US20160186298A1 - Micro-alloyed high-strength multi-phase steel containing silicon and having a minimum tensile strength of 750 mpa and improved properties and method for producing a strip from said steel - Google Patents

Micro-alloyed high-strength multi-phase steel containing silicon and having a minimum tensile strength of 750 mpa and improved properties and method for producing a strip from said steel Download PDF

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US20160186298A1
US20160186298A1 US14/908,471 US201414908471A US2016186298A1 US 20160186298 A1 US20160186298 A1 US 20160186298A1 US 201414908471 A US201414908471 A US 201414908471A US 2016186298 A1 US2016186298 A1 US 2016186298A1
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steel
strip
cooling
steel strip
temperature
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Inventor
Thomas Schulz
Marion Calcagnotto
Sascha Kluge
Sebastian Westhäuser
Tobias Klinkberg
Thorsten Michaelis
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Salzgitter Flachstahl GmbH
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Salzgitter Flachstahl GmbH
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Assigned to SALZGITTER FLACHSTAHL GMBH reassignment SALZGITTER FLACHSTAHL GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CALCAGNOTTO, Marion, KLINKBERG, Tobias, KLUGE, Sascha, MICHAELIS, Thorsten, SCHULZ, THOMAS, WESTHÄUSER, Sebastian
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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Definitions

  • the invention relates to a high-strength multi-phase steel according to the preamble of claim 1 .
  • the invention also relates to a method for producing a hot and/or cold rolled strip made of such a steel according to patent claim 13 .
  • the invention relates in particular to steels with a tensile strength in the range of at least 750 MPa up to maximally 920 MPa with low yield to tensile ratios of maximally 73% for producing components, which have an excellent formability and improved welding properties, such as the failure of the welding seam.
  • High-strength and ultra-high-strength steels enable lighter vehicle components, which leads to reduced fuel consumption and reduced pollution due to the reduced CO 2 proportion.
  • Newly developed steels thus must met the demands placed on weight reduction, the increasing material demands on ultimate yield strength, strain hardening behavior and elongation at fracture while still being well formable, as well as the demands placed on the component of high tenacity, border crack resistance, energy absorption and strength ? via the work hardening effect and the bake hardening effect, but also improved suitability for joining in the form of improved weldabiltiy,
  • Improved edge crack resistance means increased hole expansion capacity during forming and is also known as low edge crack (LEC) or high hole expansion (HHE)
  • the steel according to the invention also has the goal to selectively reduce the thickness of particular components made of micro-alloyed ferritic steels already used in automobile manufacturing in order to save weight.
  • the specific material properties of the dual-phase steels such as for example a low yield-to-tensile ratio at very high tensile strength, strong strain hardening and good cold formability, are well known.
  • multi-phase steels which include for example complex-phase steels, ferritic-bainitic steels, TRIP steels as wells as the above-described dual-phase steels, which are characterized by different microstructure compositions.
  • Complex-phase steels are according to EN 10346 steels that contain small proportions of martensite, residual austenite and/or perlite in a ferritic/bainitic basic structure, wherein a delayed re-crystallization or precipitations of micro-alloy elements cause a strong grain refinement.
  • Ferritic-bainitic steels are according to EN 10346 steels, which contain bainite or strain-hardened bainite in a matrix of ferrite and/or strain hardened ferrite.
  • the strength of the matrix is caused by a high dislocation density, by grain refinement and by the precipitation of micro-alloy elements.
  • Dual-phase steels are according to EN 10346 steels with a ferritic basic microstructure in which a martenisitc second phase is incorporated island like, possibly also with proportions of bainite as second phase. Dual-phase steels possess high tensile strength while exhibiting a low yield-to-tensile ratio and strong strain hardening.
  • TRIP-steels are according to EN 10346 steels with a predominantly ferritic basic microstructure in which residual austenite is incorporated, which can transform into marteniste during forming (TRIP effect). Due to its strong strain hardening the steel has very good uniform elongation characteristics and high tensile strength.
  • the high-strength steels with single-phase microstructure also include for example bainitic and martensitic steels.
  • Bainitic steels are according to EN 10346 steels that are characterized by a very high yield strength and tensile strength at a sufficiently high expansion for cold forming processes.
  • the chemical composition results in a good weldability.
  • the microstructure typically consists of bainite. In some cases small proportions of other phases such as marteniste and ferrite can be contained.
  • Martensitic steels are according to EN 10346 steels that as a result of thermo mechanical rolling contain small proportions of ferrite and/or bainite in a basic structure of martensite. This steel type is characterized by a very high yield strength and tensile strength at sufficiently high elongation for cold forming processes. Within the group of multi-phase steels the martenisititc steels have the highest tensile strength values.
  • the suitability for deep drawing is limited.
  • the martensitic steels are predominantly suited for forming processes that involve bending, such as roilforming.
  • High-strength steels are used in structural components, chassis components and crash-relevant components as steel plates, Tailored Blanks (welded steel plates) as well as flexibly cold tolled strips, so called TRB®s.
  • the Tailor Rolled Blank lightweight construction technology (TRB®) enables a significant weight reduction as a result of the load-adjusted selection of sheet thickness over the length of the component or steel type.
  • a special heat treatment is performed for setting a defined microstructure in which the steel is provided with its low yield strength by relatively soft components such as ferrite or bainitic ferrite and obtains its strength by its hard components such as martensite or carbon-rich bainite.
  • the pickled hot strip in typical thicknesses between 1.50 mm to 4.00 mm, or cold strip in typical thicknesses of 0.50 mm to 3.00 mm, is heated in the continuous annealing furnace to such a temperature that the required microstructure forms during the cooling.
  • Widened process windows are necessary in order to enable the demanded strip properties at same process parameters also in the case of greater differences in cross section of the strips to be annealed.
  • the problem of a too narrow process window is especially pronounced in the annealing treatment when stress-optimized components made of hot or cold strip are to be produced, which have sheet thicknesses that vary across the strip length and strip width (for example as a result of flexible rolling).
  • a method for producing a steel strip with different thickness across the strip length is for example described in DE 100 37 867 A1.
  • the annealing is usually carried out in a continuous annealing furnace arranged upstream of the hot dip galvanizing bath.
  • the demanded microstructure is not established until the annealing in the continuous furnace, in order to realize the demanded mechanical properties.
  • Deciding process parameters are thus the adjustment of the annealing temperatures and the speed as well as the cooling rate (cooling gradient) in the continuous annealing because the phase transformation is temperature and time dependent.
  • the narrow process window makes it already difficult during the continuous annealing of strips with different thicknesses to establish uniform mechanical properties over the entire length and width of the strip.
  • the too narrow process window either causes the regions with lower sheet thickness to have excessive strengths resulting from excessive martensite proportions due to the transformation processes during the cooling, or the regions with greater sheet thickness achieve insufficient strengths as a result of insufficient martensite proportions.
  • Homogenous mechanical-technological properties across the strip length or width can practically not be achieved with the known alloy concepts in the continuous annealing.
  • the goal to achieve the resulting mechanical-technological properties in a narrow region across the strip width and strip length through controlled adjustment of the volume proportions of the microstructure phases has highest priority and is therefore only possible through a widened process window.
  • the known alloy concepts for multiphase steels are characterized by a too narrow process window and are therefore not suited for solving the present problem, in particular in the case of flexibly rolled strips. With the alloy concepts known to date only steels of one strength class with defined cross sectional regions (sheet thickness and strip width) can be produced, hence requiring different alloy concepts for different strength classes or cross sectional ranges.
  • the state of the art is to increase the strength by increasing the amount of carbon and/or silicone and/or manganese (solid solution hardening) and to increase strength via the microstructure adjustments at adjusted temperature profile.
  • the hole expansion test according to ISO 16630 is used as one of multiple possible testing methods.
  • PCM C+(Mn+Cu+Cr)/20+Ni/60+Mo/15/+/V10+5B
  • the characteristic standard elements such as carbon and manganese as well as Chromium or Molybdenum and Vanadium are taken into account.
  • Silicone plays a minor role for calculating the carbon equivalent. This is of deciding importance with regard to the invention. The lowering of the carbon equivalent through lower contents of carbon and manganese is to be compensated by increasing the silicone content. Thus the edge crack resistance and welding suitability are improved at same strengths.
  • a low yield-tensile ratio (Re/Rm) of below 65 is typical for a dual-phase steel and serves in particular for the formability in stretching and deep drawing processes. This provides the constructor with information regarding the distance between ensuing plastic deformation and failing of the material at quasi-static load. Correspondingly lower yield strength ratios represent a greater safety margin for component failure.
  • a higher yield to tensile ratio (Re/Rm) of over 65, as it is typical for complex-phase steels, is also characterized by a resistance against edge cracks. This can be attributed to the smaller differences in the strengths of the individual microstructure components, which has a positive effect on a homogenous deformation in the region of the cutting edge.
  • the norms provide for an overlap region within which an attribution to complex-steels as well as dual-phase steels is possible
  • the analytical landscape for achieving multi-phase steels with minimal strengths of 750 MPa is very diverse and reveals very broad alloy ranges regarding the strength-promoting elements carbon, silicone, manganese, phosphorous, aluminum and also chromium and/or molybdenum as well as regarding the addition of micro-alloys such as titanium niobium, vanadium and/or boron and regarding the material-characterizing properties.
  • the spectrum of dimensions is broad and lies in the thickness range of 0.50 to 4.00 mm. Predominantly strips of up to about 1850 mm are used but also slit strip dimensions, which are generated by longitudinally separating the strips. Sheets or plates are generated by transverse separation of the strips.
  • the invention is therefore based on the object to set forth a new alloy concept for a high-strength, multi-phase steel with a minimal tensile strength of 750 to 920 MPa longitudinally and transversely to the rolling direction, preferably with dual-phase microstructure and a yield strength ratio of at most 73% with which the process window for the continuous annealing of hot and cold rolled strips can be widened so that beside strips with different cross sections also steel strips with thicknesses that vary over the strip length or strip width and the correspondingly varying cold rolling reduction degrees can be generated with mechanical technological properties that are as homogenous as possible.
  • a hot dip coating hot dip galvanizing capacity
  • a method for producing a strip made of this steel is provided.
  • the steel according to the invention is very well suited for hot dip galvanizing and has a significantly widened process window compared to the known steels. This results in an increased process reliability during continuous annealing of cold and hot strip with dual-phase or multi-phase microstructure. Thus more homogenous mechanical-technological properties can be ensured in the strip for continuously annealed hot or cold strips also in the case of different cross sections and otherwise same process parameters.
  • stress-optimized components can advantageously be produced from this material by forming.
  • the produced material can be produced as cold strip and also as hot strip via a hot dip galvanizing line or a pure continuous annealing line in the skin passed or non skin passed state and also in the heat treated state (intermediate annealing).
  • steel strips can be produced by an inter-critical annealing between A c1 and A c3 or an austenitic annealing above A c3 with final controlled cooling, which leads to a dual-phase or multi-phase microstructure.
  • Annealing temperatures of 700 to 950° C. have proven advantageous. Depending on the overall process there are different approaches for realizing the heat treatment.
  • the strip is cooled starting from the annealing temperature to an intermediate temperature of about 160 to 250° C. with a cooling rate of about 15 to 100° C./s.
  • cooling to a prior intermediate temperature of 300 to 500° C. can be conducted beforehand with a cooling rate of 15 to 100° C./s.
  • cooling to room temperature occurs with a cooling rate of about 2 to 30° C. (Variant 1 FIG. 6 a ).
  • the second variant of the temperature profile in the case of hot dip coating includes holding the temperature for about 1 to 20 s at the intermediate temperature of 200 to 350° C. and subsequent reheating to the temperature of 400 to 470° C. required for the hot dip coating. After the hot dip coating the strip is cooled again to 200 to 250° C. The cooling to room temperature is conducted again with a cooling rate of 2 to 30° C./s. (Variant 3 , FIG. 6 c ).
  • Beside carbon also manganese, chromium and silicone, are responsible for the transformation of austenite to martensite in classical dual-phase steels. Only the combination according to the invention of the added elements carbon, silicone, manganese and chromium ensures on one hand the demanded mechanical properties of minimal tensile strengths of 750 MPa and yield strength ratios of below 73% at simultaneous significantly widened process window in the continuous annealing.
  • a characteristic of the material is also that addition of manganese at increasing mass percentages shifts the ferrite region to longer times and lower temperatures during cooling.
  • the proportions of ferrite are hereby also reduced by increased proportions of bainite depending on the process parameters.
  • the multiphase steels typically have a chemical composition in which alloy components are combined with and without micro-alloying elements. Accompanying elements are unavoidable and are taken into account regarding their effect when necessary.
  • Hydrogen (H) is the only element capable of diffusing through the iron lattice without generating lattice tensions. As a result hydrogen is relatively mobile in the iron lattice and can be taken up relatively easily during manufacturing. Hydrogen can thereby only be taken up into the iron lattice in atomic (ionic) form.
  • Hydrogen has a strong embrittling effect and diffuses preferably to energetically favorable sites (defects, grain boundaries etc.).
  • the defects act as hydrogen traps and can significantly increase the retention time of the hydrogen in the material.
  • a more uniform microstructure which is achieved with the steel according to the invention inter alia by virtue of its widened process window, lowers the sensitivity against hydrogen embrittlement.
  • Oxygen can be converted into harmless states by adding certain alloy elements. For example it is common to bind oxygen via manganese, silicone and/or aluminum. However, the oxides produced thereby can cause negative properties in the material in the form of defects.
  • the oxygen content in the steel should be as low as possible.
  • Phosphorous (P) is a trace element contained in the iron ore and is solubilized in the iron lattice as substitution atom. As a result of the solid solution strengthening phosphorous increases strength and improves hardenability.
  • phosphorous is used in some steels in low amounts ( ⁇ 0.1%) as micro-alloying element for example in high strength IF-steels (interstitial free), bake hardening steels or also in some alloying concepts for dual-phase steels.
  • the steel according to the invention differs from known analysis concepts that use phosphorous as a solid solution former (for example EP 2 412 842 A1 or EP 2 128 295 A1) inter alia in that phosphorous is not added.
  • S sulfur
  • MnS manganese sulfide
  • the manganese sulfides are often rolled out band-like during rolling and function as germination sites for the transformation. Especially in the case of diffusion-controlled transformation this leads to a microstructure that is configured band-like and can lead to impaired mechanical properties in the case of strongly pronounced banding (for example pronounced martensite bands instead of distributed martensite islands, anisotropic material behavior, reduced elongation at brake).
  • the sulfur content is limited to ⁇ 0.0030%, advantageously to ⁇ 0.0020% or optimally to ⁇ 0.0010% or to unavoidable amounts during steel production.
  • Alloying elements are usually added to the steel in order to influence properties in a targeted manner.
  • An alloying element can influence different properties in different steels. The effect generally depends strongly on the amount and the solubility state in the material.
  • the interrelations can thus be very diverse and complex. In the following the effect of the alloying elements is described in more detail.
  • carbon Due to its relatively small atomic radius carbon is dissolved interstitially in the iron lattice.
  • the solubility in the ⁇ -iron is maximally 0.02% and in the ⁇ -iron maximally 2.06%.
  • solubilized form carbon significantly increases the hardenability of steel and is thus indispensible for the formation of sufficient amounts of martensite.
  • Excessive carbon contents increase the hardness difference between ferrite and martensite and limit weldability.
  • the steel according to the invention contains less than 0.105% carbon.
  • a representative, which is present in almost every steel is zementite (Fe 3 C).
  • significantly harder special carbides can form with other metals such as chromium, titanium, niobium and vanadium.
  • the minimal C-content is set to 0.075% and the maximal C-content to 0.105%.
  • Silicone (Si) binds oxygen during casting and is thus used for deoxidizing the steel.
  • he segregation coefficient is significantly lower than that of for example manganese (0.16 compared to 0.87). Segregations generally lead to a banded arrangement of the microstructure components, which impair the forming properties, for example the hole expansion.
  • silicone results in a strong solid solution hardening.
  • 0.1% silicone results in an approximate increase of the tensile strength by about 10 MPa, wherein up to 2.2% silicone only impairs expansion insignificantly.
  • the increase from 0.2% to 0.6% silicone resulted in a strength increase of about 20 MPa in yield strength and about 70 MPa in tensile strength.
  • the elongation at break hereby decreases by only about 2%.
  • the latter results inter alia from the fact that silicone lowers the solubility of carbon in ferrite, which causes the ferrite to be softer, which in turn improves formability.
  • silicone prevents the formation of carbides, which lower ductility as brittle phases.
  • the low strength increasing effect of silicone within the range of the steel according to the invention forms the basis of a wide process window.
  • a further important effect is that silicone shifts the formation of ferrite toward shorter times and thus enables generation of sufficient amounts of ferrite prior to quenching. During hot rolling this creates a basis for an improved cold rollability. As a result of the accelerated ferrite formation the austenite is enriched with carbon during hot dip galvanizing and thus stabilized. Because silicone inhibits carbide formation, the austenite is additionally stabilized. Thus the formation of bainite can be suppressed in the accelerated cooling in favor of martensite.
  • silicone has an indirect positive effect on the formation of precipitations by micro-alloying, which in turn have a positive effect on the strength of the material. Because the increase of the transformation temperatures by silicone tends to favor grain refinement, micro-alloying with niobium, titanium and boron is particularly advantageous.
  • the atmospheric conditions in a continuous hot dip galvanizing facility during the annealing treatment cause a reduction of iron oxide, which may form on the surface for example during cold rolling or as a result of storage at room temperature.
  • oxygen-affine alloy components such as silicone, manganese, chromium, boron the overall atmosphere is oxidizing, which may result in segregation and selective oxidation of these elements.
  • the selective oxidation can occur externally, i.e., on the substrate surface as well as internally in the metallic matrix.
  • the strip surface first has to be freed of scale remnants, rolling oil or other dirt particles by a chemical or thermal-hydro-mechanical pre-cleaning.
  • measures also have to be taken to promote the inner oxidation of the alloy elements below the surface of the material. Depending on the configuration of the facility, different measures are used for this purpose.
  • the inner oxidation of the alloy elements can be influenced in a targeted manner by adjusting the oxygen partial pressure of the furnace atmosphere (N 2 —H 2 protective gas atmosphere).
  • the adjusted oxygen partial pressure hereby has to satisfy the following equation, wherein the furnace temperature is between 700 and 950° C.
  • Si, Mn, Cr, B designate the corresponding alloy proportions in the steel in mass % and pO 2 the oxygen partial pressure in mbar.
  • the selective oxidation can also be influenced via the gas atmosphere of the furnace regions.
  • the oxygen partial pressure and with this the oxidation potential for iron and the alloy components can be adjusted.
  • the oxidation potential is to be adjusted so that the oxidation of the alloy elements occurs internally, below the steel surface and a thin iron oxide layer may form on the steel surface after passage through the NOF region. This is achieved for example via reducing the CO-value below 4%.
  • the iron oxide layer which may have formed and also the alloy elements are further reduced under N 2 —H 2 protective gas atmosphere.
  • the adjusted oxygen partial pressure in this furnace region hereby has to satisfy the following equation, wherein the furnace temperature is between 700 and 950° C.
  • Si, Mn, Cr, B designate the corresponding alloy proportions in the steel in mass % and pO 2 the oxygen partial pressure in mbar.
  • the dew point of the gas atmosphere N 2 —H 2 protective gas atmosphere
  • the oxygen partial pressure is to be adjusted so that oxidation of the strip is avoided prior to immersion into the melt bath.
  • Dew points in the range of from ⁇ 30 to ⁇ 40° C. have proven advantageous.
  • the minimal Si-content is set to 0.600% and the maximal silicone content to 0.800%.
  • Manganese (Mn) is added to almost every steel for de-sulfurization in order to convert the deleterious sulfur into manganese sulfides.
  • manganese increases the strength of the ferrite and shifts the ⁇ -/ ⁇ -transformation toward lower temperatures.
  • a main reason for adding manganese in dual-phase steel is the significant improvement of the hardness penetration. Due to the diffusion impairment the perlite and bainite transformation is shifted toward longer times and the martensite start temperature is lowered.
  • manganese tends to form oxides on the steel surface during the annealing treatment.
  • manganese oxides for example MnO
  • Mn mixed oxides for example Mn 2 SiO 4
  • manganese is less critical at a low Si/Mn or Al/Mn ratio because globular oxides instead of oxide films form. Nevertheless high manganese contents may negatively influence the appearance of the zinc layer and the zinc adhesion.
  • the Mn-content is set to 1.000 to 1.900%.
  • the Manganese content is preferably ⁇ 1.500%, at strip thicknesses of 1.00 to 2.00 mm at ⁇ 1.750%, and at strip thicknesses of >2.00 mm at ⁇ 1.500%.
  • a further particular aspect of the invention is that the variation of the manganese content can be compensated by simultaneous change of the silicone content.
  • the strength increase (yield strength, YS) by manganese and silicone is generally well described by the following Pickering equation:
  • the coefficient of manganese and silicone are approximately the same for the yield strength as well as for the tensile strength, which proofs the possibility to substitute manganese by silicone.
  • Chromium (Cr) in solubilized form can on one hand significantly increase the hardenability of steel already in small amounts.
  • chromium causes precipitation hardening at a corresponding temperature profile in the form of chromium carbides.
  • the increase of the number of germination sites at simultaneously lowered carbon content leads to a lowering of the hardenability.
  • chromium In dual-phase steels addition of chromium mainly improves the hardness penetration. In the solubilized state chromium shifts perlite and bainite transformation toward longer times and at the same time lowers the martensite start temperature.
  • a further important effect is that chromium significantly increases tempering resistance so that almost no strength losses occur in the zinc bath.
  • chromium forms carbides.
  • the austenitizing temperature has to be selected high enough prior to the hardening in order to solubilize the chromium carbides. Otherwise the increased number of nuclei may impair the hardness penetration.
  • Chromium also tends to form oxides on the steel surface during the annealing treatment, which may negatively affect the galvanization quality.
  • the above-mentioned measures for adjusting the furnace regions in the continuous hot dip galvanizing lead to a reduced formation of Cr-oxides or Cr-mixed oxides at the steel surface after the annealing.
  • the Cr content is therefore set to values of 0,100 to 0.700%.
  • the total content of Mn+Si+Cr is also advantageously selected depending on the sheet thickness.
  • Advantageous for sheet thicknesses of ⁇ 1 mm is a total content of ⁇ 2.40 to ⁇ 2.70%, for sheet thicknesses of 1.00 to 2.00 mm a total content of ⁇ 2.60 to ⁇ 2.90% and for sheet thicknesses ⁇ 2 mm a total content of ⁇ 2.80 to ⁇ 3.10%.
  • the molybdenum content is usually limited to unavoidable steel accompanying amounts. When certain process parameters require an additional strength increase, molybdenum can be optionally added to up to 0.200%.
  • Copper the addition of copper can increase tensile strength and hardness penetration. In connection with nickel, chromium and phosphorous, copper can form a protective oxide layer on the surface, which significantly reduces the corrosion rate.
  • copper can form deleterious oxides at the grain boundaries, which can have negative consequences in particular for hot forming processes.
  • the copper content is therefore limited to amounts that are unavoidable during steel production.
  • alloy elements such as nickel (Ni) or tin (Sn) are limited to amounts that are unavoidable during the steel production.
  • Aluminum (Al) is usually added to the steel in order to bind oxygen and nitrogen solubilized in the iron. In this way, oxygen is converted into aluminum oxides and aluminum nitrides. These precipitations can cause grain refinement via increasing the number of nucleation sites and thus increase the tenacity and strength values.
  • Titanium nitrides have a lower formation enthalpy and are formed at higher temperatures.
  • aluminum like silicone, shifts the ferrite formation toward shorter times and thus enables the formation of sufficient amounts of ferrite in the dual-phase steel. In addition it suppresses the carbide formation and thus leads to a delayed transformation of the austenite. For this reason aluminum is also used as alloy element in residual austenite steels (TRIP steels) in order to substitute for a portion of the silicone by aluminum.
  • TRIP steels residual austenite steels
  • the Al-content is therefore limited to 0.010 to maximally 0.060% and is added for deoxidizing the steel.
  • Niobium has different effects in steel. During hot rolling in the finishing train it delays recrystallization by forming ultra-finely distributed precipitations, which increases the density of germination sites and a finer grain is generated after transformation. Also the proportion of solubilized niobium inhibits recrystallization. In the final product the precipitations increase strength. These precipitations can be carbides or carbonitrides. Oftentimes these precipitations are mixed carbides, into which also titanium can be integrated. This effect starts at 0.0050% and is most pronounced above 0.010% niobium. The precipitations also prevent grain growth during the (partial)austenitization in the hot dip galvanizing. Above 0.050% niobium no additional effect is expected, therefore this constitutes the uppermost limit in the invention.
  • Titanium (Ti) due to its high affinity to nitrogen titanium is precipitated during solidification predominantly as TIN. In addition it is present together with niobium as mixed carbide. TIN is very important for the grain size stability. The precipitations have a high temperate stability so that they, in contrast to the mixed carbides, are mostly present as particles at 1200° C., which inhibit the grain growth. Titanium also delays the recrystallization during hot rolling, however, it is hereby less effective than niobium. Titanium acts by way of precipitation hardening. The greater TiN particles are hereby less effective than the more finely distributed mixed carbides. The best effectiveness is achieved in the range from 0.005 to 0.050% titanium, therefore this constitutes the alloy range according to the invention. The proportion of titanium hereby depends on the addition of boron (see below).
  • Vanadium (V) because in the present alloy concept addition of vanadium is not required, the content of vanadium is limited to unavoidable steel accompanying amounts.
  • Boron is an extremely effective alloy agent for increasing hardness, which is already effective in very low amounts (above 5 ppm). The martensite start temperature remains hereby unaffected.
  • boron has to be present in solid solution. Because of its high affinity to nitrogen, the nitrogen first has to be bound, preferably by the stoichiometrically required amount of titanium. Due to its low solubility in iron, the solubilized boron is preferentially present at the austenite grain boundaries. There it partially forms Fe—B carbides, which are coherent and lower the grain boundary energy. Both effects have a delay the ferrite and perlite formation and thus increase the hardenability of the steel.
  • the boron content in this invention is limited to 5 to 40 ppm.
  • Nitrogen (N) can be an alloy element as well as an accompanying element of the steel production. Excessive amounts of nitrogen cause a strength increase associated with a fast loss of tenacity and ageing effects.
  • nitrogen in connection with the micro-alloy elements titanium and niobium a fine grain hardening via titanium nitrides and niobium(carbo)nitrides can be achieved. In addition the coarse grain formation is suppressed during reheating prior to the hot rolling.
  • the N-content is therefore set to a ⁇ 0.0020% to ⁇ 0.0120%.
  • the content of nitrogen is set to ⁇ 0.0020% to ⁇ 0.0100%.
  • the content of nitrogen is set to ⁇ 0.00400% to ⁇ 00120%.
  • the annealing temperatures for the dual-phase microstructure to be achieved are between about 700 and 950° C.; depending on the temperature range, this achieves a partially austenitic (dual-phase region) microstructure or a fully austenitic microstructure (austenitic region).
  • the hot dip coated material can be manufactured as hot strip as well as cold re-rolled hot strip or cold strip in the skin-passed rolled (cold re-rolled) or non-skin-pass rolled state and/or in the stretch leveled or not stretch leveled state and also in the heat treated state (overageing).
  • Steel strips in the present case as hot strips, cold re-rolled hot strip or cold strip, made from the alloy composition according to the invention, are in addition characterized by a high resistance against edge-proximate crack formation during further processing.
  • the plate cutting can be conducted independent of the rolling direction (for example transversely, longitudinally and diagonally or at an angle to the rolling direction to the rolling direction).
  • the hot strip is produced according to the invention with final rolling temperatures in the austenitic range above A C3 and coiling temperatures above the bainite start temperature (variant A).
  • the hot strip is produced according to the invention with final rolling temperatures in the austenitic region above A c3 and coiling temperatures below the bainite start temperature (variant B).
  • FIG. 1 a process chain (schematically) for the production of a strip from the steel according to the invention
  • FIG. 2 a Time-temperature-course (schematically) of the process steps hot rolling and cold rolling (optionally) and continuous annealing, exemplary for the steel according to the invention
  • FIG. 3 an example for analytical differences of the steel according to the invention relative to a carbon-rich (C ⁇ 0.120%) and micro-alloyed comparative grade
  • FIG. 4 examples for mechanical characteristic values (Longitudinal to the rolling direction) of the steel according to the invention
  • FIG. 5 Results of he hole expansion tests according to ISO 16630 (sheet thickness 1.00 mm and 2.00 mm) exemplary for the steel according to the invention relative to a carbon rich (C ⁇ 1.120%) and micro-alloyed comparative grade.
  • FIGS. 6 a, b, c Temperature-time curves (annealing variants schematically)
  • FIG. 1 schematically shows the process chain for the production of the steel according to the invention. Shown are the different process routes relating to the invention. Up to the hot rolling (final rolling temperature) the process route is the same for all steel according to the invention, thereafter different process routes are followed depending on the desired results.
  • the pickled hot strip can be galvanized or can be cold rolled with different reduction degrees and galvanized.
  • soft annealed hot strip or soft annealed cold strip can be cold rolled and galvanized.
  • material can be optionally processed without zinc pot (continuous annealing) with and without subsequent electrolytic galvanization.
  • FIG. 2 shows schematically the time-temperature-course of the process steps hot tolling and continuous annealing of strips having the alloy composition according to the invention. Shown are the time and temperature dependent transformation for the hot rolling process as well as for a heat treatment after the cold rolling.
  • FIG. 3 exemplarily shows the essential alloy elements of the steel according to the invention, compared to the comparative grade.
  • the steel according to the invention is significantly Si-alloyed.
  • the comparative steel (standard grade) differs also regarding the carbon content, which is at ⁇ 0.120%, but also regarding the elements titanium and boron.
  • the standard grade is niobium micro-alloyed like the steel according to the invention.
  • FIG. 4 shows examples of mechanical characteristic values longitudinal relative to the rolling direction of the steel according to the invention.
  • FIG. 5 shows results of the hole expansion tests according to ISO 16630 (absolute values and relative values to the comparative grade). Shown are the results of the hole expansion tests for variant A (coiling temperature above bainite start temperature) and variant B (coiling temperature below the bainite start temperature), respectively for process 2 and process 3.
  • the materials have a sheet thickness of 1.00 mm or 2.000.
  • the results apply for the test according to ISO 16630. It can be seen that the steels according to the invention have better or approximately same expansion values for punched holes as the comparative grades with same processing.
  • the method 2 hereby corresponds to an annealing for example on a hot dip galvanizing with combined direct-fired furnace and radiant tube furnace as described in FIG. 6 b .
  • the method 3 corresponds for example to a process control in a continuous annealing plant as described in FIG. 6 c .
  • a reheating of the steel can be achieved directly prior to the zinc bath by means of induction furnaces.
  • the different temperature profiles according to the invention within the stated range result in characteristic values or different hole expansion results that are different from each other, that are significantly improved for the method 3 according to FIG. 6 c compared to the comparative grades.
  • a principle difference are also the temperature time parameters during the heat treatment and the following cooling.
  • FIG. 6 schematically show three variants of the temperature time courses according to the invention at the annealing treatment and cooling and respectively different austenitization conditions.
  • the method 1 shows the annealing and cooling of produced cold or hot rolled or cold rerolled steel strip in a continuous annealing facility.
  • First the strips is heated to a temperature in the range of about 700 to 950° C.
  • the annealed steel strip is then cooled from the annealing temperature to an intermediate temperate of about 200 to 250° C. with a cooling rate between about 15 and 100° C./s.
  • a second intermediate temperature (about 300 to 500° C.) is not shown in this schematic representation.
  • the steel strip is cooled at room temperature with a cooling rate between about 2 and 30° C./s until reaching room temperature or the cooling is maintained at a cooling rate of about 15 and 100° C./s until reaching room temperature.
  • the method 2 ( FIG. 6 b ) shows the process according to method 1 , however the cooling of the steel strip for the purpose of the hot dip galvanization is briefly interrupted during passage through the hot dip galvanizing container, in order to then continue the cooling with a cooling rate of between about 15 and 100° C./s until reaching an intermediate temperature of about 200 to 250° C.
  • the steel strip is then cooled at air with a cooling rate of between about 2 and 30° C./s until reaching room temperature.
  • the method 3 ( FIG. 6 c ) also shows the process according to method 1 in case of a hot dip coating, however, the cooling of the steel strip is interrupted by a brief brake (about 1 to 20 s) at an intermediate temperature in the range of about 200 to 400° C. and is reheated to the temperature which is required for the hot dip coating (about 400 to 470° C.). Subsequent thereto the steel strip is again heated to an intermediate temperature of about 200 to 250° C. The final cooling of the steel strip at air to room temperature is conducted with a cooling rate of about 2 and 30° C./s.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting facility, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and transported into the furnace at a reel temperature of 500° C. with a thickness of 2.30 mm for a simulated reel cooling. After sand blasting the cold rolling was conducted with a cold rolling degree of 15% from 2.30 to 2.00 mm.
  • the steel according to the invention after the heat treatment has a microstructure which consists of ferrite, martensite, bainite and residual austenite.
  • yield strength (Rp0.2) 461 MPa tensile strength (Rm) 821 MPa elongation at break (A80) 15.4% bake-hardening-index (BH2) 48 MPa hole expansion ratio according to ISO 16630 36% longitudinal to the rolling direction and corresponds for example to a CR440y780T-DP according to VDA 239-100.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 56%.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting plant, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and inserted in the furnace at a reel target temperature of 500° C. with a thickness of 2.30 mm for a simulated reel cooling. After the sand blasting the cold rolling was conducted with a cold rolling degree of 15% from 2.30 to 2.00 mm.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 72%.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting plant, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and inserted in the furnace at a reel target temperature of 710° C. with a thickness of 2.02 mm for a simulated reel cooling. After the sand blasting the cold rolling was conducted with a cold rolling degree of 50% from 2.30 to 2.00 mm.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • the yield tensile ratio Re/Rm in longitudinal direction is 56%.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting plant, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and inserted in the furnace at a reel target temperature of 710° C. with a thickness of 2.02 mm for a simulated reel cooling. After the sand blasting the cold rolling was conducted with a cold rolling degree of 50% from 2.02 to 0.99 mm.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • yield strength (Rp0.2) 520 MPa tensile strength (Rm) 780 MPa elongation at break (A80) 14.2% bake-hardening-index (BH2) 46 MPa hole expansion ratio according to ISO 16630 67% longitudinal to the rolling direction and corresponds for example to a CR570y780T-CP according to VDA 239-100.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 67%.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting plant, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and inserted in the furnace at a reel target temperature of 710° C. with a thickness of 2.02 mm for a simulated reel cooling. After the sand blasting the annealing was conducted.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 69%.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting plant, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and inserted in the furnace at a reel target temperature of 710° C. with a thickness of 2.02 mm for a simulated reel cooling. After sand blasting the annealing was conducted.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 72%.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 68%.
  • a steel according to the invention with 0.091% C; 0.705% Si; 1.801% Mn; 0.010% P; 0.0030% S; 0.0054% N; 0.035 Al; 0.344% Cr; 0.012% Mo; 0.016% Ti; 0.001% V; 0.016% Nb; 0.0031% B was melted in a high vacuum melting and casting plant, hot rolled in a hot rolling stand at a final rolling target temperature of 910° C. and inserted in the furnace at a reel target temperature of 500° C. with a thickness of 2.30 mm for a simulated reel cooling. After the sand blasting the annealing was conducted.
  • the steel according to the invention has a microstructure which consists of ferrite, martensite and residual austenite.
  • the yield to tensile ratio Re/Rm in longitudinal direction is 73%.
  • FIG. 1 process chain (schematic) for the production of a strip made of the steel according to the invention.

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US14/908,471 2013-07-30 2014-05-27 Micro-alloyed high-strength multi-phase steel containing silicon and having a minimum tensile strength of 750 mpa and improved properties and method for producing a strip from said steel Abandoned US20160186298A1 (en)

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CN110777329A (zh) * 2019-11-05 2020-02-11 常州大学 一种提高钢材在锌液中润湿性的方法
CN111705265A (zh) * 2020-06-29 2020-09-25 张家港联峰钢铁研究所有限公司 一种高寒地区汽车防滑链用钢及其转炉冶炼工艺
CN111733367A (zh) * 2020-07-08 2020-10-02 东莞理工学院 一种具有纳米、分层和亚稳骨骼组织高强钢及其制备方法
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WO2022243461A1 (en) * 2021-05-20 2022-11-24 Nlmk Clabecq Method for manufacturing a high strength steel plate and high strength steel plate
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CN109308378A (zh) * 2018-08-22 2019-02-05 清华大学天津高端装备研究院 一种模拟冷轧带钢乳液斑迹形成过程的方法
CN109308378B (zh) * 2018-08-22 2021-09-14 清华大学天津高端装备研究院 一种模拟冷轧带钢乳液斑迹形成过程的方法
CN110777329A (zh) * 2019-11-05 2020-02-11 常州大学 一种提高钢材在锌液中润湿性的方法
CN111705265A (zh) * 2020-06-29 2020-09-25 张家港联峰钢铁研究所有限公司 一种高寒地区汽车防滑链用钢及其转炉冶炼工艺
CN111733367A (zh) * 2020-07-08 2020-10-02 东莞理工学院 一种具有纳米、分层和亚稳骨骼组织高强钢及其制备方法
RU2751072C1 (ru) * 2020-09-02 2021-07-07 Публичное Акционерное Общество "Новолипецкий металлургический комбинат" Способ производства высокопрочной холоднокатаной стали
WO2022243461A1 (en) * 2021-05-20 2022-11-24 Nlmk Clabecq Method for manufacturing a high strength steel plate and high strength steel plate
WO2022242859A1 (en) * 2021-05-20 2022-11-24 Nlmk Clabecq Method for manufacturing a high strength steel plate and high strength steel plate
WO2024120028A1 (zh) * 2022-12-05 2024-06-13 南京钢铁股份有限公司 一种抗应力腐蚀球罐用800MPa级高强度钢板的制造方法

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