CN113832387B - Low-cost ultra-thick 1000 MPa-grade steel plate and manufacturing method thereof - Google Patents
Low-cost ultra-thick 1000 MPa-grade steel plate and manufacturing method thereof Download PDFInfo
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Abstract
A low-cost ultra-thick 1000 MPa-level steel plate and a manufacturing method thereof are disclosed, wherein a component system of medium C-ultra-low Si-medium Mn- (Cu + Ni + Mo + Cr) alloying- (Ti + Nb + V + B) microalloyed steel is used as a basis, the microstructure of a finished steel plate is fine low-carbon tempered martensite and a small amount of tempered lower bainite, the average grain size of the microstructure is below 25 mu m, the ultra-thick steel plate is enabled to obtain ultra-high strength, excellent low-temperature toughness and fracture elongation, meanwhile, the steel plate not only has excellent obdurability and plastic toughness matching, but also has good weldability, the yield strength of the steel plate is more than or equal to 890MPa, the tensile strength is more than or equal to 950MPa, -40 ℃ Charpy transverse impact work (single value) is more than or equal to 47J, and the fracture elongation delta is more than or equal to δ 5 ≥14％。
Description
Technical Field
The invention relates to a low-carbon high-strength low-alloy steel manufacturing technology, in particular to a low-cost ultra-thick 1000 MPa-grade steel plate and a manufacturing method thereof.
Background
As is well known, low carbon (high strength) low alloy steel is one of the most important engineering structural materials, and is widely used in petroleum and natural gas pipelines, offshore platforms, shipbuilding, hydroelectric engineering, bridge structures, boiler containers, building structures, the automotive industry, railway transportation and mechanical manufacturing. The properties of low carbon (high strength) low alloy steel depend on its chemical composition and manufacturing process, where strength, toughness, plasticity, weldability and the match between them are the most important properties of low carbon (high strength) low alloy steel, which ultimately depend on the microstructure and dislocation substructure of the finished steel.
With the continuous forward development of metallurgical technology, people put forward higher requirements on the toughness, plasticity and weldability of high-strength steel, namely that the steel plate has the brittle fracture resistance and plasticity instability fracture resistance under the condition of low temperature (minus 40 ℃), and simultaneously the fracture elongation and uniform elongation reach the level of the steel plate with the tensile strength of 800 MPa; under the conditions of lower alloy content, particularly precious metal content and relatively lower manufacturing cost, the comprehensive mechanical property and the service performance of the steel plate are greatly improved, the alloy consumption of steel is reduced, the cost is saved, the self weight, the stability and the safety of the steel member are reduced, and more importantly, the cold and hot workability of the steel member and the safety and the reliability in the service process are further improved; at present, research booms for developing new-generation high-performance steel materials are raised in the range of Japan and Korean, better microstructure matching is obtained through alloy combination design optimization design, control of a sub-microstructure fine structure and an innovative manufacturing process technology, and the ultra-fine metallographic microstructure and the sub-structure (dislocation configuration, packet, block and variant) fine structure are tried to be obtained, so that the ultra-high-strength steel obtains more excellent matching of strong plasticity, toughness and weldability.
In the prior art, when a high-strength steel plate with the tensile strength of more than or equal to 950MPa is manufactured, the high-strength steel plate is mainly produced by an off-line hardening and tempering process (namely RQ + T); but the thickness of the steel plate is less than or equal to 60mm, and the steel plate can also be produced by adopting an online hardening and tempering process (namely DQ + T); in order to obtain ultra-high strength, the steel plate must have sufficiently high hardenability and hardenability, i.e. the steel plate hardenability index DI ≥ 3.50 × finished steel plate thickness (DI =0.311 (% C) 1/2[ (1 +0.64 (% Si) ] × [ (1 +4.10 (% Mn) ] × [ (1 +0.27 (% Cu) ] × [ (1 +0.52 (% Ni) ] × [ (1 +2.33 (% Cr) ] × [ (1 +3.14 (% Mo) ] × 25.4 (mm)) to ensure that the steel plate has sufficiently high strength, excellent low-temperature toughness and uniformity of microstructure and performance along the plate thickness direction, so that a large amount of alloy elements such as C, cr, mo, ni, cu, V and the like, especially a large amount of noble alloy elements such as Cu, ni, mo, V and the like, are not only cause high alloy cost of the steel plate, but also cause high carbon and cold sensitivity of the steel plate, and seriously affect the weldability of the steel plate.
In addition, the surface layer (sub) of the steel plate with high carbon and high alloy content is easy to over-quench, and coarse martensite structure is formed, so that the low-temperature toughness and elongation of the surface layer (sub) of the steel plate are seriously deteriorated (see, "electric power and civil engineering (japanese), 1986, vol.201, P33; iron と stainless steel, 1986, vol.72, S612; an iron と stainless steel, 1986, vol.72, S614, iron と,1985, vol.71, S1523, iron と,1986, vol.72, S615, iron と,1986, vol.73, S1398, kawasaki iron technical report (Japanese), 1988, vol.20, P233, iron manufacturing research (Japanese), 1986, vol.322, P99, CAMP-ISIJ (Japanese), 1989, vol.3, P207, NKK technical report (Japanese), 1990, vol.133, P37, electric civil engineering (Japanese), vol.249, P1, youyu friend metal (Japanese), 1995, P1, P3947, sp 3926, sp 3947, sp.35; the low elongation and low-temperature toughness are not only adverse to the cold and hot processability of the steel plate, but also have great influence on the fatigue resistance, stress concentration sensitivity resistance, crack resistance and structural stability of the steel plate; when the composite material is used on fatigue heavy-load structures such as pressure steel pipes, steel branch pipes and turbine shells, thermal power turbine generators, ocean oil production platform structures and the like in hydroelectric engineering, great potential safety hazards exist; therefore, when the large-scale fatigue heavy-duty steel structure adopts ultrahigh-strength steel, the 1000 MPa-grade high-strength steel is generally expected to have excellent strength and toughness, strong plasticity matching and weldability, and the elongation is ensured to be more than 14% so as to ensure the processability and the fatigue resistance of the steel plate.
A large number of prior patents and technical documents only describe how to achieve the strength and low-temperature toughness of a base steel plate, improve the welding performance of the steel plate, and obtain an excellent welding heat affected zone HAZ low-temperature toughness, and do not relate to how to improve the tensile strength of the steel plate and the uniformity of tensile elongation and mechanical properties in the thickness direction of the steel plate, and further do not teach how to prevent the over-quenching of the surface (sub) layer of the steel plate (japanese patents sho 63-93845, sho 63-79921, sho 60-258410, sho 4-285119, japanese Patent 4-308035, hei 3-264614, hei 2-250917, hei 4-143246, US patents US Patent application 5798004, european Patent EP 0288054A2, and seiki shan technologies P35160-159, P79-P79).
The Chinese patent ZL201010227961.8 discloses a 960 MPa-grade quenched and tempered steel plate with excellent obdurability and strong plasticity and a manufacturing method thereof, although the comprehensive mechanical property of the steel plate also reaches a higher level: the tensile strength is more than or equal to 980MPa, the yield strength is more than or equal to 890MPa, and the Charpy transverse impact energy (single value) at-60 ℃ is more than or equal to 47J, but the maximum thickness of the produced steel plate by the steel plate manufacturing technology can only reach 80mm; the 'HT 960 steel plate with excellent ductility and toughness and the manufacturing method thereof' disclosed in Chinese patent No. ZL201110071217.8 are produced by adopting a TMCP + off-line tempering process, the quenching potential of alloy elements is fully exerted, the alloy content, the manufacturing period and the manufacturing cost of the steel plate are greatly reduced, the comprehensive mechanical property and the weldability of the steel plate are also improved to a great extent, but the production thickness of the steel plate is still limited, the maximum thickness can only reach 70mm, and the steel plate with thicker specification can not be produced.
In addition, chinese patent 'ultra-high toughness, ultra-thick 1000MPa grade steel plate and manufacturing method thereof', which adopts low carbon, high nickel and high DI index design, develops the 1000MPa grade ultra-high toughness steel plate with the maximum thickness reaching 180mm through controlled rolling + DQ + QT process, the matching of the strength and toughness and the strong plasticity of the steel plate reaches the level of 800MPa grade quenched and tempered steel plate, especially the elongation, the crack resistance and the crack arrest characteristics of the steel plate are basically equivalent to the 800MPa quenched and tempered steel plate, the steel plate can be used for pressure steel pipes, volutes, steel branch pipes and steel branch pipe crescent rib plates in hydropower engineering, and the quality of products reaches the international advanced level (equivalent to the quality of similar products of Niger iron); but the manufacturing cost of the steel plate is high, particularly 1.50 to 4.00 percent of Ni which is added as a precious alloy element is added, the surface of the plate blank with high Ni content cracks frequently, and the plate blank needs to be mechanically ground; the method has the advantages of multiple manufacturing processes, long manufacturing period, low metal yield, high waste steel recovery difficulty (containing a large amount of Ni elements), extremely high steel plate manufacturing cost, and limitation of wide batch socialization, and can only be used for special engineering members such as bearing members of hydroelectric engineering, polar marine engineering members and related equipment.
Disclosure of Invention
The invention aims to provide a low-cost ultra-thick 1000 MPa-grade steel plate and a manufacturing method thereof, which can realize that the ultra-thick steel plate obtains ultra-high strength, excellent low-temperature toughness and fracture elongation, simultaneously the steel plate has excellent matching of obdurability and ductility, and the steel plate has excellent weldability, successfully solves the mutual contradictions between the strength and plasticity, the strength and low-temperature toughness, and the strength and weldability of the ultra-high strength steel plate, eliminates the problem of low plasticity and toughness of the surface layer of the steel plate caused by over quenching of the surface (sub) layer of the steel plate under the condition of higher C content, and is particularly suitable for manufacturing major equipment such as engineering machinery, port machinery, coal mine machinery, heavy trucks, large special loading vehicles and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention properly improves the content of acid-soluble Als in steel and Als/[ (% N) -0.292 (% Ti) by simple combination matching design of alloy elements and by taking a component system of medium C-ultralow Si-medium Mn- (Cu + Ni + Mo + Cr) alloying- (Ti + Nb + V + B) microalloyed steel as a basis]Not less than 33 percent, and controlling the ratio of (% C) to (% Mn) to not more than 0.23 and the ratio of [ (% Si) to H]/(％C)≤68、[(％C)×DI]0.285 and [0.37 (% Cr) +1.06 (% Mn) +7.16 (% Ni) +0.86 (% Cu) -1.53 (% Mo) -23.56 (% Si)]V (% C) 4.30 or more, ca treatment, ca/S ratio of 1.00 to 3.00 and (% Ca) x (% S) 0.18 ≤2.5×10 -3 And by means of metallurgical technology control measures, the microstructure of the finished steel plate is fine low-carbon tempered martensite and a small amount of tempered lower bainite, the average grain size of the microstructure is below 25 mu m, and the steel plate not only has excellent obdurability and ductility and toughness matching, but also has excellent weldability while the super-thick steel plate obtains ultrahigh strength and excellent low-temperature toughness and fracture elongation.
Specifically, the low-cost ultra-thick 1000 MPa-level steel plate comprises the following components in percentage by weight:
C：0.14％～0.18％，
Si：≤0.13％，
Mn：1.10％～1.50％，
P：≤0.013％，
S：≤0.0030％，
Cu：0.15％～0.40％，
Ni：0.35％～0.70％，
Cr：0.55％～0.90％，
Mo：0.30％～0.55％，
B：0.0008％～0.0016％，
Ti：0.006％～0.015％，
Nb：0.010％～0.030％，
Als：0.030％～0.065％，
N：≤0.0050％，
O：≤0.0030％，
Ca：0.0010％～0.0035％，
the balance of Fe and inevitable impurities; and the contents of the elements simultaneously satisfy the following relationship:
Als/[(％N)-0.292(％Ti)]≥33；
(％C)×(％Mn)≤0.23；
[ (% Si). Times.H ]/(% C) < 68, wherein H is the thickness of the steel plate and is in mm unit;
[ (% C). Times.DI ]/H.gtoreq.0.285, wherein:
DI＝0.367C 0.5 (1 + 0.7Si) (1 + 3.33Mn) (1 + 0.35Cu) (1 + 0.36Ni) (1 + 2.169r) (1 +3 Mo) (1 + 1.75V) (1 + 1.77Al) multiplied by 25.4 in unit mm;
h is the thickness of the steel plate and is in mm;
[0.37(％Cr)+1.06(％Mn)+7.16(％Ni)+0.86(％Cu)-1.53(％Mo)-23.56(％Si) ]/(％C)≥4.30；
ca treatment, ca/S ratio is between 1.00 and 3.00, and (% Ca) × (% S) 0.18 ≤2.5×10 -3 。
Preferably, the thickness of the steel plate is more than or equal to 60mm.
The microstructure of the steel plate is fine low-carbon tempered martensite and a small amount of tempered lower bainite, and the average grain size of the microstructure is below 25 mu m.
The yield strength of the steel plate is more than or equal to 890MPa, the tensile strength is more than or equal to 950MPa, the Charpy transverse impact energy (single value) at the temperature of-40 ℃ is more than or equal to 47J, and the elongation at break delta 5 ≥14％。
In the composition design of the steel of the invention:
c is the most effective hardening element, can effectively improve the hardness of the quenched steel plate and is the most effective alloy element for improving the quenched and tempered steel plate, so that C is of great importance for controlling the content range of ultra-thick and ultra-high strength steel plates; the use level of other alloy elements can be greatly reduced by properly increasing the content of C in the steel, and more importantly, when the content of C in the steel is lower than a critical value, the strength of the steel plate can not be effectively improved by adding more other alloy elements, which is particularly important for ultra-thick 1000 MPa-grade quenched and tempered steel plates. As is well known, C has great influence on the strength, low-temperature toughness, elongation and weldability of the ultrahigh-strength quenched and tempered steel plate, and the content of C in the steel is expected to be controlled to be lower from the aspect of improving the intrinsic ductility and weldability of the ultrahigh-strength quenched and tempered steel plate; however, from the aspects of hardenability, obdurability matching, weldability, microstructure control and alloy cost control of the ultrahigh steel plate, the C content is not suitable to be controlled to be too low, particularly 1000 MPa-grade low-cost ultra-thick quenched and tempered steel plate, so that the reasonable range of the C content is 0.14% -0.18%.
Si promotes molten steel deoxidation and can improve the strength of a steel plate, but the deoxidation effect of Si is not great in molten steel deoxidized by Al; although Si can improve the strength of the steel plate, si reduces the martensite phase transformation critical cooling speed, promotes martensite phase transformation, inhibits the segmentation effect of lower bainite phase transformation on original austenite grains, coarsens packet crystal cluster size and makes block lath grain boundaries small in angle, seriously damages the low-temperature toughness, crack arrest characteristics, elongation and weldability of the ultrahigh-strength steel plate, particularly under the condition of larger heat input welding, si not only promotes the formation of M-A islands, but also forms the larger M-A islands which are large in size and uneven in distribution, and seriously damages the toughness of a welding Heat Affected Zone (HAZ), so that the Si content in the steel is controlled to be as low as possible, and the Si content is controlled to be less than or equal to 0.13 percent in consideration of the economy and operability of a steel making process.
Mn, the most important alloying element, improves the strength of the steel sheet, expands the austenite phase region, and reduces Ar in the steel 3 The point temperature, the orientation difference between the block structures is increased to improve the plasticity and toughness of the steel plate, and the low-temperature phase transformation structure martensite and bainite are promoted to form to improve the strength of the steel plate; however, mn is prone to segregation during molten steel solidification, and particularly under the condition of high C content, when Mn content is high, not only casting operation is difficult, but also conjugate segregation phenomenon is prone to occur with elements such as C, P, S, mo, cr and the like, segregation and porosity at the central part of a casting blank are increased, and segregation at the central severe region of the casting blank is prone to form abnormal structures during subsequent manufacturing and welding processes, so that ultrahigh strength is causedThe low-temperature toughness of the steel plate is low, cracks appear on the welded joint, and in addition, when the alloy contains high content of C, mn increases the hardenability of martensite, coarsens the size of martensite crystal clusters (namely packet size), causes the surface of the steel plate to be over-quenched (the surface has extremely low toughness and is easy to generate environmental brittleness), promotes the formation of thick martensite laths in a welding heat affected zone, and deteriorates the toughness and the crack resistance and crack resistance of the welded joint; therefore, according to the steel component system and the content range of C, the reasonable range of Mn content is 1.10-1.50%.
P has great damage effect on the mechanical properties of steel, particularly low-temperature impact toughness, elongation and SR performance of a welding joint as harmful impurities in the steel, the lower the requirement is, the better the steel-making operability and the steel-making cost are theoretically required, but for ultrahigh-strength and ultra-thick quenched and tempered steel plates which require low cost, excellent weldability, toughness at minus 40 ℃ and excellent toughness matching, the content of P needs to be controlled to be less than or equal to 0.013 percent.
S has a great damage effect on the low-temperature toughness of steel as harmful inclusions in the steel, more importantly, the S is combined with Mn in the steel (particularly when the content of C, mn is high), mnS inclusions are easily formed, in the hot rolling process, the plasticity of MnS enables MnS to extend along the rolling direction to form a MnS inclusion band along the rolling direction, the low-temperature impact toughness, the elongation, the Z-direction performance and the weldability of the steel plate are seriously damaged, meanwhile, S is also a main element generating hot brittleness in the hot rolling process, the lower the requirement is better in theory, but considering the steel-making operability, the steel-making cost and the principle of smooth logistics, the S content needs to be controlled to be less than or equal to 0.0030 percent for the ultrahigh-strength and ultra-thick quenched and tempered steel plate which requires low cost, excellent weldability, toughness at-40 ℃ and excellent toughness matching.
Cu is also an austenite stabilizing element, and the addition of Cu can also reduce Ar 3 The point temperature improves the hardenability of the steel plate and the atmospheric corrosion resistance of the steel plate; however, if the addition amount of Cu is too much and is higher than 0.40% (for the ultrahigh-strength steel plate with high C and high Mn), the problems of copper brittleness, casting blank surface cracking and internal cracking and especially the SR performance degradation of the welding joint of the ultrahigh-strength steel plate are easily caused; for 1000MPa grade ultra-thick quenched and tempered steel plate, the addition amount of Cu is too small, less than 0.15%, and any effect is small; thus Cu containsThe amount is controlled between 0.15 percent and 0.40 percent; besides, the composite addition of Cu and Ni can reduce the copper brittleness of copper-containing steel and reduce intergranular cracking in the hot rolling process, and more importantly, both Cu and Ni are austenite stabilizing elements, and the composite addition of Cu and Ni can greatly reduce Ar 3 The driving force of austenite to ferrite phase transformation is improved, the structural size of the packet is refined, the martensite/bainite lath is promoted to grow towards each position, the meta-position difference of the martensite/bainite block is increased, and the resistance of a crack penetrating through the martensite/bainite lath is increased, so that the low-temperature toughness of the ultrahigh-strength steel plate is improved.
The addition of Ni has the following effects:
1) The low-temperature mobility of dislocation in a ferrite phase can be improved, the dislocation cross slip is promoted, and the low-temperature intrinsic toughness of a BCC (body centered cubic) crystal structure is improved;
2) Increasing the orientation difference between martensite/bainite block laths and improving the resistance of cracks to penetrate through martensite/bainite packet crystal boundaries;
3) Ni as an austenite stabilizing element to reduce Ar 3 Point temperature, and martensite/bainite packet structure size is refined, so that Ni has the function of improving the strength, the elongation and the low-temperature toughness of the quenched and tempered steel plate;
4) The addition of Ni in the steel can also reduce the copper brittleness of the copper-containing steel, reduce intergranular cracking in the hot rolling process and improve the atmospheric corrosion resistance of the steel plate;
therefore, theoretically, the higher the Ni content in the steel is within a certain range, the better the Ni content is; however, for a low-cost 1000MPa grade ultra-thick quenched and tempered steel plate, a certain Ni content is required to be provided so as to ensure that the steel plate has sufficient hardenability and uniform performance in the plate thickness direction and ensure the obdurability matching and low-temperature toughness of the steel plate; therefore, the Ni content is controlled between 0.35% and 0.70% to ensure hardenability of the steel sheet and the level of toughness of the steel sheet without impairing weldability of the steel sheet.
Cr is used as a weak carbide forming element, and the added Cr not only improves the hardenability of the steel plate and promotes the formation of martensite/bainite, but also has the functions of increasing the lath-meta-position difference of the martensite/bainite to a certain extent and increasing the resistance of cracks to penetrate through a martensite/bainite packet structure, and has the functions of improving the toughness of the steel plate to a certain extent while improving the strength of the steel plate; however, when the amount of Cr added is too large, weldability of the steel sheet, particularly toughness after weld joint annealing treatment (i.e., after SR), is seriously impaired; however, for a low-cost 1000MPa grade ultra-thick quenched and tempered steel plate, a certain Cr content is required to ensure that the steel plate has enough hardenability, so that the reasonable range of the Cr content is 0.55-0.90%.
The addition of Mo can greatly improve the hardenability of the steel plate, promote the formation of martensite/bainite, improve the tempering characteristic and tempering process window of the steel plate, and improve the toughness and strong plasticity matching of the tempered steel plate; but Mo is used as a strong carbide forming element, so that the formation of martensite/bainite is promoted, the size of martensite/bainite packets is increased, the formation of small-angle grain boundaries among martensite/bainite block laths is promoted, the resistance of cracks passing through the martensite/bainite packet grain boundaries is reduced, and in addition, the super-hardening of the surface (sub) layer of the ultra-high-strength steel is promoted by Mo; therefore, mo greatly improves the strength of the steel plate, reduces the low-temperature toughness and the elongation of the ultrahigh-strength steel plate, and induces the over-quenching of the surface (sub) surface layer of the steel plate; when Mo is excessively added (particularly when the content of C, mn is high), the elongation, weldability and welded joint SR performance of the steel plate are seriously damaged, and the steel plate SR brittleness and production cost are increased; however, for a low-cost, 1000MPa grade ultra-thick quenched and tempered steel plate, a certain Mo content is required to ensure that the steel plate has sufficient hardenability and temper softening resistance. The phase change strengthening effect of Mo and the influence on the low-temperature toughness, the elongation and the weldability of the base steel plate are comprehensively considered, so that the reasonable range of the Mo content is 0.30-0.55%.
The addition of B element ensures the hardenability of the steel plate and does not damage the weldability, HAZ toughness and slab surface quality of the steel plate, so the reasonable range of B content is 0.0008% -0.0016%.
Adding a trace amount of Ti into the steel aims to inhibit austenite grains from excessively growing in the processes of heating, rolling and quenching and tempering heat treatment of the plate blank, improve the low-temperature toughness of the steel plate, and more importantly inhibit HAZ grains from growing in the welding process and improve the HAZ toughness; in addition, ti has the function of fixing N, eliminates free N in steel and ensures that B element exists in a solid solution B form; however, when the Ti content exceeds 0.015%, under the condition of high acid-soluble aluminum content, excessive Ti precipitates as TiC coherent on martensite/bainite laths and at the grain boundaries, seriously embrittling the microstructure of the steel sheet, and therefore the optimum control range of the Ti content is 0.006% to 0.015%.
The purpose of adding trace Nb element in the steel is to perform non-recrystallization controlled rolling, refine the microstructure of the steel plate, especially refine grains on the surface (sub) layer of the steel plate, reduce the hardenability of the surface (sub) layer of the ultra-high strength steel plate, inhibit the over quenching of the surface (sub) layer of the ultra-high strength steel plate, and improve the matching of the low-temperature toughness and the obdurability of the 1000MPa grade ultra-thick quenched and tempered steel plate; when the addition amount of Nb is less than 0.010 percent, the effect of controlling rolling and refining grains cannot be effectively exerted; when the addition amount of Nb exceeds 0.030 percent, coarse upper bainite (Bu) formation and Nb (C, N) secondary precipitation embrittlement are easily induced in the welding process, and the low-temperature toughness and crack resistance and crack arrest characteristics of a welding Heat Affected Zone (HAZ) are seriously damaged, so that the Nb content is controlled between 0.010 percent and 0.030 percent, the optimal rolling control effect is obtained, the toughness matching of 1000 MPa-grade ultra-thick quenched and tempered steel plates is realized, the surface (sub) surface layer is inhibited from being over quenched, and the toughness of the HAZ is not damaged during welding and multi-pass welding.
Als in the steel plate can fix free [ N ] in the steel, reduce free [ N ] of a welding Heat Affected Zone (HAZ), improve the low-temperature toughness of the welding HAZ, more importantly ensure certain solid solution [ B ] in the steel and improve the hardenability of the steel plate, so the lower limit of Als is controlled to be 0.030%; however, excessive addition of Als to steel not only causes difficulty in casting, but also forms a large amount of dispersed needle Al2O3 inclusions in the steel, and impairs the soundness of the steel sheet, low-temperature toughness and weldability, so the upper limit of Als is controlled to 0.065%, and therefore, the optimal control range of the optimal Als content is 0.030% -0.065%.
In order to ensure the existence of enough solid solution [ B ] in the steel plate and prevent a great amount of coarse AlN from precipitating along the prior austenite grain boundary and damaging the transverse impact toughness and plasticity of the steel plate, the content of N in the steel is less than or equal to 0.0050 percent.
In order to ensure the plasticity and toughness of the 1000 MPa-level ultra-thick quenched and tempered steel plate, the inclusion in the steel must be reduced, wherein the aluminum oxide inclusion harm is the largest, so the O content in the steel is less than or equal to 0.0030 percent.
Performing Ca treatment on steel, namely further purifying the molten steel on one hand, and performing denaturation treatment on sulfides in the steel on the other hand to ensure that the sulfides are changed into non-deformable, stable and fine spherical sulfides, inhibit the hot brittleness of S, improve the low-temperature toughness, the elongation and the Z-direction performance of the steel plate, and improve the anisotropy and the weldability of the toughness of the steel plate; the addition amount of Ca depends on the content of S in steel, the addition amount of Ca is too low, and the treatment effect is not great; the Ca addition is too high, the formed Ca (O, S) has too large size and increased brittleness, and can be used as a starting point of fracture crack, reduce the low-temperature toughness and elongation of steel and the weldability of a steel plate, and simultaneously reduce the purity of steel and pollute molten steel; the Ca content is generally controlled according to ESSP = (wt% Ca) [1-1.24 (wt% O) ]/1.25 (wt% S), wherein ESSP is a sulfide inclusion shape control index, and the value range is preferably 0.80-4.00, so that the proper range of the Ca content is 0.0010-0.0035%.
The following are specifically controlled in the composition design of the invention:
als/[ (% N) -0.292 (% Ti) ] > 33: elimination of steel and weld heat affected zone free [ N ]:
1) Ensuring that the steel contains enough solid solution [ B ], keeping the steel plate to have enough hardenability and stable hardenability, and realizing the matching of the strength, the low-temperature toughness and the obdurability of the ultra-thick 1000MPa steel plate;
2) Reduce the free N content of the welding heat affected zone and improve the microstructure and low-temperature toughness of the welding heat affected zone.
(％C)×(％Mn)≤0.23：
1) The degree of conjugate segregation in the solidification process of molten steel with high carbon, high manganese and high alloy content is reduced, the integrity and homogeneity of the internal quality of the steel plate are improved, and the UT qualification rate and low-temperature toughness of the steel plate are improved;
2) The excessive quenching of the surface (sub) of the steel plate with high carbon, high manganese and high alloy content is inhibited, the low-temperature toughness and the environmental brittleness of the surface (sub) layer of the steel plate are improved, and the crack resistance and the crack arrest characteristics of the steel plate are improved;
3) The hardenability of the steel plate is balanced, the generation of the size of a coarse martensite packet is inhibited, and the strength and toughness matching and the low-temperature toughness of the steel plate are improved; this is one of the key core technologies of the present invention.
[ (% Si) xH ]/(% C) ≦ 68: the method has the advantages of improving the martensite phase transformation critical cooling speed, forming a gradient phase transformation mode, segmenting original austenite grains, thinning the martensite packet size and improving the strength and toughness matching and low-temperature toughness of the steel plate, and is one of the key technologies of the method.
[ (% C). Times.DI ]/H.gtoreq.0.285: the method balances the hardenability of the ultra-high strength steel plates with different thicknesses, ensures that the ultra-thick quenched and tempered steel plates have enough hardenability and strength, and ensures that the ultra-thick quenched and tempered steel plates have uniform performance in the thickness direction, matched obdurability and excellent low-temperature toughness, which is one of the key technologies of the invention.
[0.37 (% Cr) +1.06 (% Mn) +7.16 (% Ni) +0.86 (% Cu) -1.53 (% Mo) -23.56 (% Si) ]/(% C) ≧ 4.30: the position difference between martensite block laths is increased, the resistance of cracks penetrating through martensite packet crystal boundaries is improved, and the ultrahigh-strength quenched and tempered steel plate has excellent obdurability matching; the steel plate has excellent low-temperature toughness, and particularly has excellent crack resistance and crack arrest characteristics, which is one of the key technologies of the invention.
Ca treatment, ca/S ratio is between 1.00 and 3.00, (% Ca) × (% S) 0.18 ≤1.0×10 -3 : the low-temperature toughness, the obdurability matching, the weldability and the lamellar tearing resistance of the ultrahigh-strength steel plate are improved, and the environmental brittleness sensitivity (particularly the delayed hydrogen-induced crack at the central part of the plate thickness) of the ultrahigh-strength steel plate is inhibited.
The invention relates to a manufacturing method of a low-cost ultra-thick 1000 MPa-level steel plate, which comprises the following steps:
1) Smelting and casting
Smelting and continuously casting the components into a plate blank; the pouring temperature of the tundish is 1520 to 1550 ℃, the wire drawing speed is 0.6 to 1.0m/min, and the fluctuation of the liquid level of the crystallizer is less than or equal to 5mm;
2) Rolling of
The first stage is recrystallization rolling, the heating temperature is controlled to be 1130-1180 ℃, the rolling pass reduction rate is more than or equal to 5 percent, and the final rolling temperature is more than or equal to 960 ℃;
in the second stage, rolling is controlled by non-recrystallization, the rolling start temperature of controlled rolling is less than or equal to 820 ℃, the rolling average pass reduction rate is more than or equal to 8 percent, the cumulative reduction rate is more than or equal to 30 percent, and the final rolling temperature is 770-810 ℃;
3) Cooling down
After rolling control is finished, slowly cooling the steel plate, wherein the slow cooling process is to keep the temperature of the surface of the steel plate to be more than or equal to 300 ℃ for more than 36 hours, and then naturally cooling the steel plate to room temperature;
4) Hardening and tempering process
Quenching according to the hardenability index, ac of the steel sheet 3 The temperature is controlled, the quenching temperature of the steel plate is adjusted, the quenching temperature is 880-930 ℃, the quenching holding time is more than or equal to 15min, and the quenching holding time is the heat preservation time for starting timing when the central temperature of the steel plate reaches the quenching target temperature;
tempering, wherein the tempering temperature (plate temperature) of the steel plate is 530-590 ℃, the tempering retention time is more than or equal to 30min, and the tempering retention time is the heat preservation time when the central temperature of the steel plate reaches the tempering target temperature; and naturally cooling the steel plate to room temperature after tempering.
In the manufacturing process design of the steel plate, the steel plate comprises the following steps:
the casting technology of the invention recommends a continuous casting technology, the pouring temperature of the tundish is controlled between 1520 ℃ and 1550 ℃, the drawing speed is controlled between 0.6m/min and 1.0m/min, and the fluctuation of the liquid level of the crystallizer is controlled to be less than or equal to 5mm.
The first stage is recrystallization rolling, and aims to ensure that Nb is completely dissolved in solution in the heating and rolling processes, the heating temperature of the plate blank is controlled between 1130 and 1180 ℃, the pass reduction rate is more than or equal to 5 percent, and the final rolling temperature is more than or equal to 960 ℃.
In the second stage, rolling is controlled by non-recrystallization, the rolling start temperature is less than or equal to 820 ℃, the rolling average pass reduction rate is more than or equal to 8%, the accumulated reduction rate is more than or equal to 30%, the final rolling temperature is 770-810 ℃, and the steel plate grains before heat treatment are refined and adjusted, so that the foundation is laid for finally obtaining fine and uniform martensite structures.
After the controlled rolling is finished, the steel plate is immediately subjected to slow cooling, the slow cooling process is more than 300 ℃, and the temperature is kept for more than 36 hours; and then the steel plate is naturally air-cooled to room temperature.
The heat treatment process adopts off-line (quenching and tempering)The process is a hardening and tempering process for production according to the hardenability index and Ac of the steel plate 3 And adjusting the quenching temperature of the steel plate to realize the matching between the hardenability and the quenching temperature of the steel plate and obtain fine and uniform low-carbon martensite and a small amount of low-carbon bainite structures so as to obtain the performance requirement of the steel plate, wherein the quenching temperature is 880-930 ℃, the quenching holding time is not less than 15min, and the quenching holding time is the heat preservation time for starting timing when the central temperature of the steel plate reaches the quenching target temperature.
The tempering temperature (plate temperature) of the steel plate is 530-590 ℃, the tempering retention time is more than or equal to 30min, and the tempering retention time is the heat preservation time when the central temperature of the steel plate reaches the tempering target temperature; and naturally cooling the steel plate to room temperature after tempering.
The invention has the beneficial effects that:
the invention adopts low-cost alloy combination design (high-carbon, medium-high content Mn, low Mo and alloy design technical means such as microalloying treatment of properly adding Cu, ni, nb, ti and Ca) and the like), and is matched with a special controlled rolling and quenching and tempering process, thereby not only fully playing the quenching and hardening potentials of alloy elements, but also effectively refining steel plate packets (crystal clusters), increasing the large-angle grain boundary density between martensite laths (varients), effectively refining martensite and bainite substructures, and obtaining ultra-high strength, excellent ultra-low temperature toughness and toughness matching of ultra-thick steel plates under the condition of less precious alloy content (particularly Ni, mo and the like), thereby not only further reducing the manufacturing cost, but also improving the weldability of the steel plates, and particularly greatly reducing the welding cold cracking sensitivity of the ultra-high strength steel plates, reducing the welding preheating and post-heating temperature, widening the range of proper welding heat input quantity and correspondingly reducing the manufacturing cost of users.
The low-cost 1000 MPa-grade super-thick quenched and tempered steel plate is obtained, meanwhile, the low-temperature toughness and the obdurability matching of the steel plate are also excellent, the mutual contradiction between the strength of the 1000 MPa-grade quenched and tempered steel plate and the super-thick (more than or equal to 60 mm), low-temperature toughness, crack resistance and crack arrest characteristics, environmental brittleness resistance and weldability are successfully solved, and the safety and the stability of a large heavy steel structure are improved; the good weldability saves the manufacturing cost of the ultrahigh-strength steel plate member of the user, shortens the manufacturing time of the steel member of the user, and creates great value for the user, so that the steel plate is not only a product with high added value and environmental protection.
Drawings
FIG. 1 is a photograph showing the microstructure (1/4 thickness) of the steel of example 4 of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The steel plate components of the embodiments of the invention are shown in table 1, tables 2 to 4 are process parameters of the embodiments of the invention, and table 5 is performance parameters of the embodiments of the invention.
As can be seen from FIG. 1, the microstructure of the steel sheet was fine low-carbon tempered martensite plus a very small amount of tempered lower bainite, and the average grain size of the microstructure was 25 μm or less.
The invention combines the combined design of alloy elements with the special controlled rolling and low-temperature rapid quenching heat treatment process, realizes that the super-thick steel plate obtains super-high strength, excellent low-temperature toughness and elongation at break, simultaneously the steel plate has excellent toughness and ductility matching, and the steel plate has good weldability, the yield strength is more than or equal to 890MPa, the tensile strength is more than or equal to 950MPa, the-40 ℃ Charpy transverse impact work (single value) is more than or equal to 47J, and the elongation at break delta is more than or equal to 47J 5 ≥14％。
At present, all domestic large steel mills (except for Bao steel) can not produce the steel; the 1000MPa grade ultra-thick quenched and tempered steel plate required by domestic large engineering machinery, port machinery, coal mine machinery, heavy trucks, large special loading vehicles and the like is imported from Europe (German Di Lin Gen, SSAB and the like) and Japan (Japanese iron and JFE); not only the steel sheet import price and additional technical service expense are expensive, and the delivery date can not be guaranteed moreover, forces the user to order in advance the steel sheet that has certain size surplus before the design drawing comes out to after the design drawing comes out, cut out the steel sheet according to the steel sheet size requirement that the design drawing required, lead to the huge waste of material.
As a strategic base material, the 1000MPa grade ultra-thick quenched and tempered steel plate has wide market prospect; the method can be widely used for manufacturing heavy equipment such as large engineering machinery, port machinery, coal mine machinery, heavy trucks, large special loading vehicles and the like.
Claims (6)
1. A low-cost ultra-thick 1000 MPa-grade steel plate comprises the following components in percentage by weight:
C：0.14％～0.18％，
Si：≤0.13％，
Mn：1.10％～1.50％，
P：≤0.013％，
S：≤0.0030％，
Cu：0.15％～0.40％，
Ni：0.35％～0.70％，
Cr：0.55％～0.90％，
Mo：0.30％～0.55％，
B：0.0008％～0.0016％，
Ti：0.006％～0.015％，
Nb：0.010％～0.030％，
Als：0.030％～0.065％，
N：≤0.005％，
O：≤0.003％，
Ca：0.0010％～0.0035％，
the balance of Fe and other inevitable impurities; and the content of the elements must satisfy the following relation at the same time:
Als/[(％N)-0.292(％Ti)]≥33；
(％C)×(％Mn)≤0.23；
[ (% Si) xH ]/(% C) < 68, wherein H is the thickness of the steel plate and is unit mm;
[ (% C). Times.DI ]/H.gtoreq.0.285, wherein:
DI＝0.367C 0.5 (1 + 0.7Si) (1 + 3.33Mn) (1 + 0.35Cu) (1 + 0.36Ni) (1 + 2.169r) (1 + 3Mo) (1 + 1.75V) (1 + 1.77Al) multiplied by 25.4 in unit mm;
h is the thickness of the steel plate and is in mm;
[0.37(％Cr)+1.06(％Mn)+7.16(％Ni)+0.86(％Cu)-1.53(％Mo)-23.56(％Si)]/(％C)≥4.30；
ca treatment, the ratio of Ca/S is 1.00-3.00, and (% Ca) × (% S) 0.18 ≤2.5×10 -3 ；
The yield strength of the steel plate is more than or equal to 890MPa, the tensile strength is more than or equal to 950MPa, the single value of charpy transverse impact energy at-40 ℃ is more than or equal to 47J, and the fracture elongation delta 5 ≥14％。
2. The low-cost ultra-thick 1000 MPa-grade steel plate according to claim 1, wherein the thickness of the steel plate is more than or equal to 60mm.
3. The low-cost ultra-thick 1000MPa grade steel sheet according to claim 1 or 2, wherein the microstructure of the steel sheet is fine low-carbon tempered martensite + a small amount of tempered lower bainite, and the average grain size of the microstructure is below 25 μm.
4. A method for manufacturing a low-cost ultra-thick 1000 MPa-grade steel sheet according to any one of claims 1 to 3, comprising the steps of:
1) Smelting and casting
Smelting and continuously casting the components according to the claim 1 into a slab; the pouring temperature of the tundish is 1520-1550 ℃, the wire drawing speed is 0.6-1.0 m/min, and the fluctuation of the liquid level of the crystallizer is less than or equal to 5mm;
2) Rolling of
The first stage is recrystallization rolling, the heating temperature is controlled to be 1130-1180 ℃, the rolling pass reduction rate is more than or equal to 5 percent, and the final rolling temperature is more than or equal to 960 ℃;
in the second stage, rolling is controlled by non-recrystallization, the rolling start temperature of controlled rolling is less than or equal to 820 ℃, the rolling average pass reduction rate is more than or equal to 8 percent, the cumulative reduction rate is more than or equal to 30 percent, and the final rolling temperature is 770-810 ℃;
3) Cooling down
After rolling control is finished, slowly cooling the steel plate, wherein the slow cooling process is that the surface temperature of the steel plate is kept more than or equal to 300 ℃ for more than 36 hours, and then the steel plate is naturally cooled to room temperature;
4) Hardening and tempering process
Quenching, wherein the quenching temperature is 880-930 ℃, the quenching holding time is more than or equal to 15min, and the quenching holding time is the heat preservation time for starting timing when the central temperature of the steel plate reaches the quenching target temperature;
tempering, wherein the tempering temperature of the steel plate, namely the plate temperature, is 530-590 ℃, the tempering retention time is more than or equal to 30min, and the tempering retention time is the heat preservation time when the central temperature of the steel plate reaches the tempering target temperature; and naturally cooling the steel plate to room temperature after tempering.
5. The method for manufacturing a low-cost ultra-thick 1000 MPa-grade steel plate according to claim 4, wherein the thickness of the steel plate is greater than or equal to 60mm.
6. The method for manufacturing a low-cost ultra-thick 1000 MPa-grade steel sheet according to claim 4 or 5, wherein the microstructure of the steel sheet is fine low-carbon tempered martensite plus a small amount of tempered lower bainite, and the average grain size of the microstructure is less than 25 μm.
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