CN103103441A - Pressure container steel with high toughness at -140 DEG C and production method thereof - Google Patents
Pressure container steel with high toughness at -140 DEG C and production method thereof Download PDFInfo
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Abstract
The invention relates to pressure container steel with high toughness at -140 DEG C. The pressure container steel comprises the following components by weight: less than or equal to 0.05 of C, less than or equal to 0.05 of Si, 0.50-1.00 of Mn, less than or equal to 0.006 of P, less than or equal to 0.003 of S, 0.015-0.050 of Alt, 4.50-5.30 of Ni, 0.02-0.05 of Nb, 0.008-0.025 of Ti, less than or equal to 0.004 of N and one or more of less than or equal to 0.50 of Cr, less than or equal to 0.50 of Mo, less than or equal to 0.30 of Cu and less than or equal to 0.005 of Ca. A process of the pressure container steel comprises the following steps: smelting and continuously casting to form a blank; heating a casting blank; rough rolling at a first stage; rough rolling at a second stage after cooling for the first time; finish rolling after cooling for the second time; and carrying out heat treatment according to the thickness of a steel plate for later use. When the pressure container steel is at -140 DEG C, KV2 is not less than 100J, a transverse crack thickness rate CTR is less than or equal to 3%, a transverse crack length rate CLR is less than or equal to 10%, a transverse crack sensitivity rate is less than or equal to 1.5%, the content of Ni is low, and the welding performance is excellent.
Description
Technical field
The present invention relates to container with steel alloy and production method thereof, belong to particularly a kind of low-temperature pressure vessel steel and production method thereof, further for being suitable for pressure vessel steel and the production method thereof of 140 ℃ of ﹣.
Background technology
Before the present invention proposed, although existing Ni is some research work of low-temperature steel, its thought channel was the mode that the content of the Ni that adds along with the reduction of temperature will increase thereupon, and this causes production cost higher.As, through retrieval, Japanese documentation JP60059032 discloses " a kind of excellent low-temperature flexibility and the nickelic steel plate of low yield strength ratio and manufacture method thereof ", and its composition quality per-cent is C≤0.03, Si:0.02 ~ 0.22, Mn:0.05 ~ 0.47, P≤0.005, S≤0.005, Ni:7.5 ~ 12.0, C, Mn or Nb(0.005 ~ 0.03 can be added in Al:0.01 ~ 0.10 when needing) or V(0.005 ~ 0.03) etc. more than one elements, all the other are Fe and inevitable impurity ".Although the disclosed steel grade of the document can satisfy i.e.-160 ℃ of environment for use requirements of extremely low temperature, it has added 7.5 ~ 12.0 Ni, causes production cost high, and application is restricted.
Japanese Patent JP7173534 " a kind of Ni high tenacity low temperature steel plate and manufacture method thereof of containing ", its composition quality per-cent is C:0.01 ~ 0.12, Si:0.10 ~ 0.30, Mn:0.1 ~ 1.0, P≤0.010, S≤0.005, Al:0.005 ~ 0.050, Ni:7.5 ~ 10.0, all the other are Fe and inevitable impurity.The not enough nickel content of its existence is still higher, namely 7.5 ~ 10.0%.
It is also 201110331478.9 document just like the Chinese patent number of patent application, " a kind of high-tenacity-130 DEG C low-temperature steel and manufacture method thereof " disclosed, related steel has following ingredients and mass percent is C≤0.12, Si:0.10 ~ 0.35, Mn:0.30 ~ 1.00, P≤0.015, S≤0.005, Ni:4.70 ~ 5.30, Al:0.005 ~ 0.10, contain in addition Nb≤0.040, V≤0.06, Cr≤0.25, Mo≤0.50, Zr≤0.050, one or more in RE≤0.020, all the other are Fe and inevitable impurity.In the document, Ni is content 4.70 ~ 5.30%, and its Japanese Patent is lower relatively, but its adaptive temperature only has-130 ℃, can not be applicable to the making of the pressurized vessel under the lower temperature environment.
Summary of the invention
Especially Ni content is higher with the alloy of steel steel grade to the object of the invention is to overcome existing low-temperature (low temperature) vessel, temperature with contain the be inversely proportional to deficiency of relation of Ni, a kind of-140 ℃ lower KV is provided
2Be not less than 100J, transverse crack thickness rate CTR≤3%, transverse crack length rate CLR≤10%, the responsive rate CSR of transverse crack≤1.5%, Ni content is low, the pressure vessel steel and the production method thereof that are suitable for 140 ℃ of ﹣ that welding property is good.
Realize the measure of above-mentioned purpose:
The steels for pressure vessel use that has high tenacity under 140 ℃ of a kind of ﹣, its component and weight percent content are: C≤0.05, Si≤0.05, Mn:0.50 ~ 1.00, P≤0.006, S≤0.003, Alt:0.015 ~ 0.050, Ni:4.50 ~ 5.30, Nb:0.02 ~ 0.05, Ti:0.008 ~ 0.025, N≤0.004 is contained Cr≤0.50 in addition, Mo≤0.50, Cu≤0.30, Ca≤0.005, in a kind of or more than one, surplus is Fe and inevitably being mingled with.
The steels for pressure vessel use that has high tenacity under 140 ℃ of a kind of ﹣, its component and weight percent content are: C≤0.03, Si≤0.05, Mn:0.60 ~ 1.00, P≤0.006, S≤0.003, Alt:0.015 ~ 0.050, Ni:4.50 ~ 5.00, Nb:0.02 ~ 0.05, Ti:0.008 ~ 0.025,, N≤0.004, Cu:0.10 ~ 0.30, Ca:0.002 ~ 0.005, surplus are Fe and inevitably are mingled with.
The steels for pressure vessel use that has high tenacity under 140 ℃ of a kind of ﹣, its component and weight percent content are: C:0.03 ~ 0.05, Si≤0.05, Mn:0.50 ~ 0.80, P≤0.006, S≤0.003, Alt:0.015 ~ 0.050, Ni:5.00 ~ 5.30, Nb:0.02 ~ 0.05, Ti:0.008 ~ 0.025,, N≤0.004, Cr:0.10 ~ 0.40, Mo:0.20 ~ 0.40, Ca:0.002 ~ 0.005, surplus is Fe and inevitably is mingled with.
Produce the method that has the steels for pressure vessel use of high tenacity under 140 ℃ of a kind of ﹣, the steps include:
1) smelting also, continuous casting becomes base: carry out Ca and process in the LF stove, in the control molten steel, Ca is within target; Control the RH vacuum processing time and be not less than 20 minutes;
2) to the strand heating, control Heating temperature at 1200 ~ 1300 ℃, control heating rate at 9 ~ 12 minutes/centimetre;
3) carry out the first rough rolling step, the start rolling temperature of controlling this stage is not less than 1100 ℃;
4) through for the first time after temperature, be to carry out the subordinate phase roughing under 1000 ℃ ~ 1050 ℃ at start rolling temperature;
5) through for the second time after temperature, be to carry out finish rolling under 930 ℃ ~ 960 ℃ at start rolling temperature, controlling finishing temperature is 760 ~ 820 ℃;
6) heat-treat according to steel plate thickness:
During at 10 ~ 20 millimeters, the mode that adopts normalizing to add cooling+tempering is fast carried out when steel plate thickness, and normalizing temperature is 800 ~ 900 ℃, the normalizing time be (minute): t+30, tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50; In formula: t is the thickness of steel plate, and unit is millimeter; Quick when cooling red temperature be controlled at 400 ~ 600 ℃;
When steel plate thickness greater than 20 when being no more than 40 millimeters, adopt the mode of quenching+tempering to carry out, quenching temperature is 800 ~ 900 ℃, the cool time be (minute): t+30, tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50;
In formula: t is the thickness of steel plate, and unit is millimeter;
When steel plate thickness greater than 40 when being no more than 60 millimeters, adopt the mode of two quenching+temperings to carry out, quenching temperature is 800 ~ 900 ℃ for the first time, the cool time be (minute): t+30; Quenching temperature is 750 ~ 850 ℃ for the second time, the cool time be (minute): t+30; Tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50;
In formula: t is the thickness of steel plate, and unit is millimeter;
7) stand-by.
Composition and the main production of steel of the present invention below are described in detail in detail set reason:
The maximum difficult point of this steel is to guarantee having simultaneously excellent toughness (140 ℃), welding property and resistance against hydrogen cracking (HIC) performance.Therefore, to strictly control the purity of molten steel during steel-making, prevent that P, S content are on the impact of this steel anti-H 2 S stress corrosion performance.The design mix of Mn, Nb, Cu, Ti, Ni has guaranteed intensity, toughness and the welding property of steel, wherein the Ni alloy is mainly used to improve the low-temperature flexibility of steel, the Ti alloy can the refinement Plate Welding heat affected zone tissue, improve toughness levels, Cu, Mo can improve the stability after steel plate SR.Generally speaking, adopt on the combined microalloying of Ni, Ti, Cu, Cr, Mo and other elements, give full play to the characteristics of each element.P≤0.008% is set, S≤0.003%, N≤0.004% is mainly to consider that these elements are larger to this steel low-temperature flexibility and resistance against hydrogen cracking (HIC) performance impact, strictly limit its content.
C:C improves the most effective element of steel strength, along with the increase of C content, and Fe in steel
3C increases, and hardenability also increases, and the tensile strength of steel and yield strength improve.But, increase C content in steel, the unit elongation of steel and impact toughness decreased are especially larger on the low-temperature flexibility impact.Therefore, consider low-temperature flexibility and the welding property requirement of steel, adopt low C design that the C content of steel of the present invention should be controlled in 0.05%.
The avidity of Si:Si and carbon is very weak, carburet not in steel, but can dissolve in ferrite, and produce solution strengthening effect, make ferritic intensity and hardness improve, but plasticity and toughness descend to some extent.Consider that this steel is mainly that the steel plate low-temperature flexibility is had relatively high expectations, therefore should select low Si design, the Si content of steel of the present invention is controlled in 0.05%.
Mn:Mn improves the yield strength of steel and the one of the chief elements of tensile strength, can add appropriate Mn at the low-carbon (LC) steel grade and improve armor plate strength, and cost is lower, therefore generally add more than 0.40%.But the Mn element is a kind of element of easy segregation, as line of segragation Mn, when C content reaches certain proportion, can produce martensitic phase in steel production and welding process, this is met and shows very high hardness, and steel plate low-temperature flexibility and resistance against hydrogen cracking performance are had considerable influence.Simultaneously, Mn content Gao Shihui causes the steel plate superheated susceptivity to increase, in the situation that slightly have overheatedly, alligatoring will occur crystal grain, and is larger on the low-temperature flexibility impact.Therefore, consider Mn content is limited in 0.50% ~ 1.00% scope.
Al:Al is the main deoxidant element in steel, and the crystal grain that the Al of certain content can also the refinement steel plate improves intensity and the toughness of steel plate.But when Al content is higher, easily causes being mingled with in steel and increase, unfavorable to the toughness of steel, can reduce simultaneously hardenability and the toughness of steel, reduce the resistance against hydrogen cracking performance of steel.Therefore Alt content in steel of the present invention is controlled in 0.015% ~ 0.050%.
Ni:Ni can be molten mutually with any ratio with iron, improves the low-temperature flexibility of steel by the refinement ferrite crystal grain, can obviously reduce the low temperature ductile-brittle transition temperature of steel plate.From domestic and international similar steel grade, 4.50% Ni content is the most basic requirement.Lower than this numerical value, the use temperature of steel does not reach-120 ℃ of requirements, will increase the smelting difficulty but Ni content is too high, significantly improves production cost.Therefore, steel of the present invention is set in Ni content in 4.50% ~ 5.30%.
Ti: Ti is a kind of strong carbide and nitride forming element, the TiN of formation, Ti(CN) etc. particle highly stable, can effectively stop grain growth when forming core, therefore can crystal grain thinning, improve intensity and the toughness of steel plate.But Ti is obvious not as good as Nb to the intensity contribution, and the too much formed carbide of Ti can reduce the steel plate low-temperature flexibility simultaneously.The effect of steel plate Ti when welding is also apparent in view, effectively refinement welded heat affecting zone tissue.Consider that the steel plate low-temperature flexibility requires and on the impact of welding property, be controlled at 0.008% ~ 0.025% during the content of design Ti.
Cu: Cu mainly plays the precipitation strength effect in steel, useful to the low-temperature flexibility of steel after stress-removal thermal treatment, can improve the fatigue crack extended capability that can also improve in addition steel.But when the Cu too high levels, steel is prone to map cracking when rolling.Consider Cu to the impact of steel plate comprehensive mechanical property and corrosion resistance, Cu content is controlled in 0.30%.
Cr:Cr is element commonly used in the hydrogen sulfide corrosion resistant steel, can obtain stable tissue after under thermal treatment, can improve steel anti-hydrogen embrittlement ability and anti-H 2 S stress corrosion performance.Simultaneously, consider cost of alloy and service requirements, Cr content is controlled at 0.50%.
Mo:Mo is the element that effectively improves the steel plate temper resistance, can improve armor plate strength and resistance against hydrogen cracking performance.If addition is too high, can cause the steel plate low-temperature flexibility to descend, therefore, steel Mo content of the present invention is controlled in 0.50%.
Nb:Nb is a kind of carbide, forms NbC, Nb(CN in steel) etc. the second-phase particle, hinder growing up of austenite crystal, crystal grain thinning improves intensity and the low-temperature flexibility of steel plate.The operative temperature of Nb element will be higher than Ti and V, and the contribution of armor plate strength also greater than Ti and V, is easily produced intergranular crack during its too high levels.Therefore, consider Nb content of the present invention is controlled in 0.040%.
Ca:Ca is that steel carries out the element that increases when Ca processes, and when its content is high, element itself does not have no significant effect plate property, but through after the Ca processing, the steel inclusion appearance changes, size reduces, and the nodularization rate improves, and is conducive to the hydrogen sulfide corrosion resistance energy of steel.But consider that Ca processes impurity element increase in rear steel, therefore, add-on is unsuitable excessive, and after this steel will be processed, Ca content is controlled in 0.005%.
The impact of impurity element and gas antagonism H 2 S stress corrosion rigidity energy
Low-temperature pressure vessel steel will be guaranteed the use in low temperature environment.Impurity element in steel and gas are larger on the low-temperature flexibility impact of steel plate, therefore will reduce as much as possible the content of P, S, N.
P:P can cause the meltable eutectic inclusion of steel red crisp (hot-short) and Plasticity Decreasing except forming in steel, also hydrogen atom is reconfigured process and play restraining effect, making steel increase the hydrogen effect increases, thereby improves the fragility of steel, reduces low-temperature flexibility level and resistance against hydrogen cracking performance.Therefore, P should be controlled in 0.006% for this steel.
The S:S too high levels can make steel plate have anisotropy and toughness drop, makes the stability of steel sharply worsen.Therefore, S should be controlled in 0.003% for this steel.
In addition, this steel should reduce gas content in steel as far as possible, reduces the segregation of steel.Simultaneously, in order to reduce the influence of time effect of steel, the content of N is controlled in 0.004%.
The reason that production technique is set
(1) process for making
Why the present invention carries out at the LF stove that Ca processes and vacuum processing time is not less than 18 minutes: carrying out at the LF stove purpose that Ca processes is exactly so that inclusion is carried out sex change, and effectively reduce inclusion size, change the shape of inclusion, be conducive to the hydrogen sulfide corrosion resistance energy of steel; Adopting in vacuum-treat and be not less than 20 minutes, is in order to reduce impurity and gas content in steel.
(2) steel rolling process
The present invention has taked two stage rolling modes when rolling carrying out roughing, i.e. the first rough rolling step → treat for the first time temperature → second rough rolling step → treat for the second time temperature, and this kind rolling technology is highly profitable to the low-temperature flexibility that improves steel plate.
During roughing, also to according to finished steel plate thickness, control the thickness of intermediate blank when rough rolling step is rolling to be finished.Treating for the first time temperature, is in order to ensure avoiding the mixed crystal temperature range; Treating for the second time temperature, is in order to avoid austenite part recrystallization zone temperature, and finish rolling is carried out in austenite non-recrystallization district.And after making finish rolling finish to gauge, the deformation dislocation will occur to reply and polygonization, thereby thinning microstructure improves the low-temperature flexibility of steel plate, can be also useful to the hydrogen sulfide corrosion resistance of steel.
(3) processing, thermal treatment process
Because this steel will be at life-time service under low temperature environment, and the resistance against hydrogen cracking performance to steel is had relatively high expectations, so characteristics for this steel, consider simultaneously different steel plate thickness, and adopt different heat treating regimes: when steel plate thickness during at 10 ~ 20 millimeters, the mode that adopts normalizing to add cooling+tempering is fast carried out, thereby the metallographic structure that obtains is a kind of more stable ferrite+pearlitic structure.
When steel plate thickness greater than 20 when being no more than 40 millimeters, adopt the heat treatment mode of quenching+tempering, thereby the metallographic structure that obtains is a kind of more stable ferrite+bainite structure.
When steel plate thickness greater than 40 when being no more than 60 millimeters, adopt the heat treatment mode of two quenching+temperings, thereby the metallographic structure that obtains is a kind of more stable ferrite+bainite structure.
The present invention compared with prior art, at-140 ℃ of lower KV
2Be not less than 100J, transverse crack thickness rate CTR≤3%, transverse crack length rate CLR≤10%, the responsive rate CSR of transverse crack≤1.5%, Ni content is low, and welding property is good, and the Ni consumption is few, and cost is relatively low, closer to large production.
Embodiment
The below is described in detail the present invention:
Table 1 is the value list of various embodiments of the present invention and Comparative Examples;
Table 2 is the main technologic parameters list of various embodiments of the present invention and Comparative Examples;
Table 3 is the embodiment of the present invention and the thermal treatment process list that contrasts steel grade;
Table 4 is the embodiment of the present invention and the mechanics assay that contrasts steel grade;
Table 5 is the embodiment of the present invention and the hydrogen sulfide corrosion resistant assay that contrasts steel grade.
Various embodiments of the present invention are according to following steps production:
Its step:
1) smelting also, continuous casting becomes base: carry out Ca and process in the LF stove, in the control molten steel, Ca is within target; Control the RH vacuum processing time and be not less than 20 minutes;
2) to the strand heating, control Heating temperature at 1200 ~ 1300 ℃, control heating rate at 9 ~ 12 minutes/centimetre;
3) carry out the first rough rolling step, the start rolling temperature of controlling this stage is not less than 1100 ℃;
4) through for the first time after temperature, be to carry out the subordinate phase roughing under 1000 ℃ ~ 1050 ℃ at start rolling temperature;
5) through for the second time after temperature, be to carry out finish rolling under 930 ℃ ~ 960 ℃ at start rolling temperature, controlling finishing temperature is 760 ~ 820 ℃;
6) heat-treat according to steel plate thickness:
During at 10 ~ 20 millimeters, the mode that adopts normalizing to add cooling+tempering is fast carried out when steel plate thickness, and normalizing temperature is 800 ~ 900 ℃, the normalizing time be (minute): t+30, tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50; In formula: t is the thickness of steel plate, and unit is millimeter; Quick when cooling red temperature be controlled at 400 ~ 600 ℃;
When steel plate thickness greater than 20 when being no more than 40 millimeters, adopt the mode of quenching+tempering to carry out, quenching temperature is 800 ~ 900 ℃, the cool time be (minute): t+30, tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50;
In formula: t is the thickness of steel plate, and unit is millimeter;
When steel plate thickness greater than 40 when being no more than 60 millimeters, adopt the mode of two quenching+temperings to carry out, quenching temperature is 800 ~ 900 ℃ for the first time, the cool time be (minute): t+30; Quenching temperature is 750 ~ 850 ℃ for the second time, the cool time be (minute): t+30; Tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50;
In formula: t is the thickness of steel plate, and unit is millimeter;
7) stand-by.
Table 1 embodiment of the present invention and contrast steel grade chemical composition (wt%)
Table 2 embodiment of the present invention and the main processes that contrasts steel grade
Table 3 embodiment of the present invention and the heat treatment process that contrasts steel grade
Table 4 embodiment of the present invention and the mechanics assay that contrasts steel grade
Table 5 embodiment of the present invention and the hydrogen sulfide corrosion resistant assay that contrasts steel grade
Can find out from table 4 ~ 5, steel grade steel of the present invention is pure, and good low-temperature flexibility, resistance against hydrogen cracking performance are arranged, and can be used for making petrochemical industry and the fertilizer industry pressure vessel and equipment that uses under-100 ℃ ~-140 ℃ low temperature environments.
Above-described embodiment only exemplifies for the best, and is not to be restriction to embodiments of the present invention.
Claims (4)
1. the steels for pressure vessel use that has high tenacity under 140 ℃ of ﹣, its component and weight percent content are: C≤0.05, Si≤0.05, Mn:0.50 ~ 1.00, P≤0.006, S≤0.003, Alt:0.015 ~ 0.050, Ni:4.50 ~ 5.30, Nb:0.02 ~ 0.05, Ti:0.008 ~ 0.025, N≤0.004 is contained Cr≤0.50 in addition, Mo≤0.50, Cu≤0.30, Ca≤0.005, in a kind of or more than one, surplus is Fe and inevitably being mingled with.
2. the steels for pressure vessel use that has high tenacity under 140 ℃ of ﹣, its component and weight percent content are: C≤0.03, Si≤0.05, Mn:0.60 ~ 1.00, P≤0.006, S≤0.003, Alt:0.015 ~ 0.050, Ni:4.50 ~ 5.00, Nb:0.02 ~ 0.05, Ti:0.008 ~ 0.025,, N≤0.004, Cu:0.10 ~ 0.30, Ca:0.002 ~ 0.005, surplus are Fe and inevitably are mingled with.
3. the steels for pressure vessel use that has high tenacity under 140 ℃ of ﹣, its component and weight percent content are: C:0.03 ~ 0.05, Si≤0.05, Mn:0.50 ~ 0.80, P≤0.006, S≤0.003, Alt:0.015 ~ 0.050, Ni:5.00 ~ 5.30, Nb:0.02 ~ 0.05, Ti:0.008 ~ 0.025,, N≤0.004, Cr:0.10 ~ 0.40, Mo:0.20 ~ 0.40, Ca:0.002 ~ 0.005, surplus is Fe and inevitably is mingled with.
4. produce as having the method for the steels for pressure vessel use of high tenacity under 140 ℃ of claim 1 or 2 or 3 described a kind of ﹣, the steps include:
1) smelting also, continuous casting becomes base: carry out Ca and process in the LF stove, in the control molten steel, Ca is within target; Control the RH vacuum processing time and be not less than 20 minutes;
2) to the strand heating, control Heating temperature at 1200 ~ 1300 ℃, control heating rate at 9 ~ 12 minutes/centimetre;
3) carry out the first rough rolling step, the start rolling temperature of controlling this stage is not less than 1100 ℃;
4) through for the first time after temperature, be to carry out the subordinate phase roughing under 1000 ℃ ~ 1050 ℃ at start rolling temperature;
5) through for the second time after temperature, be to carry out finish rolling under 930 ℃ ~ 960 ℃ at start rolling temperature, controlling finishing temperature is 760 ~ 820 ℃;
6) heat-treat according to steel plate thickness:
During at 10 ~ 20 millimeters, the mode that adopts normalizing to add cooling+tempering is fast carried out when steel plate thickness, and normalizing temperature is 800 ~ 900 ℃, the normalizing time be (minute): t+30, tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50; In formula: t is the thickness of steel plate, and unit is millimeter; Quick when cooling red temperature be controlled at 400 ~ 600 ℃;
When steel plate thickness greater than 20 when being no more than 40 millimeters, adopt the mode of quenching+tempering to carry out, quenching temperature is 800 ~ 900 ℃, the cool time be (minute): t+30, tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50;
In formula: t is the thickness of steel plate, and unit is millimeter;
When steel plate thickness greater than 40 when being no more than 60 millimeters, adopt the mode of two quenching+temperings to carry out, quenching temperature is 800 ~ 900 ℃ for the first time, the cool time be (minute): t+30; Quenching temperature is 750 ~ 850 ℃ for the second time, the cool time be (minute): t+30; Tempering temperature is 600 ~ 680 ℃, tempering time be (minute): t+50;
In formula: t is the thickness of steel plate, and unit is millimeter;
7) stand-by.
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