiment 0.25nm.
[evaluation of resistance to SSCC]
Resistance to SSCC carries out tubing by using a part of these each steel plates to evaluate.Tubing passes through the end to steel plate
Retaining wall on slope is carried out, after steel pipe shape, utilizes submerged-arc welding inner surface and outer surface using C compacting, U compacting, O compression moulding
Docking section carry out seam weld, manufactured by expansion process.As shown in Figure 1, the template cut out from obtained steel pipe is flattened
Afterwards, the SSCC test film of 5 × 15 × 115mm is taken from steel pipe internal-surface.At this point, the inner surface as plane was seized, in order to retain
The state on most surface layer and directly have casting skin.The actual yield strength (0.5% of each steel pipe is loaded to the SSCC test film taken
YS 90% stress), using NACE standard TM0177Solution solution A, in hydrogen sulfide sectional pressure: under 1bar, foundation
4 points of bending SSCC of EFC16 standard are tested and are carried out.After 720 hours dippings, it will be judged as resistance to the case where can't see crackle
SSCC is good, is denoted as zero, in addition, the case where cracking, is judged as bad, be denoted as ×.Show the result in table 2.
Resistant to HIC by using the HIC test of 96 hours of NACE standard TM0177 Solution solution A dippings and into
Row investigation.For Resistant to HIC, the situation that crack length rate (CLR) is 15% or less in HIC test is judged as good
It is good, the case where being denoted as zero, will being more than 15% is judged as ×.Show the result in table 2.
Target zone of the invention is as follows: as acid resistance line-pipes high-strength steel sheet, tensile strength: 520MPa with
On, the microstructure of the position 0.5mm and the position t/2 is all bainite structure under the surface, and the HV0.1 of 0.5mm is 230 under surface
Hereinafter, can't see crackle in SSCC test, and in HIC for using the steel plate to carry out high tensile steel tube obtained by tubing
Crack length rate (CLR) is 15% or less in test.
As shown in table 2, No.1~No.15 is at being grouped as the invention for meeting proper range of the invention with manufacturing condition
Example.It is all tensile strength: 520MPa or more as steel plate, the microstructure of the position 0.5mm and the position t/2 is bayesian under surface
Body tissue, the HV0.1 of 0.5mm is 230 hereinafter, resistance to SSCC in the high tensile steel tube obtained by using the steel plate tubing under surface
It is good with Resistant to HIC.
In contrast, No.16~No.23, which is into, is grouped as within the scope of the invention but manufacturing condition is of the invention
Comparative example outside range.No.16 since slab heating temperature is low, do not fill by the solid solution of microstructure to homogenize with carbide
Point and intensity is low.No.17 becomes and ferritic lamellar tissue has been precipitated, therefore intensity is low since cooling start temperature is low, and
Resistant to HIC after tubing is deteriorated.No.18 is due to cooling down control condition outside the scope of the present invention, as microstructure in plate thickness
Center portion cannot get bainite structure, become ferrite+pearlitic structrure, therefore intensity is low, and the Resistant to HIC after tubing becomes
Difference.No.19 is since cooling stopping temperature is low, and the dislocation density of 0.5mm is got higher under surface, and HV0.1 is more than 230, therefore after tubing
Resistance to SSCC it is poor.In addition, Resistant to HIC is also deteriorated since the hardness in center segregation portion is also got higher.No.20 and No.23 by
750 → 550 DEG C of the average cooling rate of 0.5mm is more than 80 DEG C/s under surface of steel plate, thus under surface 0.5mm dislocation it is close
Degree is got higher, and HV0.1 is more than 230, and the resistance to SSCC after tubing is poor.In addition, the Resistant to HIC of surface section is also deteriorated in No.23.
No.21 and No.22 is since 550 DEG C of average cooling rates below of 0.5mm under surface of steel plate are less than 150 DEG C/s, steel plate
Inhomogeneous cooling become significantly, although HV0.1 meets average out to 230 hereinafter, hardness deviation is big, part generates with high hardness
Part, thus the resistance to SSCC after tubing is poor.No.24~No.27 is since steel plate is at being grouped as out of the range of the present invention, table
The dislocation density of 0.5mm is got higher under face and HV0.1 is more than 230, therefore the resistance to SSCC after tubing is poor.In addition, No.24~
For No.27 since the hardness in center segregation portion increases, Resistant to HIC is also poor.
Industrial availability
In accordance with the invention it is possible to which it is excellent but also resistance under harsher corrosive environment to provide a kind of not only Resistant to HIC
SSCC also excellent acid resistance line-pipes high-strength steel sheet.Therefore, the steel pipe (electricity for cold forming being carried out to the steel plate and being manufactured
Welding resistance steel pipe, spiral steel pipe, UOE steel pipe etc.) it can be preferred for requiring crude oil or natural gas acid proof, containing hydrogen sulfide
Conveying.
Claims (7)
1. a kind of acid resistance line-pipes high-strength steel sheet, which is characterized in that have as follows at being grouped as: being contained in terms of quality %
C:0.02~0.08%, Si:0.01~0.50%, Mn:0.50~1.80%, P:0.001~0.015%, S:0.0002~
0.0015%, Al:0.01~0.08% and Ca:0.0005~0.005%, remainder is by Fe and inevitable impurity structure
At,
The structure of steel of 0.5mm is dislocation density 1.0 × 10 under surface of steel plate14~7.0 × 1014m-2Bainite structure,
Under surface of steel plate the deviation of the Vickers hardness of 0.5mm be calculated as 30HV when standard deviation is set as σ with 3 σ hereinafter,
Tensile strength with 520MPa or more.
2. acid resistance line-pipes high-strength steel sheet according to claim 1, wherein described at being grouped as in terms of quality %
Further containing a kind in Cu:0.50% or less, Ni:0.50% or less, Cr:0.50% or less and Mo:0.50% or less
Or two or more.
3. acid resistance line-pipes high-strength steel sheet according to claim 1 or 2, wherein described at being grouped as with matter
% meter is measured further containing selected from Nb:0.005~0.1%, V:0.005~0.1%, Ti:0.005~0.1%, Zr:0.0005
~0.02%, one kind or two or more in Mg:0.0005~0.02% and REM:0.0005~0.02%.
4. a kind of manufacturing method of acid resistance line-pipes high-strength steel sheet, which is characterized in that will have as follows at being grouped as
After steel disc is heated to 1000~1300 DEG C of temperature, carries out hot rolling and steel plate is made, it is described to be contained in terms of quality % at being grouped as
C:0.02~0.08%, Si:0.01~0.50%, Mn:0.50~1.80%, P:0.001~0.015%, S:0.0002~
0.0015%, Al:0.01~0.08% and Ca:0.0005~0.005%, remainder be Fe and inevitable impurity,
Thereafter, cooling control is carried out to the steel plate with following condition:
Surface of steel plate temperature when cooling beginning: (Ar3- 10 DEG C) more than,
Average cooling rate in terms of the steel billet temperature of 0.5mm under surface of steel plate from 750 DEG C to 550 DEG C: 80 DEG C/s hereinafter,
Average cooling rate in terms of steel plate mean temperature from 750 DEG C to 550 DEG C: 15 DEG C/s or more,
From 550 DEG C to the average cooling rate of temperature when cooling stopping in terms of the steel billet temperature of 0.5mm under surface of steel plate: 150
DEG C/s or more, and
The cooling temperature that stops in terms of steel plate mean temperature: 250~550 DEG C.
5. the manufacturing method of acid resistance line-pipes high-strength steel sheet according to claim 4, wherein described at being grouped as
Further containing selected from Cu:0.50% or less, Ni:0.50% or less, Cr:0.50% or less and Mo:0.50% in terms of quality %
It is one kind or two or more in below.
6. the manufacturing method of acid resistance line-pipes high-strength steel sheet according to claim 4 or 5, wherein the ingredient
Composition in terms of quality % further containing selected from Nb:0.005~0.1%, V:0.005~0.1%, Ti:0.005~0.1%,
It is one kind or two or more in Zr:0.0005~0.02%, Mg:0.0005~0.02% and REM:0.0005~0.02%.
7. a kind of high tensile steel tube is using acid resistance line-pipes high-strength steel sheet described in any one of claims 1 to 33
Obtained by.
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| PCT/JP2017/034800 WO2018179512A1 (en) | 2017-03-30 | 2017-09-26 | High-strength steel plate for sour resistant line pipe, method for manufacturing same, and high-strength steel pipe using high-strength steel plate for sour resistant line pipe |
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| JP (1) | JP6521197B2 (en) |
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| CN109517959A (en) * | 2018-12-17 | 2019-03-26 | 包头钢铁（集团）有限责任公司 | Effective hot rolled strip of a kind of low cost conveying and preparation method thereof |
| WO2023231981A1 (en) * | 2022-05-30 | 2023-12-07 | 宝山钢铁股份有限公司 | High-strength petroleum pipe casing and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6665822B2 (en) * | 2017-03-30 | 2020-03-13 | Ｊｆｅスチール株式会社 | High strength steel sheet for sour resistant line pipe, method for producing the same, and high strength steel pipe using high strength steel sheet for sour resistant line pipe |
| EP3859027B1 (en) * | 2018-09-28 | 2023-08-02 | JFE Steel Corporation | High strength steel plate for sour-resistant line pipe and method for manufacturing same, and high strength steel pipe using high strength steel plate for sour-resistant line pipe |
| WO2020067210A1 (en) * | 2018-09-28 | 2020-04-02 | Ｊｆｅスチール株式会社 | High-strength steel sheet for sour-resistant line pipe, method for producing same, and high-strength steel pipe using high-strength steel sheet for sour-resistant line pipe |
| US20220010418A1 (en) * | 2018-10-26 | 2022-01-13 | Posco | High-strength steel having excellent resistance to sulfide stress cracking, and method for manufacturing same |
| BR112022001623A2 (en) * | 2019-07-31 | 2022-03-22 | Jfe Steel Corp | High strength steel plate for acid resistant line pipe, production method thereof, and high strength steel pipe |
| WO2021176590A1 (en) * | 2020-03-04 | 2021-09-10 | 日本製鉄株式会社 | Steel pipe and steel sheet |
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Also Published As
| Publication number | Publication date |
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| BR112019019696A2 (en) | 2020-04-14 |
| KR20190129957A (en) | 2019-11-20 |
| EP3604584A4 (en) | 2020-03-04 |
| JP6521197B2 (en) | 2019-05-29 |
| JPWO2018179512A1 (en) | 2019-04-18 |
| KR102478368B1 (en) | 2022-12-15 |
| BR112019019696B1 (en) | 2022-07-19 |
| EP3604584A1 (en) | 2020-02-05 |
| KR20210118961A (en) | 2021-10-01 |
| CN110462080B (en) | 2022-01-04 |
| WO2018179512A1 (en) | 2018-10-04 |
| EP3604584B1 (en) | 2022-05-18 |
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