METHOD FOR MANUFACTURING HIGH RESISTANCE STRUCTURAL STEEL AND HIGH RESISTANCE STRUCTURAL STEEL PRODU

专利摘要:
The method for manufacturing a high strength structural steel and a high strength structural steel product The invention relates to a method for manufacturing a high strength structural steel and a high strength structural steel product. The method comprises a delivery step for the supply of a steel plate, a heating step (1) for heating said steel plate to 950 to 1,300 ° C, a temperature equalization step (2) for the equalization of the steel plate. steel plate temperature, a hot rolling step including a type i (5) hot rolling stage for hot rolling the steel plate in the temperature range without recrystallization below the recrystallization stop temperature (rst ), but above the ferrite forming temperature a3, a quenching step (6) for quenching said hot-rolled steel at a cooling rate of at least 20 ° C / s for a quenching temperature (qt) between temperatures ms and mf, a partitioning treatment step (7, 9) for partitioning said hot rolled steel to transfer carbon from martensite to austenite and a cooling step (8) for cooling said l steel hot melted to room temperature.
公开号:BR112013033860B1
申请号:R112013033860-1
申请日:2012-07-02
公开日:2019-10-08
发明作者:Mahesh Chandra Somani；David Arthur Porter；Leo Pentti Karjalainen；Tero Tapio Rasmus；Ari Mikael Hirvi
申请人:Rautaruukki Oyj；
IPC主号:

专利说明:

METHOD FOR MANUFACTURING A HIGH STRENGTH STRUCTURAL STEEL AND A HIGH STRENGTH STRUCTURAL STEEL PRODUCT [0001] The invention disclosed in this patent application was produced by inventors Mahesh Chandra Somani, David Arthur Porter, Leo Pentti Karjalainen, at University of Oulu, and by Tero Tapio Rasmus and Ari Mikael Hirvi in Rautaruukki Oyj. The invention was transferred to the transferee, Rautaruukki Oyj, by a separate agreement made between the parties.
Field of the Invention [0002] The invention relates to a method for the manufacture of structural steel with high strength as defined in claim 1 and to a structural steel product with high strength as defined in claim 25. Especially, the invention relates to to the Q&P method (Quenching & Partitioning) applied in a hot to hot strip laminator and to a structural steel product, hard, malleable and with high resistance that has an essentially martensitic microstructure with small fractions of finely divided retained austenite.
Background of the Invention [0003] Conventionally, quenching and tempering are used to obtain highly resistant structural steels with impact toughness and elongation. However, tempering is an additional process step that requires time and energy due to the reheating of temperatures below Mf after quenching.
[0004] In recent years, sophisticated high-strength steels with improved toughness are advantageously achieved by direct tempering. However, the ductility of these steels in terms of their elongation or reduction of area for rupture in a uniaxial strain test is generally acceptable, but their uniform elongation, that is, their hardening capacity could be improved. This deficiency is an important factor that limits the wider application and greater demand for such steels due to the
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2/41 the fact that localization of deformation during manufacture or as a result of overload in the final application can be detrimental to the integrity of the structure.
[0005] Due to a still growing demand for advanced high strength steels (AHSS) with excellent toughness and reasonable ductility and weldability, new efforts have been directed towards developing new compositions and / or processes to meet industry challenges. Within this category, dual phase (DP), complex phase (CP), strain-induced transformation (TRIP) and maclation-induced transformation (TWIP) steels have been developed over the past few decades, primarily to meet the requirements of the automotive industry . The main objective has been to save energy and raw materials, improve safety standards and protect the environment. In addition, the yield strength of AHSS steels above with carbon content in the range of 0.05 to 0.2% by weight were usually restricted to about 500 to 1,000 MPa.
[0006] Patent publication US2006 / 0011274 A1 reveals a relatively new process called quenching and partitioning (Q&P) that allows the production of steel with microstructures that contain retained austenite. This known tempering and partitioning process consists of a two-stage heat treatment. After reheating in order to obtain a partially or completely austenitic microstructure, the steel is cooled to a suitable predetermined temperature between the start (Ms) and end (Mf) temperatures of martensite. The desired microstructure at this tempering temperature (QT) consists of ferrite, martensite and austenite or untransformed martensite and untransformed austenite. In a second partitioning stage, the steel is kept in the QT or brought to a higher temperature, the so-called partitioning temperature (PT), that is, PT> QT. The objective of the last stage is to enrich the non-transformed austenite with carbon by depleting supersaturated martensite
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3/41 with carbon. In the Q&P process, the formation of iron carbides or bainite is intentionally suppressed and the retained austenite is stabilized to obtain the advantage of deformation-induced transformation during subsequent forming operations.
[0007] The above developments were aimed at improving the mechanical properties and properties related to the formation of thin sheet steel to be used in automotive applications. In such applications, impact toughness is not required and the yield strength is limited to below 1,000 MPa.
[0008] The purpose of this invention is preferably to perform, without additional heating from temperatures below Mf after quenching, a structural steel product that has an elasticity limit R _p02 of at least 960 MPa and excellent toughness for impact , such as transition temperature Charpy V 27J <-50 ° C, preferably <- 80 ° C together with good total uniform elongation.
[0009] However, although the best practice is to use the invention within the field of structural steels, it should be understood that the method and steel product referenced in accordance with the invention can also be used as a method for manufacturing rolled steels. wear-resistant hot-rolled steel and that the referenced high-strength structural steel product can be used as wear-resistant hot-rolled steel, although such impact toughness and ductility is not always required in wear-resistant steel applications.
Brief Description of the Invention [0010] In the method, a steel plate, billet or billet (hereinafter simply referred to as a steel plate) is heated in a heating step to a specified temperature and then thermomechanically rolled in one step hot rolling mill. Thermomechanical rolling includes a type I hot rolling stage for hot rolling of the steel plate in
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4/41 a temperature range below the recrystallization stop temperature (RST) and above the ferrite formation temperature A3. If the heating step for heating the steel plate includes heating to a temperature in the range 1,000 to 1,300 ° C, the thermomechanical lamination additionally includes a type II hot rolling stage for the hot rolling of the steel plate in the static recrystallization domain above the recrystallization limit temperature (RLT), whose type II hot rolling stage is performed before the type I hot rolling stage for hot rolling of the steel plate in the temperature range below the recrystallization stop temperature (RST) and above ferrite formation temperature A3. In the event that the heating step is performed at lower heating temperatures, such as 950 ° C, the resulting smaller initial austenite grain size eliminates the need for the type II hot rolling stage to be performed above the limit temperature of recrystallization (RLT) and consequently most of the hot rolling can occur below the recrystallization stop temperature (RST).
[0011] The deformation accumulated below the recrystallization stop temperature (RST) is preferably at least 0.4. Subsequent to this thermomechanical rolling, that is, the hot rolling step, the hot rolled steel is cooled directly in a quenching step to a temperature between Ms and Mf temperatures to achieve the desired fractions of martensite-austenite and subsequently the hot-rolled steel is maintained at a quench temperature (QT), slowly cooled from QT or further heated to a PT> QT partitioning temperature to increase austenite stability by performing a partitioning step to partition carbon of supersaturated martensite in austenite. After carbon partitioning, that is, the partitioning step, a cooling step for cooling hot rolled steel to room temperature is
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5/41 executed. During the cooling step, some of the austenite may turn into martensite, but some of the austenite remains stable at or below room temperature. Unlike the case of tempering, the formation of iron carbides and the decomposition of austenite are intentionally suppressed during partitioning through the appropriate choice of the chemical composition of the steel, mainly through the use of a high silicon content together with or without aluminum in such content, which could provide such an effect.
[0012] The method for supplying a structural steel that has high strength and high impact toughness requires control of the austenite state, that is, grain size and shape, and displacement density, before tempering, which means preferably deformation both in the recrystallization regime and in the regime without recrystallization followed by DQ&P (Direct Tempering & Partitioning) processing. Thermomechanical lamination followed by direct tempering results in the formation of thin bundles and blocks of thin martensitic slats, shortened and randomized in different directions. Such a microstructure intensifies the resistance. This also intensifies impact and break toughness making crack propagation more tortuous. Additionally, partitioning increases the stability of austenite that exists after cooling to QT, thus leading to the presence of austenite retained at room temperature and at lower temperatures.
[0013] Retained austenite is, however, partly metastable and partly turns into martensite during plastic deformation as occurs in intentional deformation of the steel, steel deformation test, or overload of the steel structure in the final application. This transformation from austenite to martensite increases the hardening rate and the uniform elongation of the steel product which helps to prevent the localization of deformation and premature structural failure due to malleable rupture. Along with the thin, shortened and randomized martensitic slats, these austenite films
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Retained 6/41 enhance toughness against impact and breakage.
[0014] The advantage of the type I lamination stage that results in previously tensioned austenite grains (PAG) is the finer distribution of austenite during the subsequent tempering for QT. When this type of austenite is further stabilized by partitioning, the enhanced combination of mechanical properties is achieved, particularly with regard to total uniform elongation and toughness for impact.
[0015] In this way, the method according to the invention provides a structural steel with high strength that has an improved combination of toughness for impact, preferably also toughness against breakage and total uniform elongation. The structural steel product according to the invention can be used in broader applications where impact and break toughness is essential and / or better deformation capacity without malleable break is required. The use of high strength steel means that lighter structures can be produced.
[0016] The invented method was called TMR-DQP, that is, thermomechanical lamination followed by direct tempering & partitioning.
Description of the Drawings [0017] Figure 1 reveals a temperature-time curve according to the modalities of the invention, [0018] Figure 2 reveals the microstructure of a structural steel with high strength that has retained austenite and thin packages / blocks of thin martensitic slats, shortened and randomized in different directions, [0019] Figure 3 reveals a TEM micrograph of a simulated specimen of Gleeble that has thin martensitic slat packs / blocks (white) and austenite interpolates (dark), [0020] A Figure 4 reveals a temperature - time curve of a modality according to the invention, [0021] Figure 5 reveals a temperature - time curve of
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7/41 a modality according to the invention, and [0022] Figure 6 reveals the test results of the first main modality (called a modality with a high Si content) related to impact toughness compared to directly cooled steel without partitioning , [0023] Figure 7 reveals a temperature-time curve of a modality according to the invention, [0024] Figure 8 reveals the test results of the second main modality (called a modality with a high content of Al) related to impact toughness compared to steel directly cooled without partitioning, and [0025] Figure 9 shows a schematic microstructure drawing according to an embodiment of the invention.
Description of Abbreviations and Symbols [0026] ε True strain ει, ε ₂ , ε ₃ Main plastic true stresses in three parallel perpendicular directions ε ^ Equivalent plastic true strain ε 'Constant rate of true strain
A Total elongation
AC Air cooling
AF Alloy factor
A _g Uniformly plastic elongation
A _gt Total uniform elongation
A ₃ Temperature below which austenite becomes supersaturated in relation to ferrite
Carbon equivalent CEV
CP Complex phase
CS Winding simulation
DI Ideal critical diameter
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8/41
DP Dual phase
DQ&P Direct quenching and partitioning
EBSD Electron backscatter diffraction
FRT Finish Lamination Temperature
GAR Grain aspect ratio h Length of a volume element after plastic deformation
H Length of a volume element before plastic deformation
Mf Final temperature of martensite
Ms Initial martensite temperature
PAG Previous austenite grain
PT Partitioning temperature (if partitioning reached a temperature greater than QT).
Q&P Quenching and partitioning
QT Quenching or quenching temperature
RLT Recrystallization limit temperature
R _m Final tensile strength
Rp ₀ , ₂ 0.2% yield strength
Rpi, ₀ 1.0% firm resistance
RST Recrystallization stop temperature
RT ambient temperature
SEM Scanning electron microscopy t time
T27J Temperature corresponding to the impact energy of 27 J
T50% Temperature corresponding to 50% shear failure
TEM Transmission electron microscopy
TMR Thermomechanical lamination
TMR-DQP Thermomechanical lamination followed by quenching
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9/41 direct and partitioning
TRIP Deformation-induced transformation
TWIP Maclation-induced transformation
XRD X-ray diffraction
Z Area reduction
List of reference numbers and explanation
Heating step
Temperature equalization step
Type II hot rolling stage in the recrystallization temperature range
Waiting period for temperature to fall below RST
Type I hot rolling stage in the temperature range without recrystallization
Tempering step
Partitioning step
Cooling step
Alternative partitioning step
Retained austenite
Martensita
Detailed Description of the Invention [0027] The method for manufacturing a structural steel with high strength according to independent claim 1 comprises the following steps:
- A supply step for the supply of a steel plate (not shown in the Figures),
- A heating step 1 for heating the steel plate to a temperature in the range 950 to 1,300 ° C,
- A temperature equalization step 2 for the steel plate temperature equalization,
- A hot rolling stage that includes a
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10/41 type I 5 hot rolling for hot rolling of the steel plate in the temperature range without recrystallization below RST, but above the ferrite formation temperature A3,
- A quenching step 6 for quenching hot-rolled steel at a cooling rate of at least 20 ° C / s for quenching temperature (QT), whose quenching temperature (QT) is among the Ms and Mf temperatures,
- A partitioning step 7, 9 to partition hot-rolled steel in order to transfer carbon from martensite to austenite, and
- A cooling step 8 for cooling said hot-rolled steel to room temperature through forced or natural cooling.
[0028] The preferred modalities of the method are revealed in the attached claims 2 to 24.
[0029] The method comprises a heating step 1 for heating the steel plate to a temperature in the range 950 to 1,300 ° C in order to obtain the microstructure completely austenitic.
[0030] Heating step 1 is followed by a temperature equalization step 2 that allows all parts of the plate to reach essentially the same temperature level.
[0031] If heating step 1 for heating the steel plate to a temperature in the range 950 to 1,300 ° C includes heating the steel plate to a temperature in the range 1,000 to 1,300 ° C, the hot rolling step also comprises a type II 3 hot rolling stage, which is performed before the type I 5 hot rolling stage, for hot rolling of the steel plate at a temperature above the RLT in the recrystallization regime in order to refine austenite grain size. In order to achieve the principles of this invention, the hot rolling stage includes a type I 5 hot rolling stage that runs in the temperature range without
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11/41 recrystallization, that is, below the RST and above the ferrite formation temperature A3. If the hot rolling stage comprises both a type I 5 hot rolling stage which is carried out in the temperature range without recrystallization, that is, below the RST and above the ferrite formation temperature A3, as well as a hot rolling stage type II hot plate for hot rolling of the steel plate at a temperature above the RLT in the recrystallization regime, there may be a waiting period 4 without including any hot rolling between the type II hot rolling stage 3 and the hot rolling stage type I 5. One purpose of such a waiting period 4 between the hot rolling stage type II 3 and the hot rolling stage type I 5 is to let the temperature of the hot rolled steel drop below the RST temperature. It is also possible to have other waiting periods during the type II hot rolling stage 3 and the type 1 hot rolling stage 5. It is also possible that the hot rolling stage includes a type hot rolling stage III that runs in the waiting period 4 in the temperature range below the RLT and above the RST. Such a practice may be desirable for reasons of productivity, for example.
[0032] If the hot rolling stage comprises a type I hot rolling stage, a type II hot rolling stage, and a type III hot rolling stage, the steel plate is preferably but not necessarily, continuously rolled during the type I hot rolling stage, during the type II hot rolling stage, and during the type III hot rolling stage and when moving from the hot rolling stage of the type II for the type III hot rolling stage and correspondingly when moving from the type III hot rolling stage to the type I hot rolling stage.
[0033] Hot rolling is not carried out below A3, as otherwise the high yield strength is not reached.
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12/41 [0034] The type I 5 hot rolling stage in the temperature range without recrystallization followed by tempering step 6 results in thin martensite slabs and thin blocks shortened and randomized in different directions in the microstructure. The correct state of austenite before tempering step 6 and partitioning step 7 is essential to ensure the fineness of the subsequent martensite and the nature of carbon partitioning for finely divided and sized sub-micron austenite clusters and strips. The finely divided and dimensioned nano / submicron clusters / austenite strips between the martensite strips provide the necessary hardening capacity thereby improving the elongation balance for breaking and tensile strength for this high strength structural steel. According to one embodiment, the type I 5 hot rolling stage in the temperature range without recrystallization includes at least 0.4 total accumulated equivalent deformation. This is due to the fact that an accumulated total von Mises deformation of 0.4 below the RST is considered the preferential minimum necessary to provide sufficient austenite conditioning before tempering step 6 and partitioning step 7.
[0035] This means that the grain aspect ratio (GAR) of anterior austenite grain (PAG) can be such as 2.2 to 8.0 or 2.3 to 5.0 corresponding to the total accumulated equivalent deformation of 0.4 to 1.1 and 0.4 to 0.8, respectively, for example.
[0036] In this description, the term deformation means the equivalent true plastic deformation von Mises. This describes the extent of plastic deformation during rolling passes or the compression steps in the Gleeble simulation experiments described below or the pre-deformation given to the steel before use. This is confirmed by the following equation:
Seq = {2 (ε1 ² + S2 ² + £ 3 ² ) / 3} ^1/2 where ε1, ε ₂ and ε ₃ are the true plastic stresses
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Major 13/41 in steel such that £ 1 + £ 2 + £ 3 = 0.
[0037] The true deformation is given by the natural logarithm of the ratio of the length of a volume element after the plastic deformation (h) to that before the plastic deformation (H), that is, £ = 1n (h / H) [0038 ] It can be seen that while the true strain can be positive or negative, the equivalent strain is always a positive amount regardless of whether the main strain is tense or compressive.
[0039] As an example of the above, an accumulated true equivalent deformation of 0.4 corresponds to a thickness reduction of 29% in sheet rolling or a reduction of area of 33% in bar rolling.
[0040] The hot rolling step is preferably carried out so that the final thickness of hot rolled steel is 3 to 20 mm and according to the modalities described in more detail later in this description, the thickness ranges are 3 to 11 and 11 to 20 mm.
[0041] Immediately after the hot rolling step, the hot rolled plate is in a quenching step 6 cooled to a temperature between the temperatures Ms and Mf at a cooling rate of at least 20 ° C / s. This tempering step 6, that is, forced cooling provides a mixture of martensite and austenite. During the partitioning step 7, the carbon divisions in austenite thereby increase their stability in relation to the transformation into martensite in a subsequent cooling step 8 to room temperature. It can be understood that during the partitioning step 7 some, but not all, of the carbon is transferred from martensite to austenite. In this way, after cooling to room temperature, a small fraction of finely divided austenite 10 is retained between the martensite slats
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14/41 transformed 11. As a result, the martensitic matrix provides the required strength, while the small fraction of retained austenite distributed very finely between the martensitic slats improves the hardening rate, total uniform elongation and impact toughness.
[0042] As generally known, direct tempering means that all thermomechanical processing operations, that is, hot rolling stages 3, 5 are completed before performing tempering 6 directly from the heat available in the hot rolling process . This means that any separate post-heating steps for hardening temperatures are not necessary in any case.
[0043] Additionally, as understood from the aforementioned, the method does not include any additional heating steps of temperatures below Mf after quenching, such as tempering steps, which would require more heating energy.
[0044] According to one embodiment, in the tempering step 6, the hot-rolled steel plate is cooled to a temperature between the Ms and Mf temperatures at a cooling rate of at least corresponding to the critical cooling rate (CCR) .
[0045] The Ms and Mf temperatures vary according to the chemical composition of the steel. They can be calculated using the formulas available in the literature or measured experimentally with the use of dilatometric measurements.
[0046] According to one modality, the quenching temperature (QT) is less than 400 ° C, but greater than 200 ° C.
[0047] The quench quench temperature (QT) is preferably selected in such a way that an adequate amount of austenite remains in the microstructure after quenching step 6 in QT at the beginning of the partitioning step 7. This means that QT needs be greater than Mf. An adequate amount of austenite is at least 5% to ensure sufficient retained austenite at room temperature to
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15/41 improved ductility and toughness. On the other hand, the amount of austenite at QT immediately after quenching cannot be greater than 30%. The microstructures in this description are given in terms of volume percentages.
[0048] According to a preferred embodiment shown in Figure 1 with a reference number 7, the partitioning step 7 is preferably carried out substantially at the quenching temperature (QT). According to an alternative embodiment shown in Figure 1 with a reference number 9, partitioning step 9 is carried out substantially above the quenching temperature (QT), preferably above the temperature Ms. Heating to a temperature above quenching temperature (QT) can be achieved, for example, by induction heating equipment in a hot to hot strip mill.
[0049] It is preferable that the partitioning step (7 or 9) is carried out at a temperature in the range 250 to 500 ° C.
[0050] Partitioning step 7, 9 is preferably performed so that the average cooling rate during partitioning step 7, 9 is less than the average cooling rate in free air cooling at the temperature in question. The maximum average cooling rate during this stage can be, for example, 0.2 ° C / s, that is, much lower than the cooling rate with free air cooling at the temperature in question (QT). The delay in the cooling rate can be accomplished in several ways.
[0051] According to one modality, the method comprises a winding step that is performed after tempering step 6 and before partitioning step 7, 9. In this modality, the cooling rate is reduced by winding strip material subsequent to the tempering step 6. The coil allows very fast cooling, but in some cases, it may be preferable to also use thermal shields in the
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16/41 coils in order to additionally decrease the cooling rate. In this case, partitioning step 7, 9 is performed after the coil is wound and is indistinguishable from the final cooling step 8.
[0052] According to one modality, the cooling rate is limited by thermal shields applied to hot rolled steel sheets or bars.
[0053] According to one embodiment, partitioning step 7, 9 is performed at an essentially constant temperature. This can be done, for example, in a furnace.
[0054] It is preferable that partitioning step 7 is carried out for 10 to 100,000 s, preferably within the 600 to 10,000 s time period calculated from reaching the quench temperature (QT).
[0055] Cooling step 8 occurs naturally after partitioning step 7, 9. This can be free air cooling or accelerated cooling to room temperature.
[0056] The method can provide a structural steel that has an elastic limit R _p02 > 960 MPa, preferably R _p02 > 1,000 MPa.
[0057] According to one modality, a pre-strain step is performed subsequent to partitioning step 7, 9. Pre-strain of 0.01 to 0.02 subsequent to partitioning step 7, 9 can result in structural steel with a limit of elasticity R _p02 > 1,200 MPa. It is preferred, but not necessarily, that the steel plate as well as the hot-rolled structural steel product with high strength includes, in terms of percentages of mass, iron and unavoidable impurities, and in addition at least the following:
C: 0.17 to 0.23%,
Si: 1.4 to 2.0% or Si + Al: 1.2 to 2.0%, where Si is at least 0.4% and Al is at least 0.1%, preferably at least 0, 8%,
Mn: 1.4 to 2.3%, and
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17/41
Cr: 0.4 to 2.0%.
[0058] The reasons for the limits of this preferred chemistry are as follows:
[0059] Carbon, C, in the specified range is necessary to achieve the desired resistance level together with sufficient toughness and weldability. The lower levels of carbon will result in very low resistance, while the upper levels will impair the toughness and weldability of the steel.
[0060] Both silicon, Si, and aluminum, Al, prevent the formation of carbide (such as iron carbide, cementite) and promote the partitioning of supersaturated martensite into finely divided austenite. These alloy-forming elements help carbon to remain in solution in austenite during and after partitioning 7, 9 through the disturbance of carbide formation. As the high silicon content can cause poor surface quality, a partial replacement of silicon with aluminum, Al, is possible. This is due to the fact that the effect of aluminum on the stabilization of austenite is somewhat weaker compared to silicon. Aluminum is known to raise transformation temperatures and, therefore, chemistry needs to be carefully controlled to prevent the extension of the intercritical or ferrite region induced by deformation during lamination and / or subsequent accelerated cooling. This is because the steel plate as well as the hot-rolled structural steel with high strength preferably includes, in terms of percentage of mass, Si: 1.4 to 2.0% or alternatively Si + Al: 1.2 to 2 , 0%, where Si is at least 0.4% and Al is at least 0.1%, preferably at least 0.8%, in terms of percentages by weight of the steel plate or structural steel. This definition includes both the first main modality (called a high Si content) and a second main modality (called a high Al content).
[0061] Manganese, Mn, in the specified range provides
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18/41 hardening capacity that allows the formation of martensite during tempering and prevents the formation of bainite or ferrite. This is because there is a lower limit of 1.4%. The upper limit of 2.3% manganese serves to avoid excessive segregation and structural bonding, which is harmful to ductility. Chromium, Cr, in the specified range also provides hardening capacity that allows the formation of martensite during tempering and prevents the formation of bainite or ferrite. This is because there is a lower limit of 0.4%. The upper limit of 2.0% serves to avoid excessive segregation and structural bonding, which is detrimental to ductility.
[0062] According to a first main modality (called modality with a high Si content), silicon, Si, is necessary at least 1.4% to prevent the formation of carbide and promote the partitioning of supersaturated martensite carbon in finely divided austenite. The high silicon content helps carbon to remain in solution in austenite during and after partitioning 7, 9 through the disturbance of carbide formation. According to the first modality (called a high Si content modality) the steel plate as well as the hot rolled high strength structural steel includes, in terms of percentages of mass, iron and unavoidable impurities, and additionally at least Following:
C: 0.17 to 0.23%,
Si: 1.4 to 2.0%,
Mn: 1.4 to 2.3%, and
Cr: 0.4 to 2.0%.
[0063] According to a second main modality (called modality with high content of Al), the steel plate as well as the structural steel with high resistance hot rolled includes, in terms of percentages of mass, iron and unavoidable impurities, and additionally at least the following:
C: 0.17 to 0.23%,
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Si + Al: 1.2 to 2.0%, where Si is at least 0.4% and Al is at least 0.1%, preferably at least 0.8%,
Mn: 1.4 to 2.3%,
Cr: 0.4 to 2.0%, and
Mo: 0 to 0.7%, preferably Mo 0.1 to 0.7%.
[0064] According to a preferred version of the second main modality (called the high Al content modality), the steel plate as well as the hot rolled high strength structural steel includes, in terms of percentages of mass, iron and unavoidable impurities, and additionally at least the following:
C: 0.17 to 0.23%,
Si + Al: 1.2 to 2.0%, where Si is 0.4 to 1.2% and Al is 0.8 to 1.6%, most preferably Si is 0.4 to 0.7% and Al is 0.8 to 1.3%,
Mn: 1.4 to 2.3%,
Cr: 0.4 to 2.0%, and
Mo: 0 to 0.7%, preferably Mo 0.1 to 0.7%.
[0065] Molybdenum, Mo, in the specified range, preferably 0.1 to 0.7%, delays the reaction of bainite thereby improving the hardening capacity. Although Mo is known to promote carbide formation from a thermodynamic point of view, but due to its strong solute drag effect, carbide precipitation is actually delayed or stopped at lower temperatures, thus facilitating the partitioning of carbon and the stabilization of austenite. In addition to improving the strength and ductility of steels, this can actually facilitate the possibility of decreasing the required silicon level.
[0066] Regardless of how carbon partitioning is performed, it is preferable that the steel chemistry provides additional adequate hardening capacity.
[0067] The hardening capacity can be determined in several ways. In this patent description, the ability to
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20/41 hardening can be determined by DI, where DI is an index of hardening capacity based on a modification of the ASTM A255-89 standard given by the following formula:
DI = 13.0C x (1.15 + 2.48Mn + 0.74Mn ² ) x (1 + 2.16Cr) x (1 + 3.00Mo) x (1 + 1.73V) x (1 + 0, 36Ni) x (1 + 0.70 Si) x (1 + 0.37Cu) (1) where the alloying elements are in% by weight and DI in mm.
[0068] In one embodiment, hot rolling is carried out so that the thickness of hot rolled steel is 3 to 20 mm, preferably 3 to 11 mm and the steel plate as well as the structural hot rolled steel with high Strength includes, in terms of mass percentages, such a composition in which the hardening index DI as calculated using formula (1) is greater than 70 mm. This ensures the hardening capacity especially of strip or sheet products that are 3 to 11 mm thick without the formation of unwanted bainite.
[0069] Table 1 shows the chemical composition ranges mentioned previously in the first main modality (called a high Si content) and respectively in the second main modality (called a high Al content), which were invented to generate the properties required especially in strip or sheet products that are 3 to 11 mm thick and produced according to the method.
[0070] In addition, Table 1 shows the upper limits for possible additional alloying elements in the first main modality (called modality with high Si content) and respectively in the second main modality (called modality with high Al content), such as Mo (<0.3%, <0.7%, respectively), Ni (<1.0%, <1.0%, respectively), Cu (<1.0%, <1.0%, respectively) and V (<0.06%, <0.06%, respectively), whose one or more alloying elements, which are also individually selected, are
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21/41 to extend the method according to the invention to thicker plates up to 20 mm, such as thicknesses from 11 to 20 mm. For example, one or more of the alloy forming elements Mo, Ni, Cu, Nb, V as given in Table 1, can be used to increase the hardening capacity especially of thicker sheets with 11 to 20mm. Also other alloying elements that increase the curing capacity can be used.
Table 1: Chemical composition ranges of preferred modalities
SteelÇ Si Mn Cr Mo Ni Ass V Nb Al DQP Min. 0.17 1.40 1.40 0.40 0.00 0.00 0.00 0.00 0.00 0.01 Si alto Max. 0.23 2.00 2.30 2.00 0.30 1.00 1.00 0.06 0.03 0.10 DQP Min. 0.17 0.50 1.40 0.40 0.00 0.00 0.00 0.00 0.00 0.70 Al high Max. 0.23 0.70 2.30 2.00 0.70 1.00 1.00 0.06 0.03 1.30
[0071] In another embodiment, hot rolling 3, 5 is carried out so that the thickness of hot rolled steel is 3 to 20 mm, preferably 11 to 20 mm and the steel plate as well as the structural steel with High strength hot-rolled includes, in terms of mass percentages, such a composition in which the hardening index DI as calculated using the formula (1) is at least 125 mm. This ensures the hardening capacity especially of strip or sheet products that are 11 to 20 mm thick without unwanted bainite formation.
[0072] In addition to the elements mentioned in equation 1, an addition of boron B, in terms of weight percentages, 0.0005 to 0.005%, can be made to increase the DI, that is, the hardening capacity, of TMR steels -DQP. The effect of boron is described by the boron multiplication factor BF described in more detail in the ASTM A255-89 standard. Boron-containing steels can be processed in the manner described for boron-free steels.
[0073] In the first main modality (called a high Si content modality), the addition of boron mentioned above will also require an addition of Ti, in terms of mass percentages, 0.01 to
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22/41
0.05% to form TiN precipitates and prevent boron B from reacting with nitrogen N in steel during thermomechanical processing. However, in such cases, steel may have slightly lower impact properties due to the presence of TiN inclusions. The detrimental effects of TiN inclusions can, however, be counteracted by an addition of Ni of up to 4%, such as 0.8 to 4%, generating impact properties equivalent to those of DQP steels without boron. In the second main modality (called a modality with a high content of Al), an addition of boron B, in terms of weight percentages, 0.0005 to 0.005% can also be added without a deliberate addition of Ti, since nitrogen N will be connected as A1N.
[0074] It is also possible, but not necessary, that the steel plate as well as structural hot rolled steel with high strength does not contain titanium, Ti, as a deliberate addition. This is because, as understood from the above, titanium can form TiN which can affect toughness. In other words, the steel plate as well as the hot rolled high strength structural steel is preferably, but not necessarily, free of Ti.
[0075] Additionally, as demonstrated later in the examples, the desired hardening capacity can also be achieved without boron, so essentially, there is not necessarily any need to form titanium alloy from this point of view. As understood from the above, the steel plate as well as the hot rolled high strength structural steel is possibly, but not necessarily, also free of B.
[0076] It is also possible, but not necessary, that the steel plate as well as the structural hot rolled steel with high strength does not contain niobium, Nb. However, small additions of Nb can be used to control RST and thereby facilitate TMR (type I 5 lamination). For this reason, steel plate as well as structural steel with high
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Hot rolled strength may comprise 0.005 to 0.05%, such as 0.005 to 0.035% Nb.
[0077] Especially in the first main modality (called modality with high Si content), Al 0.01 to 0.10% is preferred for use in order to exterminate the steel and, through this, reach levels of oxide inclusion low. In addition, the steel plate as well as the hot-rolled structural steel with high strength may include small amounts of calcium, Ca, which may be present, for example, due to the control of inclusion of steel exterminated by Al in the smelter.
[0078] Additionally, it is preferable that the maximum permitted levels of impurity elements P, S and N are, in terms of percentage of mass, the following P <0.012%, S <0.006%) and N <0.006%, which it means that these levels must be adequately controlled through good fusion practice in order to achieve impact toughness and flexibility.
[0079] In cases where there is no deliberate addition, the steel plate and the steel product may contain, in terms of percentage of mass, residual contents such as:
Cu: less than 0.05%,
Ni: less than 0.07%,
V: less than 0.010%,
Nb: less than 0.005%,
Mo: less than 0.02%,
Al: less than 0.1%,
S: less than 0.006%,
N: less than 0.006%, and / or
P: less than 0.012%.
[0080] The exact combination of alloy forming elements chosen will be determined by the thickness of the product and the cooling power of the equipment available for direct quenching. In general, the
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24/41 objective is to use the minimum level of alloy formation consistent with the need to achieve a martensitic microstructure without the formation of bainite or ferrite during tempering. In this way, production costs can be kept to a minimum.
[0081] The structural steel product with high strength has an elasticity limit R _p02 > 960MPa, preferably R _p02 > 1,000 MPa, and is characterized by a microstructure comprising at least 80% martensite and 5 to 20% austenite retained.
[0082] At least 80% of martensite is required to achieve the desired strength and 5 to 20% of retained austenite is required to achieve high toughness for impact and ductility.
[0083] It is preferable that the structural steel product with high strength has a Charpy V 27J (T27J) temperature below -50 ° C, preferably below -80 ° C.
[0084] The Charpy V 27J (T27J) temperature means the temperature at which the 27J impact energy can be achieved with impact specimens in accordance with the EN 10045-1 standard. Impact toughness is improved as the T27J decreases.
[0085] The mechanical properties are proven later in this description.
[0086] Most of the preferred modalities of the high strength structural steel product are disclosed in the attached claims 26 to 38.
[0087] Figure 2 reveals the preferred microstructure of the structural steel product with high strength as seen with the use of light microscopy, that is, thin martensitic strips, shortened and randomized in different directions and retained austenite. Figure 3 is a transmission electron micrograph showing the presence of elongated clusters of austenite (dark) 10 between the martensite strips 11. The presence of retained austenite was also visible in the
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25/41 SEM-EBSD micrographs.
[0088] The fineness of retained austenite 10 (size in submicron / nanometer) improves its stability in such a way that during deformation, such as during stretching, flexing or overloading, the retained austenite is transformed into martensite by a large deformation range. In this way, 5 to 20% of retained austenite provide improved formability and overload support capacity to the structural steel product with high strength.
[0089] As understood above, the retained austenite is stabilized by the carbon partitioning of supersaturated martensite into austenite. Stable retained austenite is thereby achieved. Although a small amount of transition carbides may be present in the steel, it can be said that the steel product according to the invention is preferably substantially free of iron carbides (such as cementite), most preferably, but not necessarily , is substantially free of carbides formed after transformation of fcc (cuboid centered on the face) into bec (cuboid centered on the body).
[0090] Figure 9 shows a schematic drawing of microstructure according to an embodiment of the invention. As can be seen, the microstructure consists of several packages. In some cases, these packages (packages 1, 2 and 3, etc.) may extend up to the size of the previous austenite grain (PAG). As can also be seen, the microstructure consists of strips of martensite and retained austenite. Each package consists of martensite strips 11, shortened and randomized in different directions, and a small fraction of finely divided retained austenite 10 between the martensite strips, which are heavily displaced. The microstructure, as outlined in Figure 9, is substantially free of carbides.
[0091] According to one modality, the structural steel product with high strength is sheet steel.
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26/41 [0092] According to another modality, the structural steel product with high resistance is a strip steel.
[0093] According to another modality, the structural steel product with high strength is a long steel product in the form of a bar.
[0094] Examples of the first main modality (called a high Si content modality) [0095] The first main modality (called a high Si content modality) of the present invention is now described by examples, in which an experimental steel which contains (% by weight) 0.2C-2.0Mn-1.5Si-0.6Cr was hot rolled, cooled directly in the range between Ms and Mf and treated by partitioning in order to prove the feasibility of the invention to produce structural steels which have an elastic limit of at least 960 MPa with an improved combination of strength, ductility and impact toughness.
[0096] Two states of austenite before quenching were investigated: tensioned and recrystallized. The thermomechanical simulations were performed in a Gleeble simulator to determine the cooling rates and the appropriate cooling stop temperatures to obtain fractions of martensite in the range of 70 to 90% at the quench quench temperature QT. Subsequent laboratory lamination experiments have shown that the desired martensite - austenite microstructures have been achieved and ductility and impact toughness have been improved in this high strength class. The invention will now be described in greater detail with the aid of 1) the results of the Gleeble simulation experiments and 2) the results of laboratory hot rolling experiments.
1. Gleeble simulation experiments [0097] Preliminary expansion tests were performed on a Gleeble simulator to approximately simulate industrial rolling with high and low finishing rolling temperatures, resulting in
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27/41 respectively in non-deformed (recrystallized) and deformed (tensioned) austenites before tempering.
[0098] For undeformed austenite, the samples were reheated at 20 ° C / s at 1150 ° C, maintained for 2 min. and cooled to 30 ° C / s to below the Ms temperature, generating initial fractions of martensite in the range of 70 to 90%. The samples were then maintained to allow carbon partitioning for 10 to 1,000 s at or above the quench quench temperature QT, followed by air cooling between Gleeble's anvils (~ 10 to 15 ° C / s below 100 ° C).
[0099] In the case of deformed austenite, the samples were reheated in a similar way, cooled to 850 ° C, maintained for 10 s, and then compressed with three strokes with a deformation of -0.2 at a deformation rate of 1 s ^-1 . The time between strokes was 25 seconds. The specimens were then kept for 25 s before cooling to 30 ° C / s to a tempering temperature below Ms, generating initial fractions of 70 to 90% martensite. Figure 4 shows a temperature vs. time of this thermomechanical simulation schedule.
[00100] The expansion curves of the specimens cooled to 30 ° C / s allowed temperature measurements of Ms (395 ° C) and Mf (255 ° C). These were as expected based on the standard equations given in the literature. The results of the dilatometer suggest that the initial fractions of martensite of about 70, 80 and 90% would be present at tempering temperatures of 340, 320 and 290 ° C, respectively.
[00101] After the direct tempering of recrystallized non-deformed austenite, the packages and blocks of crude martensite slats were seen in the microstructure. However, specimens that were compressed at 850 ° C before tempering showed thinner packages and blocks of martensite strips 11, shortened and randomized in different directions, Figure 2. The elongated clusters of austenite 10 were present between the martensite strips. An example of finely divided austenite stops 10
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28/41 is shown in Figure 3.
[00102] The final 10 austenite fractions ranged from 7 to 15%; generally increasing with quench temperature above QT (290, 320, 340 ° C) and / or PT partitioning temperature (370, 410, 450 ° C).
2. Laboratory lamination experiments [00103] Based on the results of the expansion experiments, the lamination tests were carried out using a laboratory hot strip laminator starting with 110 x 80 x 60 mm plates cut from cast ingots, with a composition by weight of 0.2C2.0Mn-1.5Si-0.6Cr. The lamination was carried out as shown in Figure 1. The temperature of the samples during hot lamination and the cooling was monitored by thermocouples placed in holes drilled at the edges of the samples in half the width and half the length. The samples were heated at 1200 ° C for 2 h (steps 1 and 2 in Figure 1) in a furnace before the two-stage lamination (steps 3 - 5 in Figure 1). Stage 3, that is, the type II hot rolling stage comprised hot rolling in four passes to a thickness of 26 mm with about 0.2 deformation / pass with the temperature of the fourth pass around 1,040 ° Ç. Waiting step 4 comprised waiting for the temperature to drop below 900 ° C, which was estimated to be the RST, and step 5 ie the type I hot rolling step comprised hot rolling to a thickness end of 11.2 mm with four passes of about 0.21 deformation / pass with a finishing lamination temperature (FRT) in the range 800 to 820 ° C (> A ₃ ), Figure 5. All lamination passes were in the same direction, that is, parallels along the plate. Immediately after hot rolling 3, 5, the samples were cooled 6, that is, cooled at a cooling rate of at least 20 ° C / s (average cooling rates about 30 to 35 ° C / s below about 400 ° C), in a water tank close to 290 or 320 ° C (QT) and then
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29/41 subjected to partitioning 7 in a furnace at the same temperature for 10 minutes, Figure 5.
[00104] The microstructural features of material with high laboratory DQ&P resistance in relation to the martensite block and package sizes were quite similar to those seen in the optical microstructures of simulated Gleeble specimens, which indicates that the deformation conditions in hot rolling and direct quenching in QT were adequately controlled. The microstructure of the laminated sheet for a low FRT consisted of thin packages and blocks of thin martensite strips 11, shortened and randomized in different directions, and the austenite contents 10 (as measured by XRD) in the 6 to 9% range, regardless of tempering temperature and furnace (290 or 320 ° C).
[00105] Table 2 presents a summary of process parameters and mechanical properties of laboratory laminated sheets A, B and C, all of which have the composition 0.2C-2.0Mn-1.5Si-0.6Cr. Table 2 clearly shows a complete improvement in properties as a result of TMR-DQP, that is, after two-stage rolling with the type I 5 hot rolling stage below the RST (FRT = 800 ° C) compared to lamination that includes only the type II 3 hot rolling stage (FRT = 1,000 ° C). It is also evident that the properties are improved in comparison to the simple hardening of a steel with a lower carbon content that has a similar elastic limit.
Table 2: Process parameters and mechanical properties for 11.2 mm thick sheets, according to the first main modality (called a high Si content modality)
Traction FRT specimen (° C) / plate
A1 800
A2
A3
B1 B2
B3
C1-R
C2-R
C3-R
QT (° C)
290
800 320
1000 320
Rp0.2 (MPa)
Rp1.0 Rm A25 (MPa) (MPa) (%)
1035 1320 1476
1093 1355 1499
1035 1341 1492
1062 1374 1463
1023 1373 1481
1046 1382 1483
966___1382
943 1397
951 1399
17.6
14.7
16.2
13.4
15.7
16.6
16.3
17.5
15.2
Agt (%) (%)
13.45.3
12.95.7
14.15.5
12.23.7
14.43.9
13.94.4
14.2 4.2
13.5 4.7
13.8 4.4
Ag (%)
4.5
4.9
4.8
2.9
3.2
3.6
3.5
3.7
Z T27J T50% (%) (° C) (° C)
52.5
54.3
58.1 -100 -6
56.9 ___
55.3
56.1 -44 15
54.4
56.4
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30/41
D1-R * 80011311454 12.5 11.4 3.6 2.9 58.5 -12 25 D2-R 10881443 12.6 11.7 3.1 2.5 54.6 D3-R 11051459 13.7 11.5 3.7 3 57.8
* completely martensitic DQ steel with low C content [00106] The mechanical properties of sheets A, B and C produced by direct tempering & Partitioning (DQ&P) were compared with the sheet D obtained using simple direct tempering below temperature Mf, that is, at room temperature, with the use of a steel with a composition that generates similar elastic limit properties, that is, in weight% 0.14C-1.13Mn-0.2Si-0.71Cr-0 , 15Mo-0.033Al-0.03Ti-0.0017B. A plate of this steel was hot rolled in the same manner as described above using the two-stage rolling schedule for a low FRT and quenched with water directly to room temperature.
[00107] For each plate, three traction specimens were extracted. The elasticity limit of 0.2% (R _{p0> 2} ) of sheets A and B is marginally lower than the 1,100 MPa obtained with D. Both the limit of elasticity and the tensile strength obtained with recrystallized C sheets DQ&P (laminated in finish at about 1,000 ° C) are lower than those of A and B that have finish laminate temperatures (FRT) of 800 ° C. This shows the importance of thermomechanical lamination, that is, austenite deformation in the subsequent phase transformation characteristics and resulting properties.
[00108] The pre-deformation of steel for some applications can be plausible or still natural and, in these cases, the elastic limit in use will be raised above the values of R _p02 in Table 2: the elastic limit can then exceed 1,100, 1,200 or 1,300 MPa depending on the pre-strain applied. This is implied by the high values of R _p10 shown by steels A and B.
[00109] As revealed in Table 2, the low finishing laminating temperature (FRT), that is, the type I 5 hot rolling stage performed below the stop temperature of
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31/41 recrystallization (RST) has a notable effect on toughness for impact in the context of DQ&P processing. For each plate approximately nine 10 x 10 mm Charpy V impact test specimens were tested at various temperatures over the malleable to brittle range. The results were used to determine the values of T27J and T50% in Table 2. The individual values of absorbed energy are shown in Figure 6. It can be seen from Figure 6 that FRT 800 ° C followed by direct tempering and partitioning treatment (plates A and B) leads to improved impact resistance compared to FRT 1,000 ° C followed by direct quenching and partitioning (plate C) or compared to simple direct quenching at room temperature for a steel with lower carbon content (plate D) .
[00110] Additionally, surprisingly, despite the fact that the carbon content of specimens A and B (0.20%) is higher than the carbon content of specimen D (0.14%), the temperature corresponding to impact energy 27J Charpy V (T27J) and 50% shear failure (T50%) for plates A and B are distinctly smaller, that is, better than plate D.
[00111] According to Table 2, the temperatures corresponding to the impact energy 27J Charpy V (T27J) of DQP steel can be less than -50 ° C through the use of thermomechanical lamination, that is, with the use of a stage type I 5 rolling mill at temperatures below RST.
[00112] The TMR-DQP plates in Table 2 (A and B) satisfy the target related to the good transition temperature from toughness to impact Charpy V T27J <-50 ° C, preferably <- 80 ° C and also elastic limit R _p02 at least 960 MPa along with good total uniform elongation.
[00113] While the total elongation (A) and the reduction of area to break (Z) vary in a narrow range, the uniform elongation
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32/41 total (A _gt ) and the uniform plastic elongation (Ag) are higher at the lower tempering temperature of 290 ° C compared to the same properties obtained at the tempering temperature 320 ° C, as can be seen in Table 2.
[00114] According to Table 2, the total elongation of A> 10%, still> 12%, has been achieved, which is also a good value at this level of resistance.
[00115] According to Table 2, the total uniform elongation of A _gt > 3.5% was achieved, still A _gt > 4.0%, which is also a good value at this level of resistance.
[00116] It is preferable especially that in the first main modality (called modality with high Si content), the quenching temperature (QT) is between the temperatures Ms and Mf and additionally less than 300 ° C, but greater than 200 ° C in order to achieve the enhanced properties related to stretching.
[00117] The mechanical properties obtained in the invention are better than those obtained in conventionally cooled and tempered steels in the same strength class. In addition, it should be noted that the general combination of mechanical properties is good, which includes strength, ductility and impact toughness properties. All of these are obtained simultaneously.
[00118] Examples of the second main modality (called modality with high content of Al) [00119] The second main modality (called modality with high content of Al) of the present invention is now described by another example, in which a steel experimental containing (% by weight) 0.2C-2.0Mn-0.5Si-1.0-Al-0.5Cr-0.2Mo was hot rolled, cooled directly in the range between Ms and Mf and treated by partitioning in order to prove the feasibility of the invention to produce structural steels that have an elastic limit of at least 960 MPa with combination
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33/41 improved strength, ductility and toughness for impact.
[00120] Two states of austenite before quenching were investigated: tensioned and recrystallized. The thermomechanical simulations were performed in a Gleeble simulator to determine the cooling rates and the appropriate cooling stop temperatures to obtain fractions of martensite in the range 75 to 95% at the quench quench temperature QT. Subsequent laboratory lamination experiments have shown that the desired martensite - austenite microstructures have been achieved, and ductility and impact toughness have been improved in this high strength class.
[00121] The second main modality of the invention will now be described in greater detail with the aid of 1) the results of the Gleeble simulation experiments and 2) the results of laboratory hot rolling experiments.
1. Gleeble simulation experiments [00122] Preliminary expansion tests were performed in a Gleeble simulator to approximately simulate industrial laminating with high and low finishing laminating temperatures, resulting in non-deformed (recrystallized) and deformed (tensioned) austenites, respectively. before tempering.
[00123] For non-deformed austenite, the samples were reheated to 20 ° C / s at 1,000 ° C, maintained for 2 min., And cooled to 30 ° C / s below the temperature of Ms, generating initial fractions of martensite in the range 75 to 95%. The samples were then maintained to allow carbon partition for 10 to 1,000 s at the quench quench temperature QT, followed by air cooling between the Gleeble anvils (~ 10 to 15 ° C / s below 100 ° C).
[00124] In the deformed austenite case, the samples were reheated in a similar way to the above, cooled to 850 ° C, maintained for 10 s, and then compressed with three strokes with a
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34/41 strain of -0.2 at a strain rate of 1 s ^-1 . The time between strokes was 25 seconds. The specimens were then kept for 25 s before cooling to 30 ° C / s to a tempering temperature below Ms, generating initial fractions of martensite of 75 to 95%. Figure 7 reveals a temperature vs. temperature scheme. time of this thermomechanical simulation schedule. The dilation curves of the specimens cooled to 30 ° C / s allowed the measurements of temperatures Ms (400 ° C) and Mf (250 ° C). These were as expected based on the standard equations given in the literature. The dilatometer results suggest the initial austenite fractions of about 25, 12 and 7% would be present at the tempering temperatures of 340, 310 and 290 ° C, respectively.
[00125] After the direct tempering of recrystallized non-deformed austenite, the crude martensite slats packages and blocks were seen in the microstructure. However, the specimens that were compressed at 850 ° C before tempering showed thinner packages and blocks of martensite slats 11, shortened and randomized in different directions, as also seen with high Si content DQP described above.
[00126] Final austenite fractions 10 varied in a narrow range of 5 to 10% regardless of tempering and partitioning temperatures (QT = PT) and / or times in the range 10 to 1,000 s (average 9, 9 and 7% in 340, 310 and 290 ° C, respectively).
2. Laboratory lamination experiments [00127] Based on the results of the expansion experiments, the lamination tests were performed using reverse lamination in a laboratory hot strip laminator that starts with 60 mm thick plates that have a length of 110 mm and width of 80 mm cut from the cast ingots, which have a composition in weight% 0.2C-2.0Mn-0.5Si-1.0 Al-0.5Cr-0.2Mo. The lamination was done as shown in Figure 1. The temperature of the samples during hot lamination and the cooling was monitored by thermocouples placed
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35/41 in holes drilled at the edges of the samples at half the width and half the length. The samples were heated to 1,200 ° C for 2 h (steps 1 and 2 in Figure 1) in a furnace before the two-stage lamination (steps 3 to 5 in Figure 1). Step 3, that is, type II hot rolling stage comprised hot rolling in four passes to a thickness of 26 mm with about 0.2 deformation / pass with the temperature of the fourth pass around 1040 ° Ç. Step 4 comprised the wait for the temperature drop to about 920 ° C, which was estimated to be the RST, and step 5, that is, type I hot rolling step, comprised the hot rolling to a thickness 11.2 mm end with four passes of about 0.21 deformation / pass with a finishing lamination temperature (FRT)> 820 ° C (> A ₃ ). All lamination passes were parallel across the board. Immediately after hot rolling 3, 5, the samples were cooled 6, that is, cooled at a cooling rate of at least 20 ° C / s (average cooling rates about 30 to 35 ° C / s below about 400 ° C), in a water tank for temperatures close to 340, 320 or 270 ° C (QT) and then subjected to partitioning 7 in a furnace at the same temperature for 10 minutes or during extremely slow cooling for 27 to 30 hours to 50 to 100 ° C. This also allowed an understanding of the influence of CS winding simulation on mechanical properties compared to those of partitioning for about 10 minutes.
[00128] The microstructural features of TMRDQP material of high laboratory resistance in relation to the martensite block and package sizes were quite similar to those seen in optical microstructures of simulated Gleebles specimen, which indicates that the deformation conditions in hot rolling and quenching direct to QT were adequately controlled. The microstructure of the laminated sheet for a low FRT consisted of thin packages and blocks of thin martensite strips 11, shortened and randomized in different directions and
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36/41 final levels of austenite 10 (as measured by XRD) in the range 4 to 7%, regardless of temper and furnace temperature (270 to 340 ° C).
[00129] Table 3 presents a summary of process parameters and mechanical properties of laboratory laminated sheets A, B, C, D and E, all of which have the composition 0.2C-2.0Mn-0.5Si-1, 0Al-0.5Cr0.2Mo. Table 3 clearly shows a balanced improvement in properties as a result of TMR-DQP, that is, after the two-stage rolling with the type I 5 hot rolling stage below the RST (FRT> 820 ° C). It is also evident that the properties are improved compared to the simple direct tempering of a steel with a lower carbon content that has a similar elastic limit.
Table 3: Process parameters and mechanical properties for 11.2 mm thick sheets, according to the second main modality (called a high Al content)
Traction specimen / plate FRT (° C) QT (° C) Rp0.2 (MPa) Rp1.0 (MPa) Rm (MPa) A25 (%) THE(%) Agt (%) Ag (%) Z(%) T27J (° C) T50%(° C) TO 1 820 340 1082 1327 1365 13.6 12 2.9 2.2 52.9 -55 -7 A2 1068 1316 1349 13.4 12.1 2.8 2.2 50.4 A3 1071 1287 1318 15.4 12.8 2.9 2.2 55 B1 825 340CS 1004 1200 1243 16.8 13.3 2.9 2.3 55.5 -100 -34 B2 1013 1214 1252 14.9 10.5 2.7 2.1 57.2 B3 998 1196 1241 15.8 13.2 2.8 2.2 58.3 C1 820 320CS 1009 1267 1390 12.7 10.6 4.3 3.6 48.3 -90 -6 C2 1030 1274 1396 14.8 11.6 4.5 3.8 48.3 D1 820 270CS 1157 1397 1484 9.2 8.2 3.7 3 45.9 -87 0 D2 1203 1428 1506 14.6 11.6 4.1 3.3 45.9 E1 890 310CS 1128 1349 1398 11.1 9.9 3.2 2.4 47.1 -67 -4 E2 1117 1346 1398 14.6 10.5 3 2.2 51.5 E3 1111 1341 1392 10.8 8.4 3.1 2.3 54.6 F1-R 800 *11311454 12.5 11.4 3.6 2.9 58.5 -12 25 F2-R 10881443 12.6 11.7 3.1 2.5 54.6 F3-R 11051459 13.7 11.5 3.7 3 57.8
completely martensitic steel with lower C content
CS = Winding simulation [00130] The mechanical properties of TMR-DQP steel sheets with high content of Al A, B, C, D and E in table 3 produced by direct tempering & partitioning (DQ&P) were compared with sheet F in table 3 obtained with the use of simple quenching directly below the temperature M _f , that is, for room temperature, with the use of a steel with
Petition 870190008037, of 01/24/2019, p. 60/66
37/41 a composition that generates similar yield strength properties, i.e., wt% 0.14C-1.13Mn-0.2Si-0.71Cr-0.15Mo-0.033Al-0.03Ti0.0017B. A plate of this steel was hot rolled in the same manner as described above using the two-stage rolling schedule for a low FRT and quenched with water directly to room temperature. The DQP A and B sheets of DQP steel with high Al content were produced by direct tempering and partitioning at 340 ° C (Table 3). While plate A was divided 10 minutes at 340 ° C in a furnace followed by air cooling, plate B was transferred to a furnace maintained at 340 ° C, followed by shutting down the furnace to allow it to cool very slowly for 27 to 30 hours, thus simulating winding in real industrial practice. The plates C and D were cooled to 320 and 270 ° C, respectively, followed by partitioning during slow cooling in the furnace.
[00131] For each plate, at least two specimens of traction were extracted. The mechanical properties of plates A and B produced by direct tempering & partitioning (DQ&P) at 340 ° C show the influence of prolonged partitioning during slow cooling (plate B) compared to short time partitioning (10 min.) And longer cooling fast (air) of plate A. Plate B has slightly lower resistance, but a much better impact transition temperature 27J CharpyV (T27J). This is because it is preferable that the average cooling rate during partitioning step 7, 9 is less than the average cooling rate in free air cooling at the temperature in question.
[00132] Decreasing the tempering temperature to 320 ° C followed by slow cooling in a furnace (sheet C) results in improved uniform elongation (3.7%), even though the reduction in area (Z) and impact properties have been marginally impaired compared to those on plate B. An additional reduction in
Petition 870190008037, of 01/24/2019, p. 61/66
38/41 tempering temperature at 270 ° C followed by slow cooling (plate D) showed higher limits of elasticity and tensile strength compared to those of reference steel (plate F), but there was only one notable change in uniform elongation without loss of toughness.
[00133] An additional lamination test (plate E) with FRT above 890 ° C required the start of controlled lamination at 970 ° C, which falls within the domain of partial recrystallization between RLT and RST, followed by tempering at 310 ° C (similar to plate C) and slow cooling in a furnace that simulates CS winding. This test showed the influence of partial recrystallization before DQP on the mechanical properties of DQP steel with a high content of Al. The lamination in the temperature regime between RLT and RST with a higher FRT temperature of 890 ° C followed by tempering and partitioning at 310 ° C (plate E) resulted in lower A _g and higher T27J temperature, as a consequence of the values of R _p02 and R _p10 compared to plate C, which was subjected to a very similar DQP treatment, but laminated in smaller FRT. This reinforces the independent claim that, in DQP treatment, the hot rolling step must include a type I 5 hot rolling stage for the hot rolling of the steel plate in the temperature range without recrystallization below the RST, but above of the ferrite formation temperature A3.
[00134] The cold pre-deformation of TMR-DQP steel for some applications may be plausible or still natural and in these cases the elastic limit in use will be raised above the values of R _p02 in Table 3: the elastic limit may then exceed 1,200 or 1,300 MPa depending on the pre-strain applied. This is implied by the high values of R _p10 shown by plates A to E.
[00135] As shown in Table 3, the low finish laminating temperature (FRT), that is, the type I 5 hot laminating step performed below the recrystallization stop temperature
Petition 870190008037, of 01/24/2019, p. 62/66
39/41 (RST) has a notable effect on impact toughness and elongation in the context of DQ&P processing. For each plate approximately nine 10 x 10 mm Charpy V impact test specimens were tested at various temperatures over the malleable to brittle range. The results were used to determine the values of T27J and T50% (50% shear rupture transition temperature) in Table 3. The individual values of absorbed energy are shown in Figure 8. It can be seen from Figure 8 that controlled lamination below FRT 820 ° C followed by accelerated cooling to quenching temperature and partitioning during slow cooling in a furnace (plates B, C and D) leads to improved impact resistance compared to simple direct quenching at room temperature. steel with a lower carbon content with a similar elastic limit (plate F).
[00136] Additionally, surprisingly, despite the fact that the carbon content of specimens A to E (0.20%) is greater than the carbon content of specimen F (0.14%), the temperatures corresponding to impact energy 27 J Charpy V (T27J) and 50% shear failure (T50%) for plates A to E are distinctly smaller, that is, better than plate F.
[00137] According to Table 3, the temperature corresponding to the impact energy 27 J Charpy V (T27J) of DQP steel can be less than -50 ° C through the use of thermomechanical lamination, that is, with the use of a stage type I 5 hot rolling mill at temperatures below RST.
[00138] The TMR-DQP plates in Table 3 (B, C and D) satisfy the target related to the transition temperature of toughness to impact Charpy V T27J <-50 ° C, preferably <-80 ° C and also limit of elasticity R _p02 at least 960 MPa together with good total uniform elongation.
[00139] While the total elongation (A) and the reduction of
Petition 870190008037, of 01/24/2019, p. 63/66
40/41 rupture area (Z) varies in a narrow range, the total uniform elongation (A _gt ) and the uniform plastic elongation (Ag) are higher at the lower tempering temperature of 320 and 270 ° C than the same properties obtained in the tempering temperature 340 ° C, as can be seen in Table 3.
[00140] According to Table 3, the total elongation of A> 8% has been achieved, which is also a good value at this level of resistance.
[00141] According to Table 3, the total uniform elongation of A _gt > 2.7% was achieved, still A _gt > 3.5%, which is also a good value in this strength class.
[00142] It is preferable that especially in the second main modality (called modality with high content of Al), the quenching temperature (QT) is between the temperatures Ms and Mf and additionally less than 350 ° C, but greater than 200 ° C in order to achieve the enhanced properties related to stretching.
[00143] The mechanical properties obtained in the invention are better than those obtained in conventionally cooled and tempered steels in the same strength class. In addition, it should be noted that the general combination of mechanical properties is good, which includes strength, ductility and impact toughness properties. All of these are obtained simultaneously, and without additional heating of temperatures below Mf after quenching.
Experiment test conditions [00144] For the deformation test, according to the standard EN 1,0002, round specimens with threaded ends (10 mm x M10 threads) and dimensions of 6 mm in diameter and total parallel length of 40 mm were machined in the direction transversal to the lamination direction.
[00145] For toughness test for impact, according to
Petition 870190008037, of 01/24/2019, p. 64/66
41/41 with the EN 10045-1 standard, Charpy V impact specimens (10 x 10 x 55 mm; 2 mm deep groove along the normal transverse direction with root radius of 0.25 + - 0.025mm) were machined in the longitudinal direction, that is, parallel to the rolling direction.
[00146] In the above, the invention was illustrated by specific examples. It should be noted, however, that the details of the invention can be implemented in many other ways within the scope of the appended claims.

权利要求:
Claims (31)
[1]
1. Method for the manufacture of structural steel with high resistance CHARACTERIZED by the fact that it comprises the following:
a supply step for supplying a steel plate, a heating step (1) for heating said steel plate to a temperature in the range of 950 to 1,300 ° C, a temperature equalizing step (2) for equalizing the steel plate temperature, a hot rolling stage that includes a type I hot rolling stage (5) for hot rolling of said steel plate in the temperature range without recrystallization below the recrystallization stop temperature (RST ), but above the ferrite formation temperature A3, and for providing a finishing rolling temperature (FRT), a quenching step (6) for quenching hot-rolled steel at a cooling rate of at least 20 ° With a quench temperature (QT), whose quench temperature (QT) is between the temperatures Ms and Mf, a partitioning treatment step (7, 9) to partition the hot rolled steel in order to in transfer carbon from martensite to austenite, whereby said partitioning treatment step (7) is carried out substantially at the quenching temperature (QT) or said partitioning treatment step (9) is carried out substantially above the stopping temperature hardening (QT), or said partitioning treatment step (7, 9) is carried out at a temperature in the range of 250 to 500 ° C, and through which said partitioning treatment step (7, 9) is carried out within a period of 10 to 100,000 seconds, preferably within a period of 600 to 10,000 seconds calculated from the quench temperature (QT), and a cooling step (8) for cooling the rolled steel hot to room temperature by forced or natural cooling.
Petition 870190052080, dated 06/03/2019, p. 13/21
[2]
2/9
2. Method, according to claim 1, CHARACTERIZED by the fact that:
the heating step (1) for heating said steel plate to a temperature in the range 950 to 1,300 ° C includes heating said steel plate to a temperature in the range 1,000 to 1,300 ° C, the hot rolling step includes a type II hot rolling stage (3) for hot rolling of said steel plate in the recrystallization temperature range above the recrystallization limit temperature (RLT), and a type II hot rolling stage (3 ) is carried out before the type I hot rolling stage (5).
[3]
3. Method, according to claim 2, CHARACTERIZED by the fact that:
the hot rolling stage includes a waiting period (4) which includes a type III hot rolling stage for hot rolling of said steel plate in the temperature range below the recrystallization limit temperature (RLT) and above recrystallization stop temperature (RST) and the waiting period (4) are carried out after the type II hot rolling stage (3) and before the type I hot rolling stage (5).
[4]
4. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the steel plate is continuously rolled during the type I hot rolling stage, the type II hot rolling stage, and the type III hot rolling stage and when moving from type II hot rolling stage to type III hot rolling stage and correspondingly when moving from type III hot rolling stage to rolling stage type I hot
[5]
5. Method according to any of claims 1 to 4, CHARACTERIZED by the fact that said quenching temperature (QT) is between the temperatures Ms and Mf in such a way that the amount of austenite at said stopping temperature quenching (QT) immediately after
Petition 870190052080, dated 06/03/2019, p. 14/21
3/9 tempering is, in terms of volume percentages, a minimum of 5%, but not more than 30%.
[6]
6. Method according to any one of claims 1 to 5, CHARACTERIZED by the fact that said partitioning step (7, 9) is carried out so that the average cooling rate during the partitioning step (7, 9) is less than the average cooling rate in free air cooling at the temperature in question.
[7]
7. Method according to any one of claims 1 to 6, CHARACTERIZED by the fact that said partitioning step (7, 9) is carried out so that the maximum average cooling rate during partitioning is 0.2 ° C /s.
[8]
8. Method according to any one of claims 1 to 7, CHARACTERIZED by the fact that said partitioning step (7, 9) is carried out by maintaining an essentially constant temperature.
[9]
9. Method according to any one of claims 1 to 8, CHARACTERIZED by the fact that the method comprises a winding step that is performed after the tempering step (6) and before the partitioning step (7, 9).
[10]
10. Method according to any one of claims 1 to 9, CHARACTERIZED by the fact that said type I hot rolling (5) includes at least 0.4 total equivalent deformation accumulated below the recrystallization stop temperature ( RST).
[11]
11. Method according to any one of claims 1 to 10, CHARACTERIZED by the fact that the quenching temperature (QT) is between the temperatures Ms and Mf and additionally below 400 ° C, but above 200 ° C in order to achieve enhanced stretching-related properties.
[12]
12. Method according to claim 11, CHARACTERIZED by the fact that the quenching temperature (QT) is between the temperatures Ms and Mf and additionally below 300 ° C, but above 200 ° C at
Petition 870190052080, dated 06/03/2019, p. 15/21
4/9 in order to achieve enhanced stretching-related properties.
[13]
13. Method according to any one of claims 1 to 12, CHARACTERIZED by the fact that the method comprises a pre-deformation step, which is performed subsequent to the partitioning step (7, 9).
[14]
14. Method according to any one of claims 1 to 13, CHARACTERIZED by the fact that the supply step includes the supply of a steel plate that includes Fe and unavoidable impurities, and additionally, in terms of mass percentages, by minus the following:
C: 0.17 to 0.23%,
Si: 1.4 to 2.0% or Si + Al: 1.2 to 2.0%, where Si is at least 0.4% and Al is at least 0.1%, preferably at least 0, 8%, Mn: 1.4 to 2.3%, and
Cr: 0.4 to 2.0%.
[15]
15. Method, according to claim 14, CHARACTERIZED by the fact that said supply stage includes the supply of a steel plate that includes Fe and unavoidable impurities, and additionally, in terms of percentage of mass, at least the following :
C: 0.17 to 0.23%,
Si: 1.4 to 2.0%,
Mn: 1.4 to 2.3%, and
Cr: 0.4 to 2.0%.
[16]
16. Method, according to claim 14, CHARACTERIZED by the fact that the supply step includes the supply of a steel plate that includes Fe and unavoidable impurities, and additionally, in terms of percentage of mass, at least the following:
C: 0.17 to 0.23%,
Si + Al: 1.2 to 2.0%, where Si is at least 0.4% and Al is at least 0.1%, preferably at least 0.8%,
Mn: 1.4 to 2.3%,
Cr: 0.4 to 2.0%, and
Mo: 0 to 0.7%, preferably 0.1 to 0.7%.
Petition 870190052080, dated 06/03/2019, p. 16/21
5/9
[17]
17. Method according to claim 14 or 16 CHARACTERIZED by the fact that the supply step includes the supply of a steel plate that includes Fe and unavoidable impurities, and additionally, in terms of percentage of mass, at least the following :
C: 0.17 to 0.23%,
Si + Al: 1.2 to 2.0%, where Si is 0.4 to 1.2% and where Al is 0.8 to
1.6%,
Mn: 1.4 to 2.3%,
Cr: 0.4 to 2.0%, and
Mo: 0 to 0.7%, preferably 0.1 to 0.7%.
[18]
18. Method according to claim 14, 16 or 17, CHARACTERIZED by the fact that said supply stage includes the supply of a steel plate that includes Fe and unavoidable impurities, and additionally, in terms of mass percentages, at least the following:
C: 0.17 to 0.23%,
Si + Al: 1.2 to 2.0%, where Si is 0.4 to 0.7% and where Al is 0.8 to
1.3%,
Mn: 1.8 to 2.3%,
Cr: 0.4 to 2.0%, and
Mo: 0 to 0.7%, preferably 0.1 to 0.7%.
[19]
19. Method according to any one of claims 1 to 18, CHARACTERIZED by the fact that the supply step includes the supply of steel plate which comprises, in terms of percentages by mass, the following:
C: 0.17 to 0.23%,
Si: 1.4 to 20% or Si + Al: 1.2 to 2.0%, where Si is at least 0.4% and Al is skin less 0.1%, preferably 0.8%,
Mn: 1.4 to 2.3%,
Cr: 0.4 to 2.0%, and optionally comprising
Petition 870190052080, dated 06/03/2019, p. 17/21
6/9
Mo: less than 0.70%,
Ni: less than 4.00%,
Cu: less than 1.00%,
V: less than 0.06%,
Nb: 0.005 to 0.5%,
B: 0.0005 to 0.005%,
Ti: 0.01 to 0.05%,
P: less than 0.012%,
S: less than 0.006%, and
N: less than 0.006%, and a remainder of Fe.
[20]
20. Method according to any one of claims 14 to 19, CHARACTERIZED by the fact that:
said hot rolling step is carried out so that the final thickness of the hot rolled steel sheet is 3 to 20 mm, preferably 3 to 11 mm, and the hardening capacity index DI as calculated using the formula (1) is greater than 70 mm.
[21]
21. Method, according to any one of claims 18 to 19, CHARACTERIZED by the fact that:
said hot rolling step is carried out so that the final thickness of the hot rolled steel sheet is 3 to 20 mm, preferably 11 to 20 mm, and the hardening capacity index DI as calculated using the formula (1) is at least 125 mm.
[22]
22. High strength structural steel product with an elasticity limit R _p02 960 MPa, preferably R _p02 1,000 MPa, also presenting a microstructure that comprises, in terms of volume percentages, at least 80% martensite and 5 to 20 % of austenite retained, CHARACTERIZED by the fact that said martensite consists of
Petition 870190052080, dated 06/03/2019, p. 18/21
7/9 in thin, shortened and randomized martensitic slats in different directions and the structural steel product with high strength includes, in terms of percentages of mass, Fe and unavoidable impurities, and additionally includes at least the following:
C: 0.17 to 0.23%,
Si: 1.4 to 2.0% or Si + Al: 1.2 to 2.0%, where Si is at least 0.4% and where Al is at least 0.1%, preferably at least 0.8%,
Mn: 1.4 to 2.3%, and
Cr: 0.4 to 2.0%, and optionally comprising:
Mo: less than 0.70%,
Ni: less than 4.00%,
Cu: less than 1.00%,
V: less than 0.06%,
Nb: 0.005 to 0.05%,
B: 0.0005 to 0.005%,
Ti: 0.01 to 0.05%,
P: less than 0.012%,
S: less than 0.006%,
N: less than 0.006%, and the rest of Fe.
[23]
23. High strength structural steel product according to claim 22, CHARACTERIZED by the fact that the steel product is substantially free of iron carbides such as cementite.
[24]
24. High strength structural steel product according to claim 23, CHARACTERIZED by the fact that the high strength structural steel product is substantially free of carbides formed after transformation from fcc (central face cuboid) into bcc (cuboid) centralized body).
[25]
25. High strength structural steel product, according to
Petition 870190052080, dated 06/03/2019, p. 19/21
8/9 any one of claims 22 to 24, CHARACTERIZED by the fact that the high strength structural steel product has a transition temperature Charpy V 27J below -50 ° C, preferably below -80 ° C.
[26]
26. High strength structural steel product, according to claim 22, FEATURED by the fact that:
the structural steel product with high strength has a thickness of 3 to 20 mm, preferably 3 to 11 mm, and the index of hardening capacity DI as calculated using the formula (1) is greater than 70 mm.
[27]
27. High strength structural steel product, according to claim 22, CHARACTERIZED by the fact that:
the structural steel product with high strength has a thickness of 3 to 20 mm, preferably 11 to 20 mm, and the index of hardening capacity DI as calculated using the formula (1) is at least 125 mm.
[28]
28. High strength structural steel product according to any one of claims 22 to 27, CHARACTERIZED by the fact that the total break elongation (A) of high strength structural steel product is A> 8% and / or the total uniform elongation (A _gt ) of high strength structural steel product is A _gt > 2.7%, preferably A _gt > 3.5%.
[29]
29. High strength structural steel product according to claim 28, CHARACTERIZED by the fact that the total break elongation (A) of high strength structural steel product is A> 10% and / or total uniform elongation ( The _gt ) of structural steel product with high strength is A _gt > 3.5%, preferably A _gt > 4.0%.
[30]
30. High strength structural steel product according to any one of claims 22 to 29, CHARACTERIZED by the fact that said elasticity limit of high strength structural steel product is R _p02 > 1,200 MPa.
[31]
31. Use of a structural steel product with high strength
Petition 870190052080, dated 06/03/2019, p. 20/21
9/9 manufactured by the method as defined in any of claims 1 to 21 or of a steel product as defined in any of claims 22 to 30, CHARACTERIZED as being a wear resistant steel.

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US20140299237A1|2014-10-09|

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IN2014MN00193A|2015-08-21|

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BR112013033860A2|2018-04-24|

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法律状态:
2018-10-30| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-03-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-08-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-10-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/07/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/07/2012, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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FI20115702|2011-07-01|

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FI20115702A|FI20115702A|2011-07-01|2011-07-01|PROCEDURE FOR MANUFACTURING HIGH-STRENGTH STRUCTURAL STEEL AND HIGH-STRENGTH STRUCTURAL STEEL PRODUCT|

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PCT/FI2012/050698|WO2013004910A1|2011-07-01|2012-07-02|Method for manufacturing a high-strength structural steel and a high-strength structural steel product|

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