WO2023234503A1 - 초고강도 냉연강판 및 그 제조방법 - Google Patents
초고강도 냉연강판 및 그 제조방법 Download PDFInfo
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- WO2023234503A1 WO2023234503A1 PCT/KR2022/019639 KR2022019639W WO2023234503A1 WO 2023234503 A1 WO2023234503 A1 WO 2023234503A1 KR 2022019639 W KR2022019639 W KR 2022019639W WO 2023234503 A1 WO2023234503 A1 WO 2023234503A1
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- C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
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- C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- 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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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Definitions
- the technical idea of the present invention relates to cold-rolled steel sheets, and more specifically, to ultra-high-strength cold-rolled steel sheets with excellent bendability and hydrogen embrittlement, and to a method of manufacturing the same.
- high-strength steel sheets are required to improve fuel efficiency and durability due to various environmental and energy use regulations.
- high yield strength and tensile strength are important for making automotive structural steel parts such as those mainly used in front bumpers and side sills.
- the microstructure to make a steel sheet with high strength must be composed of martensite and bainite, which are low-temperature structures, and the structure is prone to brittle fracture due to hydrogen remaining inside the steel or flowing in from the outside. This is called hydrogen embrittlement, and the characteristics of hydrogen embrittlement are that fracture generally occurs at a lower strength than the strength at which fracture occurs and becomes more sensitive as strength increases.
- materials can be destroyed by hydrogen embrittlement even under very small stress, ways to compensate for this problem are being sought.
- the technical problem to be achieved by the technical idea of the present invention is to provide an ultra-high strength cold-rolled steel sheet with excellent bendability and hydrogen embrittlement and a method of manufacturing the same.
- an ultra-high strength cold rolled steel sheet with excellent bendability and hydrogen embrittlement and a method for manufacturing the same are provided.
- the ultra-high-strength cold-rolled steel sheet has, in weight percent, carbon (C): 0.23% to 0.40%, silicon (Si): 0.05% to 1.0%, and manganese (Mn): 0.5% to 0.5%.
- V Vanadium
- Al Aluminum
- Al 0.01% ⁇ 0.3%
- Chromium (Cr) > 0% ⁇ 0.5%
- Titanium (Ti) > 0% ⁇ 0.1%
- Phosphorus (P) more than 0% ⁇ 0.02%
- sulfur (S) more than 0% ⁇ 0.01%
- boron (B) 0.001% ⁇ 0.005%
- the balance is ultra-high strength cold rolled steel containing iron (Fe) and other inevitable impurities.
- the final microstructure includes tempered martensite with a volume fraction of 90% or more, the average distance between precipitates in the tempered martensite is 300 nm or more, the average size of the precipitates is 200 nm or less, and the final microstructure Based on the area of 20 ⁇ m2 , the number of precipitates with an average size of 40nm or less is 25 or more.
- the cold-rolled steel sheet has a soft region in the surface layer having a hardness of less than 85% of the average hardness of the base material of the cold-rolled steel sheet, and the ratio of the thickness of the soft region region to the thickness of the base material is 0.03. It can be ⁇ 0.10.
- the cold rolled steel sheet may have a Prior Austenite Grain Size (PAGS) of 12 ⁇ m or less.
- PAGS Prior Austenite Grain Size
- the cold-rolled steel sheet may further include molybdenum (Mo): 0.01% to 0.3% or niobium (Nb): 0.01% to 0.1% by weight.
- Mo molybdenum
- Nb niobium
- the cold-rolled steel sheet has the values of [C] + [V] + [Cr] + [Mo] + [Nb] (however, the [C], [V], [Cr], [Mo] and [Nb] are weight percent values of carbon, vanadium, chromium, molybdenum and niobium) may be less than 0.63.
- yield strength (YP) 1200 MPa or more
- tensile strength (TS) 1500 MPa or more
- elongation (El) 7.0% or more
- yield ratio 70% or more
- bendability (R/t) 2.5 or less
- hydrogen embrittlement elongation reduction rate may be 35% or less.
- the method of manufacturing the ultra-high strength cold rolled steel sheet is calculated by weight percentage, carbon (C): 0.23% ⁇ 0.40%, silicon (Si): 0.05% ⁇ 1.0%, manganese (Mn): 0.5%.
- V Vanadium
- Al Aluminum
- Al 0.01% ⁇ 0.3%
- Chromium (Cr) > 0% ⁇ 0.5%
- Titanium (Ti) > 0% ⁇ 0.1%
- phosphorus (P) more than 0% ⁇ 0.02%
- sulfur (S) more than 0% ⁇ 0.01%
- boron (B) 0.001% ⁇ 0.005%
- the balance is steel containing iron (Fe) and other inevitable impurities.
- Hot rolling to provide a hot rolled steel sheet Cold rolling the hot steel sheet to provide a cold rolled steel sheet; Raising the temperature of the cold rolled steel sheet; Annealing the temperature-elevated cold-rolled steel sheet; Cooling the annealed cold rolled steel sheet; and reheating and tempering the cooled cold-rolled steel sheet; wherein, during the step of annealing the cold-rolled steel sheet, the annealing temperature ranges from 750°C to 950°C without a period of maintaining a constant temperature before cooling the cold-rolled steel sheet. It is characterized by a gradual and continuous rise within the range.
- the annealing temperature (T) in the step of annealing the cold rolled steel sheet, may satisfy the relationship of Equation 1 below depending on the time (t).
- the step of increasing the temperature of the cold-rolled steel sheet may have a temperature increase rate of 3°C/sec or more, and the step of annealing the cold-rolled steel sheet may have a temperature increase rate of less than 3°C/sec.
- the hot rolling is performed at a reheating temperature (SRT): 1180°C to 1300°C, a finish rolling temperature (FDT): 800°C to 950°C, and a coiling temperature (CT): 500°C to 700°C. It can be performed under certain conditions.
- SRT reheating temperature
- FDT finish rolling temperature
- CT coiling temperature
- the step of cooling the annealed cold-rolled steel sheet includes slowly cooling the annealed cold-rolled steel sheet to a temperature of 700-800°C at a cooling rate in the range of 3°C/sec to 15°C/sec. ; A first rapid cooling process of the slowly cooled cold-rolled steel sheet to a temperature of 300°C to 350°C at a cooling rate in the range of 80°C/sec to 150°C/sec; and secondly quenching the first quenched cold-rolled steel sheet to a temperature of room temperature to 300°C at a cooling rate in the range of 30°C/sec to 90°C/sec. may include.
- the step of reheating and tempering the cooled cold rolled steel sheet includes a tempering step of reheating the second quenched cold rolled steel sheet and maintaining it at a temperature of 150°C to 350°C for 30 to 300 seconds. It can be included.
- an ultra-high strength cold rolled steel sheet with excellent bendability and hydrogen embrittlement and a manufacturing method thereof can be implemented.
- the annealing holding section is replaced with a temperature increase according to the quadratic function to obtain an appropriate soft zone (decarburized zone) area to prevent the target bendability (R/t) below 2.5 and coarsening of PAGS (Prior Austenite Grain Size).
- PAGS Primary Austenite Grain Size
- ultra-high strength steel sheets with a yield of over 1200MPa, a tensile strength of over 1500MPa, and a high yield ratio (over 70%) are realized, and productivity is improved by reducing the process time by approximately 10% or more by replacing some of the holding sections within the annealing section with elevated temperatures. You can do it.
- Figure 1 is a process flow chart schematically showing a method of manufacturing an ultra-high strength cold-rolled steel sheet according to an embodiment of the present invention.
- Figure 2 is a time-temperature graph showing annealing, cooling, and tempering heat treatment processes after cold rolling in the method of manufacturing ultra-high strength cold-rolled steel sheets according to comparative examples and examples of the present invention.
- Figure 3 is a photograph of a representative final microstructure of an ultra-high strength cold rolled steel sheet according to an embodiment of the present invention.
- Figure 4 is a photograph observing precipitates in the microstructure of an ultra-high-strength cold-rolled steel sheet according to an embodiment of the present invention.
- Figure 1 is a process flow chart schematically showing a method of manufacturing an ultra-high strength cold-rolled steel sheet according to an embodiment of the present invention
- Figure 2 is an annealing after cold rolling in a method of manufacturing an ultra-high strength cold-rolled steel sheet according to comparative examples and examples of the present invention.
- , is a time-temperature graph showing the cooling and tempering heat treatment process.
- the method of manufacturing an ultra-high-strength cold-rolled steel sheet includes the step of hot-rolling a steel material to provide a hot-rolled steel sheet (S10); Cold rolling the hot steel sheet to provide a cold rolled steel sheet (S20); Raising the temperature of the cold rolled steel sheet (S31); Annealing the temperature-elevated cold-rolled steel sheet (S32); Cooling the annealed cold rolled steel sheet (S40, S50, S60); and reheating and tempering the cooled cold rolled steel sheet (S70).
- the ultra-high strength cold-rolled steel sheet according to an embodiment of the present invention has, in weight percent, carbon (C): 0.23% to 0.40%, silicon (Si): 0.05% to 1.0%, manganese (Mn): 0.5% to 3.0%. , Vanadium (V): 0.01% ⁇ 0.12%, Aluminum (Al): 0.01% ⁇ 0.3%, Chromium (Cr): > 0% ⁇ 0.5%, Titanium (Ti): > 0% ⁇ 0.1%, Phosphorus (P ): more than 0% ⁇ 0.02%, sulfur (S): more than 0% ⁇ 0.01%, boron (B): 0.001% ⁇ 0.005%, and the balance includes iron (Fe) and other inevitable impurities.
- the role and content of each component included in the ultra-high-strength cold-rolled steel sheet according to the present invention will be described as follows.
- the content of the component elements all refers to weight percent based on the entire steel sheet.
- the carbon content is preferably 0.23% to 0.40%. If the carbon content is less than 0.23%, it is difficult to achieve the target strength. If it exceeds 0.40%, the carbon equivalent (Ceq) increases, which is disadvantageous in weldability and bendability and hydrogen embrittlement resistance. There may be disadvantages.
- Silicon is a ferrite stabilizing element that delays the formation of carbides in ferrite and has a solid solution strengthening effect. Silicon is preferably added at 0.05% to 1.0%. If it is less than 0.05%, the effect is very small. If it exceeds 1.0%, oxides such as Mn 2 SiO 4 may be formed during the manufacturing process, and weldability may be improved by increasing the carbon equivalent. It can deteriorate. In addition, precipitation of carbides may be excessively suppressed, resulting in a result that deviates from the effect of the present invention.
- Manganese has a solid solution strengthening effect and increases hardenability, contributing to strength improvement.
- Manganese is preferably added at 0.5% to 3.0%. If it is less than 0.5%, hardenability is not sufficient and it is difficult to secure strength. If it exceeds 3.0%, processability and resistance to hydrogen embrittlement are reduced due to the formation or segregation of inclusions such as MnS. may occur and increase the carbon equivalent, which may reduce weldability.
- V Vanadium (V): 0.01% to 0.12%
- Vanadium is a major element that precipitates in the form of carbide (VC) in steel, has the effect of refining PAGS (Prior Austenite Grain Size), and contributes to improving yield strength. Vanadium is preferably added in an amount of 0.01% to 0.12% of the total weight in the ultra-high strength cold rolled steel sheet according to an embodiment of the present invention. If the vanadium content is less than 0.01%, it is difficult to expect a precipitate effect, and if it exceeds 0.12%, problems of material deterioration and increased manufacturing costs appear, problems of grain coarsening due to the formation of coarse precipitates appear, and recrystallization temperature If the temperature rises too high, a problem occurs that causes non-uniform organization.
- PAGS Primary Austenite Grain Size
- Aluminum is used as a deoxidizer and can be helpful in cleaning ferrite. If the aluminum content is less than 0.01%, the deoxidation effect may be insufficient. If the aluminum content exceeds 0.3%, AlN may be formed during slab manufacturing, causing cracks during casting or hot rolling. Therefore, it is desirable to add aluminum in an amount of 0.01% to 0.3% of the total weight of the steel sheet.
- Chromium is a ferrite stabilizing element, increases solid solution strengthening and hardenability of steel, and contributes to improving strength by refining carbides. If the chromium content exceeds 0.5%, weldability may be impaired and the manufacturing cost of steel may increase. Therefore, it is desirable to add chromium in an amount exceeding 0% to 0.5% of the total weight of the steel sheet.
- Titanium is a precipitate forming element and has the effect of precipitation of TiN and TiC and grain refinement.
- the nitrogen content inside the steel can be lowered through the precipitation of TiN, and when added together with boron, the precipitation of BN can be prevented.
- Titanium is preferably added in an amount exceeding 0% to 0.1%, and if added in excess of 0.1%, the manufacturing cost of steel increases.
- Phosphorus is an impurity included in the steel manufacturing process. Although it can help improve strength through solid solution strengthening, it can cause low-temperature brittleness when contained in large amounts. Therefore, it is desirable to limit the phosphorus content to more than 0% to 0.02% of the total weight of the steel sheet.
- Sulfur is an impurity included in the steel manufacturing process and can form non-metallic inclusions such as FeS, MnS, etc., reducing bendability, toughness, and weldability. Therefore, it is desirable to limit the sulfur content to more than 0% to 0.01% of the total weight of the steel sheet.
- Boron is a hardenable element that greatly contributes to the formation of martensite during the cooling process after annealing. Boron is preferably added in an amount of 0.001% to 0.005%. If it is less than 0.001%, the effect is insufficient and it is difficult to secure martensite, and if it is added in excess of 0.005%, it may reduce the toughness of the steel.
- the remaining component of the ultra-high strength cold rolled steel sheet is iron (Fe).
- Fe iron
- unintended impurities from raw materials or the surrounding environment may inevitably be mixed, so this cannot be ruled out. Since these impurities are known to anyone skilled in the normal manufacturing process, all of them are not specifically mentioned in this specification.
- the ultra-high-strength cold-rolled steel sheet according to a modified embodiment of the present invention may additionally include at least one or more of the elements having the following composition ranges in addition to the alloy elements described above.
- Molybdenum plays a role in improving hydrogen embrittlement resistance, has a solid solution strengthening effect, and increases hardenability, contributing to strength improvement. If the molybdenum content exceeds 0.3%, the manufacturing cost of steel may increase. Therefore, it is desirable to add molybdenum in an amount of 0.01% to 0.3% of the total weight of the steel sheet.
- Niobium has the effect of refining PAGS (Prior Austenite Grain Size) and contributes to improving yield strength by forming precipitates in the form of NbC. In other words, it is a precipitate forming element that improves the toughness and strength of steel through precipitation and grain refinement.
- Niobium is preferably added at 0.01% to 0.1%. If added in excess of 0.1%, a low-temperature transformation structure may occur due to the delay in ferrite transformation during hot rolling, which may have a negative effect on lowering impact performance and increase the manufacturing cost of steel. I order it.
- the ultra-high-strength cold-rolled steel sheet according to the present invention having the above-described composition range can satisfy the following relational expression 1.
- Equation 1 [C] + [V] + [Cr] + [Mo] + [Nb] ⁇ 0.63
- [C], [V], [Cr], [Mo], and [Nb] are weight percent values of carbon, vanadium, chromium, molybdenum, and niobium. If the above relational expression 1 is not satisfied, the precipitates become coarse and hydrogen embrittlement increases.
- a hot rolled steel sheet is provided by hot rolling a steel material having the above-described composition.
- the hot rolling can be performed under the conditions of reheating temperature (SRT): 1180°C to 1300°C, finish rolling temperature (FDT): 800°C to 950°C, and coiling temperature (CT): 500°C to 700°C.
- the slab containing the above-described alloy components and the remaining iron and inevitable impurities is reheated to a temperature of 1180°C to 1300°C.
- Slabs are manufactured in the form of semi-finished products by continuously casting molten steel obtained through the steelmaking process. By reheating the slab, component segregation occurring during the casting process is homogenized and made ready for hot rolling. If the Slab Reheating Temperature (SRT) is less than 1180°C, there is a problem that the segregation of the slab cannot be sufficiently re-employed. If it exceeds 1300°C, the size of austenite grains increases, and the process cost increases as the temperature rises. can do. Reheating of the slab can take 1 to 4 hours. If the reheating time is less than 1 hour, the degree of homogenization of the segregation is insufficient, and if it exceeds 4 hours, the austenite grain size increases, and the process cost may increase.
- SRT Slab Reheating Temperature
- the reheated slab is hot rolled.
- Hot rolling is performed at a finish delivery temperature (FDT) of 800°C to 900°C. If the finish rolling temperature is lower than 800°C, the rolling load increases rapidly, reducing productivity, and if it exceeds 900°C, the size of the grains may increase and strength may decrease. After hot rolling, it is cooled to a temperature of 500°C ⁇ 700°C and then wound. If the coiling temperature is less than 500°C, the strength increases and the rolling load during cold rolling increases, and if it exceeds 700°C, it may cause defects in the post-process due to surface oxidation, etc.
- FDT finish delivery temperature
- the hot rolled steel sheet is pickled to remove the surface scale layer, and then cold rolled. Milling is performed to remove the surface scale layer remaining even after pickling. To completely remove the uniform surface scale layer or surface scale layer, milling is performed 0.3 to 1 mm compared to the initial thickness. If the milling thickness is less than 0.3 mm, a surface scale layer generated during hot rolling may remain and it may be difficult to control a uniform decarburization layer during subsequent heat treatment. If milling exceeds 1 mm, the recovery rate may decrease and the process cost may increase as the discarded portion increases. The thickness reduction rate during cold rolling is approximately 40% to 70%.
- the temperature increase rate may be 3°C/sec or more.
- the cold rolled steel sheet can reach a temperature of A 3 to A 3 +30°C. If the temperature increase rate is less than 3°C/s in the temperature raising step (S31), it takes a long time to reach the target annealing temperature, which may reduce production efficiency and increase the size of the grains.
- the annealing temperature is within the temperature range ( ⁇ T) of 750°C to 950°C without a period of maintaining a constant temperature until the step (S40) of cooling the cold-rolled steel sheet is performed. It is characterized by a gradual and continuous rise.
- the step (S32) of annealing the cold rolled steel sheet is characterized in that the annealing temperature (T) satisfies the relationship of Equation 1 below according to time (t).
- the annealing temperature must be raised to A 3 or higher to create an austenite single phase to create tempered martensite, the final structure.
- the annealing temperature may vary depending on the steel type, and most satisfies 750°C to 950°C.
- the following advantages can be obtained by eliminating the holding section in the general annealing heat treatment section and replacing it with the temperature increase according to Equation 1 above.
- a step (S40) of slowly cooling the annealed cold rolled steel sheet is performed. This is the section where the area is cooled at a cold rate of 3 to 15°C/sec after annealing.
- the annealed cold-rolled steel sheet is slowly cooled to a temperature of 700 to 800°C at a cooling rate in the range of 3°C/sec to 15°C/sec.
- the slow cooling end temperature that is, the rapid cooling start temperature
- falls below 700°C ferrite transformation occurs, causing a decrease in strength, which may not reach the target strength.
- a first quenching treatment step (S50) is performed on the annealed cold-rolled steel sheet.
- the cold-rolled steel sheet that has undergone the slow cooling treatment may be first rapidly cooled to a temperature of 300°C to 350°C at a cooling rate in the range of 80°C/sec to 150°C/sec.
- the first rapid cooling section is a temperature section between the slow cooling end temperature and the Ms transformation point, and it is important to suppress ferrite and bainite transformation through rapid cooling in this section.
- the cold speed to suppress this is about 80°C/sec or more, and if it is slower than 80°C/sec, strength reduction may occur due to ferrite and bainite transformation.
- a step (S60) of performing a second quenching treatment on the cold rolled steel sheet that has undergone the first quenching treatment is performed.
- the cold rolled steel sheet that has been subjected to the first quenching treatment may be subjected to a second quenching treatment from room temperature to 300°C at a cooling rate ranging from 30°C/sec to 90°C/sec.
- the second rapid cooling section is the temperature section from Ms transformation point to room temperature, and martensite transformation occurs in this section.
- the Ms temperature is around 350°C and the start point of martensite transformation is 300°C to 400°C.
- tempering may occur, resulting in a tempered martensite structure with a large size of carbides, and softening of the tempered martensite may result in a decrease in strength.
- a cooling rate of 30°C/sec or more is required in the secondary cooling section to prevent this tempering.
- the average cooling speed of the first and second quenching sections is 70°C/sec or more, cooling may be performed without distinguishing between quenching sections.
- a step (S70) of reheating and tempering the cooled cold rolled steel sheet is performed.
- a tempering step may be performed in which the second quenched cold-rolled steel sheet is reheated and maintained at a temperature of 150°C to 350°C for 30 to 300 seconds.
- the tempering stage is the section where the generated martensite changes into tempered martensite.
- Tempering holding time has a small effect compared to the tempering temperature, but if it is less than 30 seconds, it is difficult to obtain a stable tempering effect. If it exceeds 5 minutes, heat treatment efficiency may decrease, carbide size may increase, and strength may decrease, so it is limited to 5 minutes or less.
- the ultra-high-strength cold-rolled steel sheet according to the embodiment of the present invention implemented by performing the above-described steps has the following weight percent: carbon (C): 0.23% ⁇ 0.40%, silicon (Si): 0.05% ⁇ 1.0%, manganese (Mn) : 0.5% ⁇ 3.0%, Vanadium (V): 0.01% ⁇ 0.12%, Aluminum (Al): 0.01% ⁇ 0.3%, Chromium (Cr): > 0% ⁇ 0.5%, Titanium (Ti): > 0% ⁇ 0.1%, phosphorus (P): more than 0% ⁇ 0.02%, sulfur (S): more than 0% ⁇ 0.01%, boron (B): 0.001% ⁇ 0.005%, and the balance includes iron (Fe) and other inevitable impurities. It is an ultra-high strength cold rolled steel plate.
- the final microstructure includes tempered martensite with a volume fraction of 90% or more, and the remainder may be martensite and bainite.
- the volume fraction of tempered martensite in the final microstructure may be 100%.
- the volume fraction of tempered martensite may be 90%, and the volume fraction of martensite and bainite may be 10%.
- the average distance between precipitates in the tempered martensite is 300 nm or more, the average size of the precipitates is 200 nm or less, and the number of precipitates with an average size of 40 nm or less based on an area of 20 ⁇ m 2 in the final microstructure is 25 or more. It is characterized by If the fraction of tempered martensite in the ultra-high strength cold rolled steel base of this embodiment is A, and the fraction occupied by precipitates is B, the relationship B/A ⁇ 0.01 is satisfied.
- the ultra-high-strength cold-rolled steel sheet according to an embodiment of the present invention implemented by performing the above-described steps may have a Prior Austenite Grain Size (PAGS) of 12 ⁇ m or less. If it is coarser than this, it is difficult to confirm the effect of improving hydrogen embrittlement characteristics by grain refinement.
- PAGS Prior Austenite Grain Size
- PAGS in order to satisfy the target tensile properties and hydrogen embrittlement characteristics, PAGS is small and the precipitates are composed of tempered martensite (90% or more), martensite, and bainite (the remainder). It is made up of organizations.
- the ultra-high-strength cold-rolled steel sheet according to an embodiment of the present invention implemented by performing the above-described steps has a soft part region in the surface layer having a hardness less than 85% of the average hardness of the base material of the cold-rolled steel sheet, and the thickness of the soft part region and The ratio of the thickness of the base material may be 0.03 to 0.10.
- the hardness of the steel plate was measured using a Vickers tester with a load of 50 g at 30 ⁇ m intervals from the surface to the center of the plate thickness cross section.
- the soft area of the surface layer of the steel sheet is an area with less than 0.85 Set it to less than 0.85.
- the hardness of the steel plate base material was determined by using the average of 5 measurements in the area of 1/4 of the plate thickness.
- the thickness of the base material is t m and the thickness of the soft part (decarburized part) area is t s , the relationship of 0.03 ⁇ t s / t m ⁇ 0.1 is satisfied. If the thickness of the soft area is too thin (within 0.03), it is difficult to obtain the effect of improving bendability, and if it exceeds 0.1, it is difficult to secure the desired physical properties.
- the ultra-high strength cold-rolled steel sheet according to an embodiment of the present invention implemented by performing the above-described steps has yield strength (YP): 1200 MPa or more, tensile strength (TS): 1500 MPa or more, elongation (El): 7.0% or more, and yield ratio. It was confirmed that it had the following physical properties: 70% or more, bendability (R/t): 2.5 or less, and hydrogen embrittlement elongation reduction rate: 35% or less.
- Table 1 shows the composition (unit: weight %, the balance is iron) of the steel according to the experimental example of the present invention.
- the composition of the steel according to Example 1 is in weight percent, carbon (C): 0.23% to 0.40%, silicon (Si): 0.05% to 1.0%, manganese (Mn): 0.5% to 3.0. %, Vanadium (V): 0.01% ⁇ 0.12%, Aluminum (Al): 0.01% ⁇ 0.3%, Chromium (Cr): > 0% ⁇ 0.5%, Titanium (Ti): > 0% ⁇ 0.1%, Phosphorus ( P): more than 0% ⁇ 0.02%, sulfur (S): more than 0% ⁇ 0.01%, boron (B): 0.001% ⁇ 0.005%, and the remainder satisfies the composition range of iron (Fe).
- carbon content is relatively low.
- Comparative Examples 1 to 4 did not contain vanadium, unlike Example 1.
- Example 1 the values of [C] + [V] + [Cr] + [Mo] + [Nb] (however, the values of [C], [V], [Cr], [Mo] and [Nb] is the weight percent value of carbon, vanadium, chromium, molybdenum and niobium) is less than 0.63, but in Comparative Examples 3 and 4, the values of [C] + [V] + [Cr] + [Mo] + [Nb] It can be confirmed that it exceeds 0.63 (Comparative Example 3: 0.686, Comparative Example 4: 0.631).
- Comparative Examples 1 to 4 and Example 1 applied the same conditions within the process range of hot rolling (S10), cold rolling (S20), and heat treatment after cold rolling (S40, S50, S60) described above. did.
- the annealing heat treatment (S32) process of Comparative Example 1 and Comparative Example 2 corresponds to process 1 shown in FIG. 2
- the annealing heat treatment (S32) process of Comparative Example 3, Comparative Example 4, and Example 1 is shown in FIG. It corresponds to process 2 shown.
- Tables 2 and 3 show the results of evaluating the physical properties of steel according to experimental examples of the present invention.
- the hydrogen embrittlement elongation reduction rate (%) was measured under hydrogen injection conditions of 5 mA 1 hr.
- Comparative Example 3 and Comparative Example 4 had a smaller PAGS (Prior Austenite Grain Size) due to the increased content of Nb and Mo compared to Comparative Example 1 and Comparative Example 2.
- PAGS Primary Austenite Grain Size
- Precipitates are generally formed by Mo, Nb, V, Ti, etc., but the higher the content of the element, the less dissolved it is.
- Comparative Example 3 and Comparative Example 4 can confirm that the value of [C] + [V] + [Cr] + [Mo] + [Nb] exceeds 0.63 (Comparative Example 3: 0.686, Comparative Example 4: 0.631 ). In other words, as the amount of undissolved carbide increases during reheating, coarse precipitates are formed. As the precipitates become coarser, the average distance becomes shorter and the number of precipitates decreases, which does not significantly contribute to improving hydrogen embrittlement.
- Example 1 fine precipitates of relatively uniform size were evenly distributed and the conditions proposed in the present invention (yield strength (YP): 1200 MPa or more, tensile strength (TS): 1500 MPa or more, elongation (El): 7.0 % or more, yield ratio: 70% or more, bendability (R/t): 2.5 or less) and that hydrogen embrittlement was significantly improved (hydrogen embrittlement elongation reduction rate: 35% or less).
- Figure 3 is a photograph of a representative final microstructure of an ultra-high strength cold-rolled steel sheet according to Example 1 of the present invention
- Figure 4 is a photograph of precipitates observed in the microstructure of an ultra-high-strength cold-rolled steel sheet according to Example 1 of the present invention. am.
- the ultra-high strength cold rolled steel sheet according to Example 1 of the present invention has a final microstructure of tempered martensite with a volume fraction of 90% or more, and the average spacing between precipitates in the tempered martensite is It can be seen that the distance is 300 nm or more, the average size of the precipitates is 200 nm or less, and the number of precipitates with an average size of 40 nm or less based on an area of 20 ⁇ m 2 in the final microstructure is 25 or more.
- the embodiment of the present invention is a method of manufacturing ultra-high strength steel using martensite similar to the comparative examples, but has the following differences and advantages.
- ultra-high strength steel sheets with a yield of over 1200MPa, a tensile strength of over 1500MPa, and a high yield ratio (over 70%) are realized, and productivity is improved by reducing the process time by approximately 10% or more by replacing some of the holding sections within the annealing section with elevated temperatures. You can do it.
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Abstract
Description
| C | Si | Mn | P | S | V | Al | Cr | Mo | Nb | Ti | B | |
| 비교예 1 | 0.233 | 0.182 | 1.18 | 0.02 | 0.0011 | 0 | 0.014 | 0 | 0 | 0.019 | 0.038 | 0.0014 |
| 비교예 2 | 0.23 | 0.203 | 0.81 | 0.014 | 0.0021 | 0 | 0.024 | 0 | 0.05 | 0 | 0.043 | 0.0025 |
| 비교예 3 | 0.296 | 0.393 | 1.015 | 0.01 | 0.0009 | 0 | 0.024 | 0.29 | 0.1 | 0 | 0.04 | 0.002 |
| 비교예 4 | 0.301 | 0.391 | 1.02 | 0.01 | 0.0011 | 0 | 0.014 | 0.3 | 0 | 0.03 | 0.04 | 0.002 |
| 실시예 1 | 0.286 | 0.39 | 1.014 | 0.01 | 0.0008 | 0.03 | 0.021 | 0.3 | 0 | 0 | 0.04 | 0.002 |
| YS (MPa) | TS (MPa) | T.EL (%) | YR(%) | R/t | |
| 비교예 1 | 1290 | 1571 | 6.1 | 82.1 | 0.7 |
| 비교예 2 | 1285 | 1543 | 5.8 | 83.3 | 0.5 |
| 비교예 3 | 1324 | 1749 | 7.2 | 75.7 | 2.2 |
| 비교예 4 | 1339 | 1745 | 7.8 | 76.7 | 2.0 |
| 실시예 1 | 1290 | 1726 | 8.3 | 74.8 | 2.0 |
| Hvs/Hvm | ts/tm | 석출물 평균거리 (nm) |
석출물 40nm이하 개수 (20㎛2 기준) |
수소취성 연신율 감소율(%) |
PAGS (㎛) |
|
| 비교예 1 | 0.63~0.81 | 0.075 | 320.6 | 20 | 79 | 13.5 |
| 비교예 2 | 0.61~0.79 | 0.078 | 365.3 | 19 | 68 | 13.2 |
| 비교예 3 | 0.74~0.83 | 0.049 | 386.8 | 16 | 72 | 7.40 |
| 비교예 4 | 0.72~0.80 | 0.050 | 313.2 | 17 | 84 | 9.69 |
| 실시예 1 | 0.72~0.82 | 0.052 | 499.1 | 54 | 27 | 8.87 |
Claims (12)
- 중량%로, 탄소(C): 0.23% ~ 0.40%, 실리콘(Si): 0.05% ~ 1.0%, 망간(Mn): 0.5% ~ 3.0%, 바나듐(V): 0.01% ~ 0.12%, 알루미늄(Al): 0.01% ~ 0.3%, 크롬(Cr): 0% 초과 ~ 0.5%, 티타늄(Ti): 0% 초과 ~ 0.1%, 인(P): 0% 초과 ~ 0.02%, 황(S): 0% 초과 ~ 0.01%, 보론(B): 0.001% ~ 0.005% 및 잔부는 철(Fe)과 기타 불가피한 불순물을 포함하는 초고강도 냉연강판이며,최종 미세조직은 부피분율이 90% 이상인 템퍼드 마르텐사이트를 포함하되, 상기 템퍼드 마르텐사이트 내 석출물 간의 평균 이격거리는 300nm 이상이며, 상기 석출물의 평균 크기는 200nm 이하이고, 상기 최종 미세조직 내 20㎛2 면적을 기준으로 평균 크기가 40nm 이하인 석출물의 개수는 25개 이상인 것을 특징으로 하는,초고강도 냉연강판.
- 제 1 항에 있어서,상기 냉연강판은 표층부에 상기 냉연강판의 모재 평균 경도의 85% 미만인 경도를 가지는 연질부 영역을 가지되, 상기 연질부 영역의 두께와 상기 모재의 두께의 비가 0.03 ~ 0.10 인 것을 특징으로 하는,초고강도 냉연강판.
- 제 1 항에 있어서,상기 냉연강판은 PAGS(Prior Austenite Grain Size)가 12㎛ 이하인 것을 특징으로 하는,초고강도 냉연강판.
- 제 1 항에 있어서,중량%로, 몰리브덴(Mo): 0.01% ~ 0.3% 또는 니오븀(Nb): 0.01% ~ 0.1%을 더 포함하는,초고강도 냉연강판.
- 제 1 항 또는 제 4 항에 있어서,상기 냉연강판은 [C] + [V] + [Cr] + [Mo] + [Nb] 의 값(단, 상기 [C], [V], [Cr], [Mo] 및 [Nb]는 탄소, 바나듐, 크롬, 몰리브덴 및 니오븀의 중량%값임)이 0.63보다 작은 것을 특징으로 하는,초고강도 냉연강판.
- 제 1 항에 있어서,항복강도(YP): 1200MPa 이상, 인장강도(TS): 1500MPa 이상, 연신율(El): 7.0% 이상, 항복비: 70% 이상, 굽힘성(R/t): 2.5 이하 및 수소취성 연신율 감소율: 35% 이하인,초고강도 냉연강판.
- 중량%로, 탄소(C): 0.23% ~ 0.40%, 실리콘(Si): 0.05% ~ 1.0%, 망간(Mn): 0.5% ~ 3.0%, 바나듐(V): 0.01% ~ 0.12%, 알루미늄(Al): 0.01% ~ 0.3%, 크롬(Cr): 0% 초과 ~ 0.5%, 티타늄(Ti): 0% 초과 ~ 0.1%, 인(P): 0% 초과 ~ 0.02%, 황(S): 0% 초과 ~ 0.01%, 보론(B): 0.001% ~ 0.005% 및 잔부는 철(Fe)과 기타 불가피한 불순물을 포함하는 강재를 열간압연하여 열연강판을 제공하는 단계; 상기 열간강판을 냉간압연하여 냉연강판을 제공하는 단계; 상기 냉연강판을 승온하는 단계; 상기 승온된 냉연강판을 소둔하는 단계; 상기 소둔된 냉연강판을 냉각하는 단계; 및 상기 냉각된 냉연강판을 재가열하여 템퍼링하는 단계;를 포함하되,상기 냉연강판을 소둔하는 단계 동안 소둔 온도는 상기 냉연강판을 냉각하기 전까지 일정한 온도를 유지하는 구간 없이 750℃ ~ 950℃의 온도범위 내에서 점진적으로 계속 상승하는 것을 특징으로 하는,초고강도 냉연강판의 제조방법.
- 제 7 항에 있어서,상기 냉연강판을 소둔하는 단계는 소둔 온도(T)가 시간(t)에 따른 하기 수학식 1의 관계를 만족하는 것을 특징으로 하는,초고강도 냉연강판의 제조방법.[수학식 1]소둔 온도(T) = A × t2 + B × t +C (단, 상기 A, B, C 는 -0.007 < A < -0.005, 2 < B < 3, 500 < C < 700 을 만족하는 상수)
- 제 7 항에 있어서,상기 냉연강판을 승온하는 단계는 승온속도가 3℃/초 이상이며,상기 냉연강판을 소둔하는 단계는 승온속도가 3℃/초 미만인 것을 특징으로 하는,초고강도 냉연강판의 제조방법.
- 제 7 항에 있어서,상기 열간압연은 재가열온도(SRT): 1180℃ ~ 1300℃, 마무리압연온도(FDT): 800℃ ~ 950℃, 권취온도(CT): 500℃ ~ 700℃인 조건에서 수행되는 것을 특징으로 하는,초고강도 냉연강판의 제조방법.
- 제 7 항에 있어서,상기 소둔된 냉연강판을 냉각하는 단계는상기 소둔된 냉연강판을 3℃/초 ~ 15℃/초 범위의 냉각속도로 700 ~ 800℃의 온도까지 서랭 처리하는 단계;상기 서랭 처리된 냉연강판을 80℃/초 ~ 150℃/초 범위의 냉각속도로 300℃ ~ 350℃의 온도까지 제1 급랭 처리하는 단계; 및상기 제1 급랭 처리된 냉연강판을 30℃/초 ~ 90℃/초 범위의 냉각속도로 상온 ~ 300℃의 온도까지 제2 급랭 처리하는 단계; 를 포함하는,초고강도 냉연강판의 제조방법.
- 제 11 항에 있어서,상기 냉각된 냉연강판을 재가열하여 템퍼링하는 단계는 상기 제2 급랭 처리된 냉연강판을 재가열하여 150℃ ~ 350℃의 온도에서 30 ~ 300초동안 유지하는 템퍼링 단계를 포함하는,초고강도 냉연강판의 제조방법.
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| CN202280096497.4A CN119278291A (zh) | 2022-05-31 | 2022-12-05 | 超高强度冷轧钢板及其制造方法 |
| EP22945041.6A EP4534721A4 (en) | 2022-05-31 | 2022-12-05 | ULTRA-HIGH STRENGTH COLD-ROLLED STEEL SHEET AND MANUFACTURING METHOD THEREOF |
| JP2024569043A JP2025517791A (ja) | 2022-05-31 | 2022-12-05 | 超高強度冷延鋼板及びその製造方法 |
| US18/961,422 US20250092482A1 (en) | 2022-05-31 | 2024-11-26 | Ultra-high strength cold-rolled steel sheet and manufacturing method therefor |
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| US (1) | US20250092482A1 (ko) |
| EP (1) | EP4534721A4 (ko) |
| JP (1) | JP2025517791A (ko) |
| KR (1) | KR102747791B1 (ko) |
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| WO (1) | WO2023234503A1 (ko) |
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| CN120006159B (zh) * | 2025-02-19 | 2025-09-05 | 东莞市华研新材料科技有限公司 | 一种耐高温金属材料 |
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| KR20090122346A (ko) * | 2007-02-23 | 2009-11-27 | 코루스 스타알 베.뷔. | 냉간압연 및 연속어닐링 고강도 강 스트립, 및 그 제조방법 |
| JP2010037652A (ja) * | 2008-07-11 | 2010-02-18 | Kobe Steel Ltd | 耐水素脆化特性および加工性に優れた高強度冷延鋼板 |
| WO2014019964A1 (en) * | 2012-07-30 | 2014-02-06 | Tata Steel Nederland Technology Bv | A method for producing a high strength strip steel with a good deep drawability and a high strength steel produced thereby |
| KR20180047388A (ko) | 2016-10-31 | 2018-05-10 | 한전케이디엔주식회사 | 선로 상태 판단 장치 |
| KR20200118445A (ko) * | 2018-02-07 | 2020-10-15 | 타타 스틸 네덜란드 테크날러지 베.뷔. | 고강도 열간 압연 또는 냉간 압연 및 어닐링된 강 및 그 제조 방법 |
| KR102403767B1 (ko) * | 2020-11-25 | 2022-05-30 | 현대제철 주식회사 | 초고강도 냉연강판 및 그 제조방법 |
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| JP4977879B2 (ja) * | 2010-02-26 | 2012-07-18 | Jfeスチール株式会社 | 曲げ性に優れた超高強度冷延鋼板 |
| KR101987570B1 (ko) * | 2015-03-25 | 2019-06-10 | 제이에프이 스틸 가부시키가이샤 | 냉연 강판 및 그 제조 방법 |
| JP7134106B2 (ja) * | 2018-03-26 | 2022-09-09 | 株式会社神戸製鋼所 | 高強度鋼板および高強度亜鉛めっき鋼板 |
| CN112930411B (zh) * | 2018-10-18 | 2022-08-30 | 杰富意钢铁株式会社 | 高屈服比高强度电镀锌系钢板及其制造方法 |
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| CN112126860B (zh) * | 2020-09-25 | 2022-03-04 | 重庆科技学院 | 一种冷成形超高强度低合金马氏体钢 |
| KR102865563B1 (ko) * | 2020-12-25 | 2025-09-29 | 제이에프이 스틸 가부시키가이샤 | 강판, 부재 및 그것들의 제조 방법 |
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2022
- 2022-05-31 KR KR1020220066958A patent/KR102747791B1/ko active Active
- 2022-12-05 JP JP2024569043A patent/JP2025517791A/ja active Pending
- 2022-12-05 WO PCT/KR2022/019639 patent/WO2023234503A1/ko not_active Ceased
- 2022-12-05 EP EP22945041.6A patent/EP4534721A4/en active Pending
- 2022-12-05 CN CN202280096497.4A patent/CN119278291A/zh active Pending
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| KR20090122346A (ko) * | 2007-02-23 | 2009-11-27 | 코루스 스타알 베.뷔. | 냉간압연 및 연속어닐링 고강도 강 스트립, 및 그 제조방법 |
| JP2010037652A (ja) * | 2008-07-11 | 2010-02-18 | Kobe Steel Ltd | 耐水素脆化特性および加工性に優れた高強度冷延鋼板 |
| WO2014019964A1 (en) * | 2012-07-30 | 2014-02-06 | Tata Steel Nederland Technology Bv | A method for producing a high strength strip steel with a good deep drawability and a high strength steel produced thereby |
| KR20180047388A (ko) | 2016-10-31 | 2018-05-10 | 한전케이디엔주식회사 | 선로 상태 판단 장치 |
| KR20200118445A (ko) * | 2018-02-07 | 2020-10-15 | 타타 스틸 네덜란드 테크날러지 베.뷔. | 고강도 열간 압연 또는 냉간 압연 및 어닐링된 강 및 그 제조 방법 |
| KR102403767B1 (ko) * | 2020-11-25 | 2022-05-30 | 현대제철 주식회사 | 초고강도 냉연강판 및 그 제조방법 |
Non-Patent Citations (1)
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| See also references of EP4534721A4 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP4534721A4 (en) | 2025-10-01 |
| US20250092482A1 (en) | 2025-03-20 |
| EP4534721A1 (en) | 2025-04-09 |
| JP2025517791A (ja) | 2025-06-10 |
| KR102747791B1 (ko) | 2024-12-31 |
| KR20230166682A (ko) | 2023-12-07 |
| CN119278291A (zh) | 2025-01-07 |
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