THEREOF

The present invention relates to cold rolled and heat treated steel sheet which is suitable for use as a steel sheet for automobiles.

Automotive parts are required to satisfy two inconsistent necessities, viz. ease of forming and strength but in recent years a third requirement of improvement in fuel consumption is also bestowed upon automobiles in view of global environment concerns. Thus, now automotive parts must be made of material having high formability in order that to fit in the criteria of ease of fit in the intricate automobile assembly and at same time have to improve strength for vehicle crashworthiness and durability while reducing weight of vehicle to improve fuel efficiency.

Therefore, intense Research and development endeavors are put in to reduce the amount of material utilized in car by increasing the strength of material. Conversely, an increase in strength of steel sheets decreases formability, and thus development of materials having both high strength and high formability is necessitated. Earlier research and developments in the field of high strength and high formability steel sheets have resulted in several methods for producing high strength and high formability steel sheets, some of which are enumerated herein for conclusive appreciation of the present invention:

EP3144406 a patent that claims a high-strength cold-rolled steel sheet having excellent ductility comprises by wt. %, Carbon (C) : 0.1 % to 0.3%, Silicon (Si) : 0.1 % to 2.0%, Aluminum (Al): 0.005% to 1 .5%, Manganese (Mn): 1 .5% to 3.0%, Phosphorus (P) : 0.04% or less (excluding 0%), Sulfur (S) : 0.015% or less (excluding 0%), Nitrogen (N): 0.02% or less (excluding 0%), and a remainder of Iron (Fe) and inevitable impurities wherein a sum of Silicon and Aluminum (Si+AI) (wt %) satisfies 1 .0% or more, and wherein a microstructure comprises: by area fraction, 5% or less of Polygonal Ferrite having a minor axis to major axis ratio of 0.4 or greater, 70% or less (excluding 0%) of Acicular Ferrite having a minor axis to major axis ratio of 0.4 or less, 25% or less (excluding 0%) of acicular Retained Austenite, and a remainder of Martensite. Further EP3144406 envisage for a high strength steel with a tensile strength of 780MPa or more. EP3128023 mentions a high-strength cold-rolled steel sheet having excellent elongation, hole expandability, and delayed fracture resistance and high yield ratio, and a method for producing the steel sheet. A high-yield-ratio, high- strength cold-rolled steel sheet has a composition containing, in terms of % by mass, C: 0.13% to 0.25%, Si: 1 .2% to 2.2%, Mn: 2.0% to 3.2%, P: 0.08% or less, S: 0.005% or less, Al: 0.01 % to 0.08%, N: 0.008% or less, Ti: 0.055% to 0.130%, and the balance being Fe and unavoidable impurities. The steel sheet has a microstructure that contains 2% to 15% of ferrite having an average crystal grain diameter of 2 μιη or less in terms of volume fraction, 5 to 20% of retained austenite having an average crystal grain diameter of 0.3 to 2.0 μιη in terms of volume fraction, 10% or less (including 0%) of martensite having an average grain diameter of 2 μιη or less in terms of volume fraction, and the balance being bainite and tempered martensite, and the bainite and the tempered martensite having an average crystal grain diameter of 5 μιη or less.

EP3009527 provides a high-strength cold-rolled steel sheet having excellent elongation, excellent stretch flangeability, and high yield ratio and a method for manufacturing the same. The high-strength cold-rolled steel sheet has a composition and a microstructure. The composition contains 0.15% to 0.27% C, 0.8% to 2.4% Si, 2.3% to 3.5% Mn, 0.08% or less P, 0.005% or less S, 0.01 % to 0.08% Al, and 0.010% or less N on a mass basis, the remainder being Fe and inevitable impurities. The microstructure comprises: ferrite having an average grain size of 5 μιη or less and a volume fraction of 3% to 20%, retained austenite having a volume fraction of 5% to 20%, and martensite having a volume fraction of 5% to 20%, the remainder being bainite and/or tempered martensite. The total number of retained austenite with a grain size of 2 μιη or less, martensite with a grain size of 2 μιη or less, or a mixed phase thereof is 150 or more per 2,000 μιη 2 of a thickness cross section parallel to the rolling direction of the steel sheet.

Another patent application WO2015/177615 also describe a double-annealed steel sheet, the composition of which comprises, the contents being expressed as weight percentage, 0.20%≤ C≤ 0.40%, 0.8%≤ Mn≤ 1.4%, 1.60%≤ Si≤ 3.00%, 0.015%≤ Nb≤ 0.150%, Al≤ 0.1 %, Cr≤ 1.0%, S≤ 0.006%, P≤ 0.030%, Ti≤ 0.05%, V≤ 0.05%, B≤ 0.003%, N≤ 0.01 %, the rest of the composition consisting of iron and unavoidable impurities resulting from the production, the microstructure consisting, in surface area proportions, of 10% to 30% of Residual Austenite, of 30% to 60% of Annealed Martensite, of 5% to 30% of Bainite, of 10% to 30% of Quenched Martensite and of less than 10% of Ferrite. Further WO2015/177615 envisages a strength of 980 MPa or more.

The purpose of the present invention is to solve these problems by making available cold-rolled steel sheets that simultaneously have:

- an ultimate tensile strength greater than or equal to 1 100 MPa and preferably above 1 180 MPa,

- a total elongation greater than or equal to 14.0% and preferably above 15%

In a preferred embodiment, the steel sheets according to the invention may also a yield strength to tensile strength ratio of 0.65 or more

Preferably, such steel can also have a good suitability for forming, in particular for rolling with good weldability and coatability. Another object of the present invention is also to make available a method for the manufacturing of these sheets that is compatible with conventional industrial applications while being robust towards manufacturing parameters shifts.

The above object and other advantages of the present invention will become more apparent by describing in detail the preferred embodiment of the present invention with reference to the attached drawings in which:

The cold rolled and heat treated steel sheet of the present invention may optionally be coated with zinc or zinc alloys, or with aluminum or aluminum alloys to improve its corrosion resistance.

Carbon is present in the Steel between 0.10% and 0.5%. Carbon is an element necessary for increasing the strength of a steel sheet by producing a low-temperature transformation phase such as Martensite, further Carbon also plays a pivotal role in austenite stabilization hence a necessary element for securing Residual Austenite.

Manganese content of the Steel of present invention is between 1 % and 3.4%. This element is gammagenous. The purpose of adding Manganese is essentially to obtain a structure that contains austenite and to impart strength to the steel. Manganese is an element which stabilizes Austenite to obtain Residual Austenite. An amount of at least about 1 % by weight of Manganese has been found in order to provide the strength and hardenability of the steel sheet as well as to stabilize Austenite. Thus, a higher percentage of Manganese is preferred by presented invention such as 3.4%. But, when Manganese content is more than 3.4%, it produces adverse effects such as it retards transformation of Austenite to Bainite during the isothermal holding for Bainite transformation. In addition the Manganese content of above 3.4% also deteriorates the weldability of the present steel, hence, the ductility targets may not be achieved. The preferable range for Manganese is 1 .2% and 2.3% and more preferable range is between 1 .2% and 2.2%.

Silicon constituent of the Steel of present invention is between 0.5% and 2.5%. Silicon is a constituent that can retard the precipitation of carbides during overageing, therefore, due to the presence of Silicon, Carbon rich Austenite is stabilized at room temperature. Further, due to poor solubility of Silicon in carbide it effectively inhibit or retard the formation of carbides, hence, also promote the formation of low density carbides in Bainitic structure which is sought as per the present invention to impart steel with its essential features. However, disproportionate content of Silicon does not proliferate the mentioned effect and leads to a problem such as hot rolling embrittlement. Therefore, the concentration is controlled within an upper limit of 2.5%.

The content of the Aluminum is 0.03-1 .5% in the present invention as Aluminum removes Oxygen existing in molten steel to prevent Oxygen from forming a gas phase and being boiled during a solidification process. Aluminum also fixes Nitrogen in the steel to form Aluminum-nitrides so as to reduce the size of the grains. Higher content of Aluminum above 1 .5% increases Ac ₃ point, thereby, increasing the necessary energy input for manufacturing the steel. Aluminum content between 1 .0% and 1 .5% can be used when high Manganese content is added in order to counterbalance the effect of Manganese on transformation points and Austenite formation evolution with temperature.

Chromium content of the Steel of present invention is between 0.05% and 1 %. Chromium is an essential element that provides strength and hardening to the Steel but when used above 1 % impairs surface finish of steel. Further Chromium contents under 1 % coarsen the dispersion pattern of carbide in Bainitic structures, hence, keeping the density of Carbides in Bainite at low level.

Phosphorus constituent of the Steel of present invention is between 0.002% and 0.02%. Phosphorus reduces the spot weldability and the hot ductility, particularly due to its tendency to segregate at the grain boundaries or co-segregate with Manganese. For these reasons, its content is limited to 0.02 % and preferably lower to 0.013%.

Sulfur is not an essential element but may be contained as an impurity in steel and from point of view of the present invention the Sulfur content is preferably as low as possible, but is 0.003% or less from the viewpoint of manufacturing cost. Further if higher Sulfur is present in steel it combines to form Sulfides especially with Manganese and Titanium and reduces their beneficial impact on the present invention which can be detrimental for formability.

Niobium is present in the steel between 0.001 % and 0.1 % and suitable for forming carbo-nitrides to impart strength to the Steel of present invention by precipitation hardening. Niobium will also impact the size of microstructural components through its precipitation as carbo-nitrides and by retarding the recrystallization during heating process. Thus finer microstructure formed at the end of the holding temperature and as a consequence after the complete annealing will lead to the hardening of the product. However, Niobium content above 0.1 % is not economically interesting as a saturation effect of its influence is observed this means that additional amount of Niobium does not result in any strength improvement of the product.

Titanium is an optional element which may be added to the steel of present invention between 0.001 % and 0.1 %. Same as Niobium, it also forms carbo-nitrides precipitation, thus, plays a role in the strengthening of steel. But it is also forms Titanium-nitrides appearing during solidification of the cast product. The amount of Titanium is so limited to 0.1 % to avoid coarse Titanium-nitrides detrimental for formability. In case the Titanium content is below 0.001 % it does not impart any effect on the Steel of present invention. Calcium is added in the Steel of present invention between 0.0001 % and 0.005%. Calcium is added to the Steel of present invention as an optional element especially during the inclusion treatment. Calcium contributes towards the refining of Steel by arresting the detrimental Sulphur content in globular form, thereby, retarding the harmful effect of Sulphur.

Molybdenum is an optional element that constitutes 0.001 % to 0.5% of the Steel of present invention; Molybdenum plays an effective role in determining hardenability and hardness, delays the appearance of Bainite and avoids carbides precipitation in Bainite. However, the addition of Molybdenum excessively increases the cost of the addition of alloying elements, so that for economic reasons its content is limited to 0.5%.

Copper may be added as an optional element in an amount of 0.01 % to 2% to increase the strength of the Steel and to improve its corrosion resistance. A minimum of 0.01 % is required to get such effects. However, when its content is above 2%, it can degrade the surface aspect.

Nickel may be added as an optional element in an amount of 0.01 % to 3% to increase the strength of the Steel and to improve its toughness. A minimum of 0.01 % is required to get such effects. However, when its content is above 3%, nickel causes ductility deterioration.

Nitrogen is limited to 0.01 % in order to avoid ageing of material and to minimize the precipitation of Aluminum nitrides during solidification which are detrimental for mechanical properties of the steel. Vanadium is effective in enhancing the strength of steel by forming carbides or carbo- nitrides and the upper limit is 0.1 % from economic points of view. Other elements such as cerium, boron, magnesium or zirconium can be added individually or in combination in the following proportions: Cerium≤0.1 %, Boron≤0.003%, Magnesium≤0.01 % and Zirconium≤0.01 % up to the maximum content levels indicated, these elements make it possible to refine the grain during solidification.

The remainder of the composition of the steel consists of iron and inevitable impurities resulting from processing.

The microstructure of the sheet claimed by the invention consists of

Bainite constitutes 50% to 85% of microstructure by area fraction for the Steel of present invention. In the present invention the Bainite cumulatively consists of Lath Bainite and Granular Bainite, where Granular Bainite has a very low density of carbides, low density of carbides herein means the presence of carbide count to be less than or equal to 100 carbides per area unit of 100μηι ² and having a high dislocation density which impart high strength as well as elongation to the Steel of present invention. The Lath Bainite is in the form of thin Ferrite laths with Austenite or carbides formed in between the laths. The Lath Bainite of steel of present invention provides the steel with adequate formability. To ensure a total elongation of 14% and preferably 15% or more it is advantageous to have 50% of Bainite.

Residual Austenite content of the Steel of the present invention is between 10% and 30% of microstructure by area fraction. Residual Austenite is known to have a higher solubility of Carbon than Bainite and, hence, acts as effective Carbon trap, therefore, retarding the formation of carbides in Bainite. Carbon percentage inside the Residual Austenite of present invention is preferably higher than 0.9% and preferably lower than 1 .1 %. Residual Austenite of the steel according to the invention imparts an enhanced ductility.

Quenched Martensite constitutes 1 % to 20 % of microstructure by area fraction. Quench Martensite imparts strength to the present invention. Quenched Martensite is formed during the final cooling of the second annealing. No minimum is required but when Quenched Martensite is in excess of 20 % it imparts excess strength but deteriorates other mechanical properties beyond acceptable limit.

Tempered Martensite constitutes 0% to 30 % of microstructure by area fraction. Martensite can be formed when steel is cooled between Tc _min and Tc _max and is tempered during the overaging holding. Tempered Martensite imparts ductility and strength to the present invention. When Tempered Martensite is in excess of 30 % it imparts excess strength but diminishes the elongation beyond acceptable limit. Further Tempered Martensite diminishes the gap in hardness of soft phases such as Residual Austenite and hard phases such as Quench Martensite.

In addition to the above-mentioned microstructure steel sheet may have ferrite which account for less than 5%, preferably less than 3%, in terms of area ratio and the microstructure is free from microstructural components, such as pearlite or cementite without impairing the mechanical properties of the steel sheets. A steel sheet according to the invention can be produced by any suitable method. A preferred method consists in providing a semi-finished casting of steel with a chemical composition according to the invention. The casting can be done either into ingots or continuously in form of thin slabs or thin strips, i.e. with a thickness ranging from approximately 220mm for slabs up to several tens of millimeters for thin strip.

For example, a slab having the above-described chemical composition is manufactured by continuous casting wherein the slab optionally underwent the direct soft reduction during the continuous casting process to avoid central segregation and to ensure a ratio of local carbon to nominal carbon kept below 1 .10. The slab provided by continuous casting process can be used directly at a high temperature after the continuous casting or may be first cooled to room temperature and then reheated for hot rolling. The temperature of the slab, which is subjected to hot rolling, is preferably at least 1200° C and must be below 1280°C. In case the temperature of the slab is lower than 1200° C, excessive load is imposed on a rolling mill and, further, the temperature of the steel may decrease to a ferrite transformation temperature during finishing rolling, whereby the steel will be rolled in a state in which transformed ferrite contained in the structure. Therefore, the temperature of the slab is preferably sufficiently high so that hot rolling can be completed in the temperature range of Ac3 to Ac3+100°C and final rolling temperature remains above Ac3. Reheating at temperatures above 1280°C must be avoided because they are industrially expensive.

A final rolling temperature range between Ac3 to Ac3+100°C is preferred to have a structure that is favorable to recrystallization and rolling. It is necessary to have final rolling pass to be performed at a temperature greater than Ac3, because below this temperature the steel sheet exhibits a significant drop in rollability. The sheet obtained in this manner is then cooled at a cooling rate above 30°C/s to the coiling temperature which must be below 600°C. Preferably, the cooling rate will be less than or equal to 200° C/s.

The hot rolled steel sheet is coiled at a coiling temperature below 600°C to avoid ovalization of the hot rolled steel sheet and preferably below 570°C to avoid scale formation. The preferable range of coiling temperature is between 350 and 570° C. The coiled hot rolled steel sheet is then cooled to room temperature before subjecting it to optional hot band annealing. The hot rolled steel sheet may be subjected to an optional scale removal step to remove the scale formed during the hot rolling. The hot rolled sheet may then subjected to an optional Hot Band Annealing at temperatures between 400°C and 750°C for at least 12 hours and not more than 96 hours while keeping the temperature below 750°C to avoid transforming partially the hot-rolled microstructure and, therefore, losing the microstructure homogeneity. Thereafter, optional scale removal step of this hot rolled steel sheet may be performed, for example such as pickling of such sheet. This hot rolled steel sheet is cold rolled with a thickness reduction between 35 to 90%. The cold rolled steel sheet obtained from cold rolling process is then subjected to two steps of annealing to impart the steel of present invention with microstructure and mechanical properties.

In first annealing, the cold rolled steel sheet is heated at a heating rate which is greater than 3°C/s, to a soaking temperature between Ac3 and Ac3+ 100° C wherein Ac3 for the present steel is calculated by using the following formula :

Ac3 = 901 - 262 ^* C - 29 ^* Mn + 31 ^* Si - 12 ^* Cr - 155 ^* Nb + 86 ^* AI wherein the elements contents are expressed in weight percentage.

Then steel sheet is held at the soaking temperature during 10 seconds to 500s to ensure a complete recrystallization and full transformation to Austenite of the strongly work hardened initial structure. The sheet is then cooled at a cooling rate greater than 20°C/s below 500°C and preferably 400°C. Further it is preferred that cooling rate is greater than 30°C/s to ensure a single phase structure of Martensite.

Then the temperature of cold rolled steel sheet is brought to room temperature. The cold rolled annealed steel sheet may be optionally tempered between temperatures 120°C and 250°C.

Second annealing of the cold rolled annealed steel sheet is performed by heating the annealed cold rolled steel sheet at a heating rate greater than 3°C/s, to a soaking temperature range between above Ac3 and Ac3 + 100°C wherein Ac3 is calculated by using the formula Ac3 = 901 - 262 ^* C - 29 ^* Mn + 31 ^* Si - 12 ^* Cr - 155 ^* Nb + 86 ^* AI during 10 seconds to 500s to ensure 100% transformation to Austenite microstructure. The sheet is then cooled at a cooling rate greater than 20°C/s to a temperature range between Tc _min and Tc _max for a duration between 1 s and 10s. These temperatures are calculated by using the proposed herein formula: - Tcmax = 565 - 601 ^* (1 - Exp(-0.868 ^* C)) - 34 ^* Mn - 13 ^* Si - 10 ^* Cr +

13*AI - 361 ^* Nb

- Tcmin = 565 - 601 ^* (1 - Exp(-1 .736 ^* C)) - 34 ^* Mn - 13 ^* Si - 10 ^* Cr + 13*AI - 361 ^* Nb

wherein the elements contents are expressed in weight percentage. Thereafter, the cold rolled and annealed steel sheet is brought to a temperature range of 350°C to 550°C and kept there during 5 seconds to 500 seconds to ensure the formation of an adequate amount of Bainite as well as to temper the Martensite to impart the steel of present invention with targeted mechanical properties. Afterwards the cold rolled and annealed steel sheet is cooled down to room temperature with a cooling rate of at least 1 °C/s or more to obtain cold rolled and heat treated steel sheet.

The cold rolled and heat treated steel sheet may undergo an additional optional heat treatment step to facilitate coating process, the said optional heat treatment step do not have any impact on the mechanical properties of the steel of present invention. The cold rolled steel sheet then may be optionally coated by any of the known industrial processes such as Electro-galvanization, JVD, PVD, Hot -dip(GI/GA) etc. The Electro-galvanization does not alter or modify any of the mechanical properties or microstructure of the steel sheet claimed. Electro-glavanization can be done by any conventional industrial process for instance by Electroplating. The following tests, examples, figurative exemplification and tables which are presented herein are non-restricting in nature and must be considered for purposes of illustration only, and will display the advantageous features of the present invention.

Steel sheets made of steels with different compositions are gathered in Table 1 , where the steel sheets are produced according to process parameters as stipulated in Table 2, respectively. The Table 3 gathers the microstructure of the steel sheets obtained during the trails and table 4 gathers result of evaluations of obtained properties.

Table 1

Table 2

Table 2 gathers the annealing process parameters implemented on steels of Table 1 . The Steel compositions 11 to I3 serve for the manufacture of sheets according to the invention. This table also specifies the reference steel compositions which are designated in table from R1 to R3. Table 2 also shows tabulation of Tc _min and Tc _max temperatures of inventive steel and reference steel. Tc _min and Tc _max arecalculated by using the following formula:

- Tcmax = 565 - 601 ^* (1 - Exp(-0.868 ^* C)) - 34 ^* Mn - 13 ^* Si - 10 ^* Cr + 13*AI - 361 ^* Nb

- Tcmin = 565 - 601 ^* (1 - Exp(-1 .736 ^* C)) - 34 ^* Mn - 13 ^* Si - 10 ^* Cr +

13*AI - 361 ^* Nb

Further, before performing the annealing treatment on the steels of invention as well as on the reference ones, the Steels were heated to a temperature between 1000° C and 1280°C and then subjected to hot rolling with finish temperature above 850° C and thereafter were coiled at a temperature below 600°C. The Hot rolled coils were then processed as claimed and thereafter cold rolled with a thickness reduction between 30 to 95%. These cold rolled steel sheets were subjected to heat treatments as enumerated in Table 2 herein:

5

I = according to the invention; R = reference; underlined values: not according to the invention.

Table 3

Table 3 exemplifies the results of test conducted in accordance of standards on different microscopes such as Scanning Electron Microscope for determining microstructural composition of both the inventive steel and reference steel.

The results are stipulated herein:

I = according to the invention; R = reference; underlined values: not according to the invention.

Table 4

Table 4 exemplifies the mechanical properties of both the inventive steel and reference steel. The tensile strength, yield strength and total elongation test are conducted in accordance of JIS Z2241 standards.

Henceforth the outcome of the various mechanical tests conducted in accordance to the standards is tabulated:

I = according to the invention; R = reference; underlined values: not according to the invention.