EP0969112B2 - Procede de preparation des toles d'acier biphasees a haute resistance mécanique et a haute capacité d'absorption d'energie de chock - Google Patents

Procede de preparation des toles d'acier biphasees a haute resistance mécanique et a haute capacité d'absorption d'energie de chock Download PDF

Info

Publication number
EP0969112B2
EP0969112B2 EP98907247.5A EP98907247A EP0969112B2 EP 0969112 B2 EP0969112 B2 EP 0969112B2 EP 98907247 A EP98907247 A EP 98907247A EP 0969112 B2 EP0969112 B2 EP 0969112B2
Authority
EP
European Patent Office
Prior art keywords
temperature
deformation
strength
ferrite
steel sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98907247.5A
Other languages
German (de)
English (en)
Other versions
EP0969112A4 (fr
EP0969112A1 (fr
EP0969112B1 (fr
Inventor
Akihiro c/o Nippon Steel Corporation UENISHI
Manabu c/o Nippon Steel Corporation TAKAHASHI
Yukihisa c/o Nippon Steel Corporation KURIYAMA
Yasuharu c/o Nippon Steel Corp. Kimitsu Works SAKUMA
Osamu c/o Nippon Steel Corp. Oita Works KAWANO
Junichi c/o Nippon Steel Corp. Oita Works WAKITA
Hidesato c/o Nippon Steel Corp. Oita Works MABUCHI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel and Sumitomo Metal Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27524972&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0969112(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from JP19029797A external-priority patent/JP3530347B2/ja
Priority claimed from JP22300897A external-priority patent/JP3936440B2/ja
Priority claimed from JP25893897A external-priority patent/JP3839928B2/ja
Priority to EP10181225.3A priority Critical patent/EP2314729B2/fr
Application filed by Nippon Steel and Sumitomo Metal Corp filed Critical Nippon Steel and Sumitomo Metal Corp
Publication of EP0969112A1 publication Critical patent/EP0969112A1/fr
Publication of EP0969112A4 publication Critical patent/EP0969112A4/fr
Publication of EP0969112B1 publication Critical patent/EP0969112B1/fr
Application granted granted Critical
Publication of EP0969112B2 publication Critical patent/EP0969112B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the present invention relates to a method of producing dual-phase type high-strength steel sheets, for automobiles use, which have excellent dynamic deformation properties and exhibit excellent impact absorption properties, and are intended to be used as structural members and reinforcing materials primarily for automobiles them.
  • high-strength steels have been increasing for the purpose of achieving lighter weight vehicle bodies in consideration of fuel consumption restrictions on automobiles and even more applications for high-strength steel are expected as domestic and foreign restrictions, relating to estimated impact absorption properties in automobile accidents, become rapidly more broad and strict.
  • front side members can allow impact energy to be absorbed through collapse of the member, thus lessening the impact experienced by passengers.
  • the present inventors have reported on the high strain rate properties and impact energy absorption properties of high-strength thin steel sheets in CAMP-ISIJ Vol.9 (1966), pp.1112-1115 , wherein they explain that the dynamic strength at a high strain rate of 10 3 (s -1 ) increases dramatically compared to the static strength at a low strain rate speed of 10 -3 (s -1 ), that absorption energy during crashes is increased by greater steel material strengths, that the strain rate dependency of materials depends on the structure of the steel, and that TRIP type steel (Transformation induced plasticity type steel) and dual-phase (hereunder, "DP”) type steel exhibit both excellent press formability and high impact absorption properties.
  • TRIP type steel Transformation induced plasticity type steel
  • DP dual-phase
  • JP-A-07-90482 discloses a cold-rolled thin steel sheet excellent in impact resistance and its production, in which a steel sheet is hot rolled preferably with a finishing hot rolling temperature of 850°C or higher, then the hot-rolled steel sheet is coiled at a temperature of 650°C or higher, and the hot-rolled steel sheet is cold-rolled, annealed at a temperature in the temperature range of 780 to 900°C, cooled to 500°C with a cooling rate of 15 to 50°C/sec and further cooled to 300°C with a cooling rate of 5 to 35°C/sec.
  • EP-A-0 719 868 discloses a steel sheet for automobiles having excellent impact resistance and method of manufacturing the steel sheet, in which a hot-rolled steel sheet is produced by the steps: hot rolling with a finishing temperature of 780 to 850°C, starting to cool the hot-rolled steel sheet within 0.5 seconds with a cooling rate of 30°C/sec or more to a temperature range of 750 to 650°C, subsequently holding the hot-rolled steel sheet in the temperature range of 750 to 600°C for 4 to 60 seconds, further cooling the hot-rolled steel sheet with a cooling rate of 30°C/sec or more and coiling in the temperature range of 500 to 100°C, and a cold-rolled steel sheet is produced by the steps: annealing a hot-rolled and cold-rolled steel sheet in the temperature range of 780 to 950°C, cooling the annealed steel sheet to 400°C at a cooling rate of 15 to 60°C/sec and further cooling the steel sheet to 150°C with a cooling rate of 3 to 15°C/sec.
  • the present invention has been proposed as a means of overcoming the problems described above, and provides a method of producing dual-phase type high-strength steel sheets for automobiles use, which have excellent impact absorption properties and excellent dynamic deformation properties.
  • the invention further provides a method of producing dual-phase type high-strength steel sheets, for automobiles, with excellent dynamic deformation properties, which are high-strength steel sheets used for automotive parts, such as front side members, and which are selected based on exact properties and standards for impact energy absorption during collisions and can reliably provide guaranteed safety.
  • the invention still further provides a method of producing dual-phase type high-strength steel sheets for automobiles with excellent dynamic deformation properties, which exhibit all the properties suitable for press forming of members, including excellent shape fixability, excellent stretchability and excellent flangeability.
  • the object above can be achieved by the features specified in the claims.
  • Impact absorbing members such as front side members of automobiles are produced by bending and press forming of steel sheets. Because impacts during automobile collisions are absorbed by such members which have undergone press forming, they must have high impact absorption properties even after having undergone the pre-deformation corresponding to the press forming. At the current time, however, no attempt has been made to obtain high-strength steel sheets with excellent impact absorption properties as actual members, with consideration of both the increase in the deformation stress by press forming and the increase in deformation stress due to a higher strain rate, as was mentioned above.
  • steel sheets with a dual-phase (DP) structure are ideal as high-strength steel sheets with excellent impact absorption properties for actual members which are press formed as described above. It was demonstrated that such steel sheets with a dual-phase microstructure, which is a composite microstructure wherein the dominating phase is a ferrite phase responsible for the increase in deformation resistance by an increased strain rate, and the second phase includes a hard martensite phase, have excellent dynamic deformation properties.
  • the microstructure of the final steel sheets is a composite structure wherein the dominating phase is ferrite and another low temperature product phase includes a hard martensite phase at a volume fraction of 3 ⁇ 50% after deformation at 5% equivalent strain of the steel sheet.
  • the volume fraction of the martensite phase since high-strength steel sheets and even steel sheets with high dynamic deformation properties cannot be obtained if the martensite phase is less than 3%, the volume fraction of the martensite phase must be at least 3%. Also, if the martensite phase exceeds 50%, this results in a smaller volume fraction of the ferrite phase responsible for greater deformation resistance due to increased deformation speed, making it impossible to obtain steel sheets with excellent dynamic deformation properties compared to static deformation strength while also hindering press formability, and therefore it was found that the volume fraction of the martensite phase must be 3 ⁇ 50%.
  • the present inventors then pursued experimentation and research based on these findings and, as a result, found that although the degree of pre-deformation corresponding to press forming of impact absorbing members such as front side members sometimes reaches a maximum of over 20%, depending on the location, the majority are locations with 0% ⁇ 10% of equivalent strain, and that by understanding the effect of pre-deformation in this range, it is possible to estimate the behavior of the member as a whole after pre-deformation. Consequently, according to the invention, a deformation of from 0% to 10% of equivalent strain was selected as the amount of pre-deformation applied to members during press forming.
  • Fig. 1 is a graph showing the relationship between the absorption energy (Eab) of a press formed member during collision and the material strength (S), for the different steel types shown in Table 5, according to an example to be described later.
  • the material strength S is the tensile strength (TS) according to the common tensile test.
  • the member absorption energy (Eab) is the absorption energy in the lengthwise direction (direction of the arrow) along a press formed member such as shown in Fig. 2 , upon collision with a 400 kg mass weight at a speed of 15 m/sec, to a crushing degree of 100 mm.
  • hat-shaped section 1 consists of a 2.0 mm-thick steel sheet formed into a hat-shaped section 1 with a steel sheet 2 of the same thickness and the same type of steel, joined together by spot welding, the hat-shaped section 1 having a corner radius of 2 mm, and with spot welding points indicated by 3.
  • Fig. 1 From Fig. 1 it is seen that the member absorption energy (Eab) tends to increase with the strength of materials under normal tensile testing, though with considerable variation.
  • the materials in Fig. 1 were subjected to pre-deformation of more than 0% and less than or equal to 10% of equivalent strain, and then the static deformation strength ⁇ swhen deformed in a strain rate range of 5 x 10 -4 - 5 x 10 -3 (s -1 ) and the dynamic deformation strength ⁇ d when deformed in a strain rate range of 5 x 10 2 - 5 x 10 3 (s -1 ) after the pre-deformation, were measured.
  • a classification was possible based on ( ⁇ d - ⁇ s).
  • the symbols plotted in Fig. 1 were as follows:
  • Fig. 3 shows the relationship between the work hardening coefficient of a steel sheet and the dynamic energy absorption which indicates the member impact absorption properties, for a class of materials with the same yield strength.
  • increased work hardening coefficients of the steel sheets result in improved member impact absorption properties (dynamic energy absorption)
  • the work hardening coefficient of a steel sheet can properly indicate the member impact absorption properties so long as the yield strength class is the same.
  • the yield strength x work hardening coefficient can be an indicator of the member impact absorption properties.
  • work hardening coefficient was expressed in terms of an n value of 5% ⁇ 10% strain in consideration of the strain undergone by members during press forming, from the viewpoint of improving the dynamic energy absorption, work hardening coefficients of under 5% strain or work hardening coefficients of even more than 10% strain may be preferred.
  • a schematic illustration of this test method is shown in Fig. 7 .
  • Fig. 5 , 4 is a worktop
  • 5 is a test piece
  • 6 is a spot welding section.
  • Fig. 6 7 is a hat-shaped test piece and 8 is a spot welding section.
  • Fig. 7 9 is a worktop
  • 10 is a test piece
  • 11 is a falling weight (150 kg)
  • 12 is a frame
  • 13 is a shock absorber.
  • the work hardening coefficient and yield strength of each steel sheet was determined in the following manner.
  • the steel sheet was shaped into a JIS-#5 test piece (gauge length: 50 mm, parallel width: 25 mm), subjected to tensile test at a strain rate of 0.001 (s -1 ) to determine the yield strength and work hardening coefficient (n value at 5% ⁇ 10% strain).
  • the steel sheet used had a sheet thickness of 1.2 mm and the steel sheet composition contained C at 0.02-0.25 wt%, either or both Mn and Cr at a total of 0.15 ⁇ 3.5 wt% and one or more of Si, Al and P at a total of 0.02-4.0 wt%, with the remainder Fe as the main component.
  • Fig. 8 is a graph showing the relationship between the average value ⁇ dyn of the deformation stress in the range of 3 ⁇ 10% of equivalent strain when deformed in a strain rate range of 5 x 10 2 - 5 x 10 3 (s -1 ) and the static material strength (TS), as an index of the impact energy absorption property upon collision, according to the invention, where the static material strength (TS) is the tensile strength (TS: MPa) in the static tensile test as measured in a strain rate range of 5 x 10 -4 - 5 x 10 -3 (s -1 ).
  • impact absorbing members such as front side members have a hat-shaped cross-sectional shape
  • the present inventors have found that despite deformation proceeding up to a high maximum strain of over 40%, at least 70% of the total absorption energy is absorbed in a strain range of 10% or lower in a high-speed stress-strain diagram. Therefore, the dynamic deformation resistance with high-speed deformation at 10% or lower was used as the index of the high-speed collision energy absorption property.
  • the index used for the impact energy absorption property was the average stress: ⁇ dyn in the range of 3 ⁇ 10% of equivalent strain when deformed in a strain rate range of 5 x 10 2 - 5 x 10 3 (s -1 ) high-speed tensile deformation.
  • the average stress: ⁇ dyn of 3 ⁇ 10% upon high-speed deformation generally increases with increasing static tensile strength ⁇ maximum stress (TS: MPa) in a static tensile test measured in a stress rate range of 5 x 10 -4 - 5 x 10 -3 (s -1 ) ⁇ of the steel material prior to pre-deformation or baking treatment. Consequently, increasing the static tensile strength (which is synonymous with the static material strength) of the steel material directly contributes to an improved impact energy absorption property of the member. However, increased strength of the steel results in poorer press formability into members, making it difficult to obtain members with the necessary shapes. Consequently, steels having a high ⁇ dyn with the same tensile strength TS are preferred.
  • steel sheets wherein the average value ⁇ dyn (MPa) of the deformation stress in the range of 3 ⁇ 10% of equivalent strain when deformed in a strain rate range of 5 x 10 2 - 5 x 10 -3 (s -1 ), after pre-deformation of more than 0% and less than or equal to 10% of equivalent strain satisfies the inequality: ⁇ dyn ⁇ 0.766 x TS + 250 as expressed in terms of the tensile strength (TS: MPa) in the static tensile test as measured in a strain rate range of 5 x 10 -4 - 5 x 10 -3 (s -1 ) prior to pre-deformation, have higher impact energy absorption properties as actual members compared to other steels, and that the impact energy absorption property is improved without increasing the overall weight of the member, making it possible to provide high-strength steel sheets with high dynamic deformation resistance.
  • TS tensile strength
  • YS(0)/TS'(5) is no greater than 0.7, which amount is dependent on the initial microstructure, the amount of solid solution elements in the low temperature product phase other than the martensite phase and the main ferrite phase, and the deposited state of carbides, nitrides and carbonitrides.
  • YS(0) is the yield strength
  • TS' (5) is the tensile strength (TS') in the static tensile test with pre-deformation at 5% of equivalent strain or after further bake hardening treatment (BH treatment). It was also demonstrated that steel sheets with even more excellent dynamic deformation properties can be obtained when the yield strength: YS(0) x work hardening coefficient is at least 70.
  • the martensite is at a volume fraction of 3-50%, and preferably 3 ⁇ 30%.
  • the average grain size of the martensite is preferably no greater than 5 ⁇ m, and the average grain size of the ferrite is preferably no greater than 10 ⁇ m. That is, the martensite is hard, and contributes to a decrease in the yield ratio and an improvement in the work hardening coefficient, by producing a mobile dislocations primarily in adjacent ferrite grains; however, by satisfying the restrictions mentioned above it is possible to disperse fine martensite in the steel, so that the improvement in the properties spreads throughout the entire steel sheet.
  • this dispersion of fine martensite in the steel can help to avoid deterioration in the hole expansion ratio and tensile strength x total elongation, which is an adverse effect of the hard martensite. Also, because it is possible to reliably achieve work hardening coefficient ⁇ 0.130, tensile strength x total elongation ⁇ 18,000 and hole expansion ratio ⁇ 1.2, it is thereby possible to improve the impact absorption properties and press formability.
  • the yield ratio With a martensite volume fraction of less than 3%, the yield ratio becomes larger while the press formed member cannot exhibit an excellent work hardening property (work hardening coefficient ⁇ 0.130) after it has undergone collision deformation, and since the deformation resistance (load) stays at a low level, and the dynamic energy absorption is low preventing improvement in the impact absorption properties.
  • the volume fraction of the martensite is preferred to be no greater than 30%.
  • the ferrite is present at a volume fraction of preferably at least 50%, and more preferably at least 70%, and its average grain size (mean circle equivalent diameter) is preferably no greater than 10 ⁇ m, and more preferably no greater than 5 ⁇ m, with the martensite preferably adjacent to the ferrite. This aids the fine dispersion of the martensite in the ferrite matrix, while effectively extending the property-improving effect, beyond simply a local effect, to the entire steel sheet, favorably acting to prevent the adverse effects of the martensite.
  • the structure of the remainder present with the martensite and ferrite may be a mixed structure comprising a combination of one or more from among pearlite, bainite, retained ⁇ , etc., and although primarily bainite is preferred in cases which require hole expansion properties, since retained ⁇ undergoes work-induced transformation into martensite by press forming, experimental results have shown that including retained austenite prior to press forming has an effect even in preferred small amounts (5% or less).
  • the ratio of the martensite and ferrite particle sizes is no greater than 0.6, and the ratio of the hardnesses to be at least 1.5.
  • Dual-phase type high-strength steel sheets with excellent dynamic deformation properties which are used according to the invention are steel sheets containing the following chemical compositions, in terms of weight percentage: C at 0.02 ⁇ 0.25%, either or both Mn and Cr at a total of 0.15 ⁇ 3.5%, one or more from among Si, Al and P at a total of 0.02 ⁇ 4.0%, if necessary also one or more from among Ni, Cu and Mo at a total of no more than 3.5%, one or more from among Nb, Ti and V at no more than 0.30%, and either or both Ca and REM at 0.0005 ⁇ 0.01% for Ca and 0.005 ⁇ 0.05% for REM, with the remainder Fe as the primary component.
  • C is the element which most strongly affects the microstructure of the steel sheet, and if its content is too low it will become difficult to obtain martensite with the desired amount and strength. Addition in too great an amount leads to unwanted carbide precipitation, inhibited increase in deformation resistance at higher strain rates and overly high strength, as well as poor press formability and weldability; the content is therefore 0.02-0.25 wt%.
  • Mn, Cr: Mn and Cr have an effect of stabilizing austenite and guaranteeing sufficient martensite, and are also solid solution hardening elements; they must therefore be added in a minimum amount of 0.15 wt%, but if added in too much the aforementioned effect becomes saturated thus producing adverse effects such as preventing ferrite transformation, and thus they are added in the maximum amount of 3.5 wt%.
  • Si, Al, P are useful elements for producing martensite, and they promote production of ferrite and suppress precipitation of carbides, thus having the effect of guaranteeing sufficient martensite, as well as a solid solution hardening effect and a deoxidization effect.
  • P can also promote martensite formation and solid solution hardening, similar to Al and Si. From this standpoint, the minimum amount of Si + Al + P added must be at least 0.02 wt%. On the other hand, excessive addition will saturate this effect and result instead in brittleness, and therefore the maximum amount of addition is no more than 4.0 wt%.
  • Si scales can be avoided by adding Si at no greater than 0.1 wt%, and conversely by adding it at 1.0 wt% or greater Si scales can be produced over the entire surface so that they are not conspicuous.
  • the P content may be kept at no greater than 0.05%, and preferably no greater than 0.02%.
  • Ni, Cu, Mo are added when necessary, and are austenite-stabilizing elements similar to Mn, which increase the hardenability of the steel, and are effective for adjustment of the strength. From the standpoint of weldability and chemical treatment, they can be used when the amounts of C, Si, Al and Mn are restricted, but if the total amount of these elements added exceeds 3.5 wt% the dominant ferrite phase will tend to be hardened, thus inhibiting the increase in deformation resistance by a greater strain rate, as well as raising the cost of the steel sheet; the amount of these elements added is therefore 3.50 wt% or lower.
  • Nb, Ti, V These elements are added when necessary, and are effective for strengthening the steel sheet through formation of carbides, nitrides and carbonitrides. However, when added at greater than 0.3 wt% they are deposited in large amounts in the dominant ferrite phase or at the grain boundaries as carbides, nitrides and carbonitrides, becoming a source of the mobile dislocation during high speed deformation, and inhibiting the increase in deformation resistance by greater strain rates. In addition, the deformation resistance of the dominant phase becomes higher than necessary, thus wasting the C and leading to higher costs; the maximum amount to be added is therefore 0.3 wt%.
  • B is an element which is effective for strengthening since it improves the hardenability of the steel by suppressing production of ferrite, but if it is added at greater than 0.01 wt% its effect will be saturated, and therefore B is added at a maximum of 0.01 wt%.
  • Ca is added to at least 0.0005 wt% for improved press formability (especially hole expansion ratio) by shape control (spheroidization) of sulfide-based inclusions, and the maximum amount thereof to be added is 0.01 wt% in consideration of effect saturation and the adverse effect due to increase in the aforementioned inclusions (reduced hole expansion ratio).
  • REM is added in an amount of from 0.005% to 0.05 wt%.
  • the amount of S is no greater than 0.01 wt%, and preferably no greater than 0.003 wt%, from the standpoint of press formability (especially hole expansion ratio) by sulfide-based inclusions, and reduced spot weldability.
  • the pre-deformation is working with a tempering rolling or tension leveler which is applied to the steel sheet material prior to its press forming.
  • a tempering roller and tension leveler may be used. That is, the means used may include a tempering rolling, a tension leveler, or a tempering roller and tension leveler.
  • the steel sheet material may also be subjected to press forming after being worked with a tempering rolling or tension leveler.
  • the amount of pre-deformation applied with the tempering rolling and/or tension leveler i.e. the degree of plastic deformation (T) will differ depending on the initial dislocation density, and T should be small if the initial density is large.
  • the plastic deformation (T) is determined based on the ratio between the yield strength YS(0) and the tensile strength TS'(5) in the static tensile test with pre-deformation at 5% of equivalent strain or after further bake hardening treatment (BH treatment), or YS(0)/TS'(5). That is, YS(0)/TS'(5) is an indicator of the sum of the initial dislocation density and the dislocation density introduced by 5% deformation, and the amount of the solid solution elements; it may be concluded that a smaller YS(0)/TS'(5) means a higher initial dislocation density and more of the solid solution elements.
  • YS(0)/TS'(5) is therefore no greater than 0.7, and is preferably provided according to the following equation: 23.5 YS 0 / TS ′ 5 ⁇ 0.5 + 15 ⁇ T ⁇ 2.5 YS 0 / TS ′ 5 ⁇ 0.5 + 0.5 wherein the upper limit for T is determined from the standpoint of press formability including impact absorption property and flexibility.
  • a continuous cast slab is fed directly from casting to a hot rolling step, or is hot rolled upon reheating after momentary cooling.
  • Thin gauge continuous casting and continuous hot rolling techniques may be applied for the hot rolling in addition to normal continuous casting, but in order to avoid a lower ferrite volume fraction and a coarser average grain size of the thin steel sheet microstructure, the bar (cast strip) thickness at the hot rolling approach side (the initial steel bar thickness) is preferred to be at least 25 mm.
  • the mean circle equivalent size of ferrite of the steel sheet is made coarser, while it is also a disadvantage against obtaining the desired martensite.
  • the final pass rolling speed for the hot rolling is preferred to be at least 500 mpm and more preferably at least 600 mpm, in light of the problems described above.
  • the mean circle equivalent diameter of ferrite of the steel sheet is made coarser, while it is also a disadvantage against obtaining the desired martensite.
  • the finishing temperature for the hot rolling is from Ar 3 - 50°C to Ar 3 + 120°C.
  • Ar 3 - 50°C deformed ferrite is produced, with inferior work hardening property and press formability.
  • Ar 3 + 120°C and the mean circle equivalent size of ferrite of the steel sheet is made coarser, while it is also becomes difficult to obtain the desired martensite.
  • the average cooling rate for cooling in the run-out table is least 5°C/sec. At less than 5°C/sec it becomes difficult to obtain the desired martensite.
  • the coiling temperature is no higher than 350°C. At higher than 350°C it becomes difficult to obtain the desired martensite.
  • the hot rolling is carried out so that when the finishing temperature for hot rolling is in the range of Ar 3 - 50°C to Ar 3 + 120°C, the metallurgy parameter A satisfies inequalities (1) and (2).
  • the average cooling rate on the run-out table is at least 5°C/sec, and the coiling to be carried out under conditions such that the relationship between the metallurgy parameter A and the coiling temperature (CT) satisfies inequality (3).
  • the cold rolled sheet according to the invention is then subjected to the different steps following hot-rolling and coiling and is cold rolled and subjected to annealing.
  • the annealing is ideally continuous annealing through an annealing cycle such as shown in Fig. 12 , and during the annealing of the continuous annealing step, it must be kept for at least 10 seconds in the temperature range of Ac 1 - Ac 3 . At less than Ac 1 austenite will not be produced and it will therefore be impossible to obtain martensite thereafter, while at greater than Ac 3 the austenite monophase structure will be coarse, and it will therefore be impossible to obtain the desired average grain size for the martensite.
  • the maximum residence time is preferably no greater than 200 seconds, from the standpoint of avoiding addition to the equipment and coarsening of the microstructure.
  • the cooling after this annealing must be at an average cooling rate of at least 5°C/sec. At less than 5°C/sec the desired space factor for the martensite cannot be achieved. Although there is no particular upper limit here, it is preferably 300°C/sec when considering temperature control during the cooling.
  • the cooled steel sheet is heated to a temperature To from Ac 1 - Ac 3 in the continuous annealing cycle shown in Fig. 12 , and cooled under cooling conditions provided by a method wherein cooling to a secondary cooling start temperature Tq in the range of 550°C-To at the primary cooling rate of 1 ⁇ 10°C/sec is followed by cooling to a secondary cooling end temperature Te which is no higher than a temperature Tem which is determined by the chemical compositions of the steel and annealing temperature To, at a secondary cooling rate of 10 ⁇ 200°C/sec.
  • T2 or the difference between the value excluding the effect of the C concentration in the austenite (T1) and the value indicating the effect of the C concentration (T2).
  • T1 is the temperature calculated from the solid solution element concentration excluding C
  • T2 is the temperature calculated from the C concentration in the retained austenite at Ac 1 and Ac 3 determined by the chemical compositions of the steel and Tq determined by the annealing temperature To.
  • Ceq represents the carbon equivalents in the retained austenite at the annealing temperature To.
  • T1 561 ⁇ 33 ⁇ Mn % + Ni + Cr + Cu + Mo / 2
  • Ac 3 910 ⁇ 203 ⁇ C % 1 / 2 ⁇ 15.2 ⁇ Ni % + 44.7 ⁇ Si % ⁇ 104 ⁇ V % + 31.5 ⁇ Mo % ⁇ 30 ⁇ Mn % ⁇ 11 ⁇ Cr % ⁇ 20 ⁇ Cu % + 70 ⁇ P % + 40 ⁇ Al % + 400 ⁇ Ti %
  • Te when Te is equal to or greater than Tem, the desired martensite cannot be obtained. Also, if Toa is 400°C or higher, the martensite obtained by cooling is tempered, making it impossible to achieve satisfactory dynamic properties and press formability. On the other hand, if Toa is less than Te - 50°C, additional cooling equipment is necessary, and greater variation will result in the material due to the difference between the temperature of the continuous annealing furnace and the temperature of the steel sheet; this temperature was therefore determined as the lower limit. Also, the upper limit for the holding time was determined to be 20 minutes, because when it is longer than 20 minutes it becomes necessary to expand the equipment.
  • the microstructure of the steel sheet is a composite microstructure wherein the dominating phase is ferrite, and the second phase is another low temperature product phase containing martensite at a volume fraction from 3% ⁇ 50% after shaping and working at 5% equivalent strain, and wherein the difference between the quasi-static deformation strength ⁇ s when deformed in a strain rate range of 5 x 10 -4 - 5 x 10 -3 (1/s) after pre-deformation of more than 0% and less than or equal to 10% of equivalent strain, and the dynamic deformation strength ⁇ d measured in a strain rate range of 5 x 10 2 - 5 x 10 3 (1/s) after the aforementioned pre-deformation, i.e.
  • the steel sheets according to the invention may be made into any desired product by annealing, tempering rolling, electronic coating or hot-dip coating.
  • the 26 steel materials listed in Table 1 were heated to 1050 ⁇ 1250°C and subjected to hot rolling, cooling and coiling under the production conditions listed in Table 2, to produce hot rolled steel sheets.
  • the steel sheets satisfying the chemical composition conditions and production conditions according to the invention have a dual-phase structure with a martensite volume fraction of at least 3% and no greater than 50%, and as shown in Fig.
  • the mechanical properties of the hot rolled steel sheets indicated excellent impact absorption properties as represented by a work hardening coefficient of at least 0.13 at 5 ⁇ 10% strain, ⁇ d - ⁇ s ⁇ 60 MPa, and ⁇ dyn ⁇ 0.766 x TS + 250, while also having suitable press formability and weldability.
  • Table 2 Production conditions Steel No. Hot rolling conditions Cooling conditions Coiling conditions Finishing temp. °C Initial steel strip thickness (mm) Final pass rolling speed (mpm) Final sheet thickness (mm) Strain rate (/sec) log A calculated ⁇ T °C Inequality (2) Aver. cooling rate (°C/sec) Note Coiling temp.
  • the 22 steel materials listed in Table 5 were heated to 1050 ⁇ 1250°C and subjected to hot rolling, cooling and coiling, followed by acid pickling and then cold rolling under the conditions listed in Table 6 to produce cold rolled steel sheets.
  • Temperatures Ac 1 and Ac 3 were then calculated from the chemical compositions for each steel, and the sheets were subjected to heating, cooling and holding under the annealing conditions listed in Table 6, prior to cooling to room temperature.
  • the steel sheets satisfying the chemical composition conditions and production conditions according to the invention have a dual-phase structure with a martensite volume fraction of at least 3% and no greater than 50% and, as shown in Fig.
  • the mechanical properties of the hot-rolled steel sheets indicated excellent impact absorption properties as represented by a work hardening coefficient of at least 0.13 at 5 ⁇ 10% strain, ⁇ d - ⁇ s ⁇ 60 MPa, and ⁇ dyn ⁇ 0.766 x TS + 250, while also having suitable press formability and weldability.
  • Table 7 Microstructure of steels Steel No.
  • the microstructure was evaluated by the following method.
  • a tensile test was conducted according to JIS5 (gauge mark distance: 50 mm, parallel part width: 25 mm) with a strain rate of 0.001/s and, upon determining the tensile strength (TS), yield strength (YS), total elongation (T. El) and work hardening coefficient (n value for 1% ⁇ 5% strain), the YS x work hardening coefficient and TS x T. El. were calculated.
  • the stretch flanging property was measured by expanding a 20 mm punched hole from the burrless side with a 30° cone punch, and determining the hole expansion ratio (d/d 0 ) between the hole diameter (d) at the moment at which the crack penetrated the plate thickness and the original hollow diameter (do, 20 mm).
  • the spot weldability was judged to be unsuitable if a spot welding test piece bonded at a current of 0.9 times the expulsion current using an electrode with a tip radius of 5 times the square root of the steel sheet thickness underwent peel fracture when ruptured with a chisel.
  • the present invention makes it possible to provide, in an economical and stable manner, high-strength hot rolled steel sheets and cold rolled steel sheets for automobiles which provide previously unobtainable excellent impact absorption properties and press formability and thus offers a markedly wider range of objects and conditions for uses of high-strength steel sheets.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Claims (2)

  1. Procédé pour produire une tôle d'acier laminé à chaud haute résistance biphasique ayant des propriétés de forte absorption de l'énergie d'impact, caractérisé en ce que
    un lingot coulé en continu contenant, en pourcentages en poids, C : 0,02 à 0,25 %, l'un ou l'autre ou les deux de Mn et Cr en une quantité totale de 0,15 à 3,5 %, un ou plusieurs choisi(s) parmi Si, Al et P en une quantité totale de 0,02 à 4,0 %, éventuellement un ou plusieurs choisi(s) parmi Ni, Cu et Mo en une quantité totale ne dépassant pas 3,5 %, éventuellement un ou plusieurs choisi(s) parmi Nb, Ti et V en une quantité ne dépassant pas 0,30 %, et éventuellement l'un ou l'autre ou les deux de Ca et REM en une quantité de 0,0005 à 0,01 % pour Ca et de 0,005 à 0,05 % pour REM, en outre éventuellement un ou plusieurs choisi(s) parmi B à raison d'au plus 0,01 %, S à raison d'au plus 0,01 % et N à raison d'au plus 0,02 %, le reste étant Fe et des impuretés inévitables, est introduit directement depuis la coulée vers une étape de laminage à chaud, ou est laminé à chaud lors du réchauffage après refroidissement momentané,
    est soumis à un laminage à chaud à une température de finissage d'Ar3 - 50°C à Ar3 + 120°C,
    le laminage à chaud est effectué de façon que le paramètre métallurgique A satisfasse aux inégalités (1) et (2) ci-dessous, la vitesse de refroidissement moyenne subséquente dans la table de sortie est d'au moins 5°C/s, et le bobinage est accompli de façon que la relation entre ledit paramètre métallurgique A et la température de bobinage (CT) satisfasse à l'inégalité (3) ci-dessous : 9 ≤ logA ≤ 18
    Figure imgb0034
     ΔT ≤ 21 × logA − 61
    Figure imgb0035
     CT ≤ 6 × logA + 242
    Figure imgb0036
     où le paramètre métallurgique A est exprimé par l'équation suivante : A = ε * × exp 75282 − 42745 × C eq / 1 , 978 × FT + 273
    Figure imgb0037
     dans laquelle :
    FT : température de finissage (°C)
    Ceq : équivalents carbone = C + Mneq/6 (%)
    Mneq : équivalents manganèse = Mn + (Ni + Cr + Cu + Mo)/2 (%)
    ε* : vitesse de déformation au passage final (s-1)
    ϵ * = v : R x h 1 x 1 / r x ⁢ ln ⁡ 1 / 1 − r
    Figure imgb0038
    h1 : épaisseur de tôle à l'approche du passage final
    h2 : épaisseur de tôle à la sortie du passage final
    r : (h1 - h2)/h1
    R : rayon du cylindre
    v : vitesse à la sortie du passage final
    Δ·T : température de finissage (température à la sortie du passage final de finissage) - température à l'approche du finissage (température à l'approche du premier passage de finissage)
    Ar3 : 901 - 325 C% + 33 Si% - 92 Mneq, et
    l'usinage avec un laminage de revenu et/ou un niveleur de tension est réalisé de sorte que le degré de déformation plastique (T) appliquée au laminage de revenu et/ou au niveleur de tension satisfait à l'inégalité (4) ci-dessous : 2 , 5 × YS 0 / TS ′ 5 − 0 , 5 + 15 ≥ T ≥ 2 , 5 × YS 0 / TS ′ 5 − 0 , 5 + 0 , 5
    Figure imgb0039
     dans laquelle :
    YS(0) : limite élastique
    TS'(5) : résistance à la traction dans un test de traction statique avec une pré-déformation à 5 % de déformation équivalente ou après de plus un traitement BH et YS(0)/TS'(5) n'est pas supérieur à 0,7.
  2. Procédé pour produire une tôle d'acier laminé à froid haute résistance biphasique ayant des propriétés de forte absorption de l'énergie d'impact, caractérisé en ce que
    un lingot coulé en continu contenant, en pourcentage en poids, C : 0,02 à 0,25 %, l'un ou l'autre ou les deux de Mn et Cr en une quantité totale de 0,15 à 3,5 %, un ou plusieurs choisi(s) parmi Si, Al et P en une quantité totale de 0,02 à 4,0 %, éventuellement un ou plusieurs choisi(s) parmi Ni, Cu et Mo en une quantité totale ne dépassant pas 3,5 %, éventuellement un ou plusieurs choisi(s) parmi Nb, Ti et V en une quantité ne dépassant pas 0,30 %, et éventuellement l'un ou l'autre ou les deux de Ca et REM en une quantité de 0,0005 à 0,01 % pour Ca et de 0,005 à 0,05 % pour REM, en outre éventuellement un ou plusieurs choisi(s) parmi B à raison d'au plus 0,01 %, S à raison d'au plus 0,01 % et N à raison d'au plus 0,02 %, le reste étant Fe et des impuretés inévitables, est introduit directement depuis la coulée vers une étape de laminage à chaud, ou est laminé à chaud lors du réchauffage après refroidissement momentané,
    est laminé à chaud, la tôle d'acier laminée à chaud et ensuite bobinée est laminée à froid après décapage acide et,
    durant le recuit dans une étape de recuit en continu pour la préparation du produit final, la tôle d'acier laminé à froid est chauffée à une température de recuit (To) comprise entre Ac1 et Ac3 et soumise au recuit tout en étant maintenue dans cette plage de température pendant au moins 10 secondes, et
    ensuite est refroidie à une vitesse de refroidissement primaire de 1 à 10°C/s jusqu'à une température de début de refroidissement secondaire (Tq) située dans la plage allant de 550 à 720°C et puis refroidie à une vitesse de refroidissement secondaire de 10 à 200°C/s jusqu'à une température de fin de refroidissement secondaire (Te) qui n'est pas supérieure à une température (Tem),
    où Tem est la température de début de transformation en martensite pour l'austénite résiduelle à la température de début de refroidissement secondaire Tq et est définie par Tem = T1 - T2, où :
    T1 = 561 - 33 x {Mn% + (Ni + Cr + Cu + Mo) / 2},
    T2 = 474 x (Ac3 - Ac1) x C / (To - Ac1) quand Ceq* = (Ac3 - Ac1) x C / (To - Ac1) + (Mn + Si/4 + Ni/7 + Cr + Cu + 1,5Mo) / 6 est supérieur à 0,6, et T2 = 474 x (Ac3 - Ac1) x C /{3 x (Ac3 - Ac1) x C + [(Mn + Si/4 + Ni/7 + Cr + Cu + 1,5Mo) / 2 - 0,85] x (To - Ac1)} quand Ceq* vaut 0,6 ou moins,
    où :
    Ac1 = 723 x 0,7 x Mn% - 16,9 x Ni% + 29,1 x Si% + 16,9 x Cr%,
    Ac3 = 910 - 203 x (C%)1/2 - 15,2 x Ni% + 44,7 x Si% + 104 x V% + 31,5 x Mo% + 30 x Mn% - 11 x Cr% - 20 x Cu% + 70 x P% + 40 x Al% + 400 x Ti%,
    et l'usinage avec un laminage de revenu et/ou un niveleur de tension est réalisé de sorte que le degré de déformation plastique (T) appliquée au laminage de revenu et/ou au niveleur de tension satisfait à l'inégalité (4) ci-dessous : 2 , 5 × YS 0 / TS ′ 5 − 0 , 5 + 15 ≥ T ≥ 2 , 5 × YS 0 / TS ′ 5 − 0 , 5 + 0 , 5
    Figure imgb0040
     dans laquelle :
    YS(0) : limite élastique
    TS'(5) : résistance à la traction dans un test de traction statique avec une pré-déformation à 5 % de déformation équivalente ou après de plus un traitement BH et YS(0)/TS'(5) n'est pas supérieur à 0,7.
EP98907247.5A 1997-03-17 1998-03-16 Procede de preparation des toles d'acier biphasees a haute resistance mécanique et a haute capacité d'absorption d'energie de chock Expired - Lifetime EP0969112B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10181225.3A EP2314729B2 (fr) 1997-03-17 1998-03-16 Feuilles d'acier biphase à haute résistance ayant d'excellentes propriétés de déformation dynamique

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
JP8243497 1997-03-17
JP8243497 1997-03-17
JP19029997 1997-07-15
JP19029797 1997-07-15
JP19029997 1997-07-15
JP19029797A JP3530347B2 (ja) 1997-07-15 1997-07-15 動的変形特性に優れた高強度鋼板の選定方法
JP22300897 1997-08-06
JP22300897A JP3936440B2 (ja) 1997-08-06 1997-08-06 耐衝突安全性と成形性に優れた自動車用高強度鋼板とその製造方法
JP25893897A JP3839928B2 (ja) 1997-07-15 1997-09-24 動的変形特性に優れたデュアルフェーズ型高強度鋼板
JP25893897 1997-09-24
PCT/JP1998/001101 WO1998041664A1 (fr) 1997-03-17 1998-03-16 Tole d'acier biphase a haute resistance ayant d'excellentes proprietes de deformation dynamique et son procede de preparation

Related Child Applications (3)

Application Number Title Priority Date Filing Date
EP10181225.3A Division EP2314729B2 (fr) 1997-03-17 1998-03-16 Feuilles d'acier biphase à haute résistance ayant d'excellentes propriétés de déformation dynamique
EP10181225.3A Division-Into EP2314729B2 (fr) 1997-03-17 1998-03-16 Feuilles d'acier biphase à haute résistance ayant d'excellentes propriétés de déformation dynamique
EP10181225.3 Division-Into 2010-09-28

Publications (4)

Publication Number Publication Date
EP0969112A1 EP0969112A1 (fr) 2000-01-05
EP0969112A4 EP0969112A4 (fr) 2003-05-21
EP0969112B1 EP0969112B1 (fr) 2011-08-17
EP0969112B2 true EP0969112B2 (fr) 2017-03-08

Family

ID=27524972

Family Applications (2)

Application Number Title Priority Date Filing Date
EP98907247.5A Expired - Lifetime EP0969112B2 (fr) 1997-03-17 1998-03-16 Procede de preparation des toles d'acier biphasees a haute resistance mécanique et a haute capacité d'absorption d'energie de chock
EP10181225.3A Expired - Lifetime EP2314729B2 (fr) 1997-03-17 1998-03-16 Feuilles d'acier biphase à haute résistance ayant d'excellentes propriétés de déformation dynamique

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP10181225.3A Expired - Lifetime EP2314729B2 (fr) 1997-03-17 1998-03-16 Feuilles d'acier biphase à haute résistance ayant d'excellentes propriétés de déformation dynamique

Country Status (7)

Country Link
EP (2) EP0969112B2 (fr)
KR (1) KR100334949B1 (fr)
CN (1) CN1080321C (fr)
AU (1) AU717294B2 (fr)
CA (1) CA2283924C (fr)
TW (1) TW426742B (fr)
WO (1) WO1998041664A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2704049C1 (ru) * 2018-10-03 2019-10-23 Общество с ограниченной ответственностью Научно-производственное предприятие "БУРИНТЕХ" (ООО НПП "БУРИНТЕХ") Долотная сталь

Families Citing this family (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3039862B1 (ja) * 1998-11-10 2000-05-08 川崎製鉄株式会社 超微細粒を有する加工用熱延鋼板
JP4369545B2 (ja) * 1998-11-30 2009-11-25 新日本製鐵株式会社 ひずみ速度依存性に優れたフェライト系薄鋼板およびそれを用いた自動車
CA2323952A1 (fr) * 1999-01-28 2000-08-03 Yasutaka Okada Produit en acier destine a des pieces structurelles de machines
CA2297291C (fr) * 1999-02-09 2008-08-05 Kawasaki Steel Corporation Feuille d'acier laminee a chaud de forte resistance a la traction et methodes pour sa production
DE19936151A1 (de) 1999-07-31 2001-02-08 Thyssenkrupp Stahl Ag Höherfestes Stahlband oder -blech und Verfahren zu seiner Herstellung
DE60116765T2 (de) * 2000-01-24 2006-11-02 Jfe Steel Corp. Feuerverzinktes stahlblech und herstellungsverfahren dafür
TW558569B (en) 2000-02-23 2003-10-21 Kawasaki Steel Co High tensile hot-rolled steel sheet having excellent strain aging hardening properties and method for producing the same
EP1195447B1 (fr) * 2000-04-07 2006-01-04 JFE Steel Corporation Tole d'acier laminee a chaud, tole d'acier laminee a froid et tole d'acier galvanisee par immersion a chaud ayant d'excellentes caracteristiques de durcissement au vieillissement par ecrouissage, et procede pour leur production
WO2001081640A1 (fr) * 2000-04-21 2001-11-01 Nippon Steel Corporation Plaque d'acier presentant une excellente aptitude a l'ebarbage et une resistance elevee a la fatigue, et son procede de production
US7591917B2 (en) * 2000-10-02 2009-09-22 Nucor Corporation Method of producing steel strip
US20030129444A1 (en) * 2000-11-28 2003-07-10 Saiji Matsuoka Composite structure type high tensile strength steel plate, plated plate of composite structure type high tensile strength steel and method for their production
JP3927384B2 (ja) * 2001-02-23 2007-06-06 新日本製鐵株式会社 切り欠き疲労強度に優れる自動車用薄鋼板およびその製造方法
FR2833617B1 (fr) * 2001-12-14 2004-08-20 Usinor Procede de fabrication de toles laminees a froid a tres haute resistance d'aciers dual phase micro-allies
FR2834722B1 (fr) * 2002-01-14 2004-12-24 Usinor Procede de fabrication d'un produit siderurgique en acier au carbone riche en cuivre, et produit siderurgique ainsi obtenu
EP1398390B1 (fr) * 2002-09-11 2006-01-18 ThyssenKrupp Steel AG Acier ferritique-martensitique possédant une resistance élevée ayant une fine microstructure
JP4180909B2 (ja) * 2002-12-26 2008-11-12 新日本製鐵株式会社 穴拡げ性、延性及び化成処理性に優れた高強度熱延鋼板及びその製造方法
WO2004059024A1 (fr) 2002-12-26 2004-07-15 Nippon Steel Corporation Feuille d'acier mince a haute resistance presentant d'excellentes caracteristiques d'expansibilite de trou, d'endurance et de traitement chimique et procede de production correspondant
FR2850671B1 (fr) * 2003-02-05 2006-05-19 Usinor Procede de fabrication d'une bande d'acier dual-phase a structure ferrito-martensitique, laminee a froid et bande obtenue
FR2855184B1 (fr) * 2003-05-19 2006-05-19 Usinor Tole laminee a froid et aluminiee en acier dual phase a tres haute resistance pour ceinture anti-implosion de televiseur, et procede de fabrication de cette tole
DE10327383C5 (de) * 2003-06-18 2013-10-17 Aceria Compacta De Bizkaia S.A. Anlage zur Herstellung von Warmband mit Dualphasengefüge
US7959747B2 (en) 2004-11-24 2011-06-14 Nucor Corporation Method of making cold rolled dual phase steel sheet
US7442268B2 (en) 2004-11-24 2008-10-28 Nucor Corporation Method of manufacturing cold rolled dual-phase steel sheet
US8337643B2 (en) 2004-11-24 2012-12-25 Nucor Corporation Hot rolled dual phase steel sheet
US11155902B2 (en) 2006-09-27 2021-10-26 Nucor Corporation High strength, hot dip coated, dual phase, steel sheet and method of manufacturing same
US7608155B2 (en) 2006-09-27 2009-10-27 Nucor Corporation High strength, hot dip coated, dual phase, steel sheet and method of manufacturing same
US20080178972A1 (en) * 2006-10-18 2008-07-31 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd) High strength steel sheet and method for producing the same
ATE432375T1 (de) * 2006-10-30 2009-06-15 Thyssenkrupp Steel Ag Verfahren zum herstellen von stahl-flachprodukten aus einem mit silizium legierten mehrphasenstahl
JP5165236B2 (ja) * 2006-12-27 2013-03-21 新日鐵住金ステンレス株式会社 衝撃吸収特性に優れた構造部材用ステンレス鋼板
BRPI0818530A2 (pt) 2007-10-10 2015-06-16 Nucor Corp Aço laminado a frio de estrutura metalográfica complexa e método de fabricar uma chapa de aço de estrutura metalográfica complexa
WO2009115877A1 (fr) 2008-03-19 2009-09-24 Nucor Corporation Appareil de coulée en bande à positionnement du rouleau lamineur
US20090236068A1 (en) 2008-03-19 2009-09-24 Nucor Corporation Strip casting apparatus for rapid set and change of casting rolls
US8882938B2 (en) 2009-12-21 2014-11-11 Tata Steel Ijmuiden B.V. High strength hot dip galvanised steel strip
PL2553132T3 (pl) * 2010-03-29 2015-10-30 Arcelormittal Investigacion Y Desarrollo Sl Produkt stalowy z ulepszoną charakterystyką nierdzewienia w warunkach zasolonych
EP2374910A1 (fr) * 2010-04-01 2011-10-12 ThyssenKrupp Steel Europe AG Acier, produit plat en acier, composant en acier et procédé de fabrication d'un composant en acier
WO2012064129A2 (fr) * 2010-11-10 2012-05-18 (주)포스코 Procédé pour fabriquer un acier à plasticité induite par transformation laminé à froid/laminé à chaud de haute résistance ayant une résistance à la traction d'une valeur de 590 mpa, une excellente usinabilité, et un faible écart de propriété mécanique
JP5856002B2 (ja) * 2011-05-12 2016-02-09 Ｊｆｅスチール株式会社 衝突エネルギー吸収能に優れた自動車用衝突エネルギー吸収部材およびその製造方法
JP5370620B1 (ja) * 2011-11-15 2013-12-18 Ｊｆｅスチール株式会社 薄鋼板およびその製造方法
DE102012013113A1 (de) * 2012-06-22 2013-12-24 Salzgitter Flachstahl Gmbh Hochfester Mehrphasenstahl und Verfahren zur Herstellung eines Bandes aus diesem Stahl mit einer Mindestzugfestigkleit von 580MPa
TWI465586B (zh) * 2013-02-07 2014-12-21 China Steel Corp 低降伏比鋼材及其製造方法
CN104018067B (zh) * 2014-04-28 2016-04-20 莱芜钢铁集团有限公司 一种高强塑性钒微合金化双相钢无缝管及其制备方法
JP6191769B2 (ja) 2014-05-28 2017-09-06 新日鐵住金株式会社 熱延鋼板及びその製造方法
CN104281774B (zh) * 2014-09-02 2017-06-13 上海交通大学 Q&p钢在不同应变率单拉后残余奥氏体含量的预测方法
CN106715742B (zh) 2014-09-17 2019-07-23 日本制铁株式会社 热轧钢板
RU2578618C1 (ru) * 2014-11-18 2016-03-27 Публичное акционерное общество "Северсталь" (ПАО "Северсталь") Способ производства полос из низколегированной свариваемой стали
MX2017008027A (es) 2014-12-19 2017-10-20 Nucor Corp Hoja de acero martensitico de calibre liviano laminada en caliente y metodo para fabricarla.
DE102015106780A1 (de) * 2015-04-30 2016-11-03 Salzgitter Flachstahl Gmbh Verfahren zur Erzeugung eines Warm- oder Kaltbandes aus einem Stahl mit erhöhtem Kupfergehalt
CN105483530A (zh) * 2015-11-30 2016-04-13 丹阳市宸兴环保设备有限公司 一种石油天然气输送管用热轧宽钢板材料
CN105568145B (zh) * 2015-12-24 2017-07-18 北京科技大学 一种具有耐腐蚀性能的汽车用冷轧超高强双相钢板及其制备方法
RU2617075C1 (ru) * 2016-02-11 2017-04-19 Иван Анатольевич Симбухов Способ производства экономно-легированного высокопрочного проката для труб магистральных газопроводов высокого давления, а также для отраслей машиностроения и оффшорного судостроения
RU2638479C1 (ru) * 2016-12-20 2017-12-13 Публичное акционерное общество "Северсталь" Горячекатаный лист из низколегированной стали толщиной от 15 до 165 мм и способ его получения
CN111363901B (zh) * 2018-12-26 2022-06-24 宝山钢铁股份有限公司 一种高表面质量的铁素体马氏体热轧双相钢及其制造方法
JP7235621B2 (ja) * 2019-08-27 2023-03-08 株式会社神戸製鋼所 低強度ホットスタンプ用鋼板、ホットスタンプ部品およびホットスタンプ部品の製造方法
CN110669913B (zh) * 2019-09-30 2021-05-28 鞍钢股份有限公司 一种高强汽车车轮用热轧酸洗双相钢及其生产方法
CN113106345B (zh) * 2021-04-07 2022-06-10 宝武集团鄂城钢铁有限公司 一种高塑性双相钢及其生产方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5123969A (en) † 1991-02-01 1992-06-23 China Steel Corp. Ltd. Bake-hardening cold-rolled steel sheet having dual-phase structure and process for manufacturing it

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196025A (en) † 1978-11-02 1980-04-01 Ford Motor Company High strength dual-phase steel
JPS59219473A (ja) 1983-05-26 1984-12-10 Nippon Steel Corp カラ−エツチング液及びエツチング方法
JP3169293B2 (ja) 1993-06-30 2001-05-21 川崎製鉄株式会社 耐衝撃性に優れた自動車用薄鋼板およびその製造方法
JP3458416B2 (ja) * 1993-09-21 2003-10-20 Ｊｆｅスチール株式会社 耐衝撃性に優れた冷延薄鋼板およびその製造方法
JP3370436B2 (ja) * 1994-06-21 2003-01-27 川崎製鉄株式会社 耐衝撃性に優れた自動車用鋼板とその製造方法
US5585184A (en) 1994-09-29 1996-12-17 Union Carbide Chemicals & Plastics Technology Corporation Colorable non-sticky resin core-shell particles
JP3533719B2 (ja) 1994-09-29 2004-05-31 村田機械株式会社 ファクシミリ装置
JP3039842B2 (ja) * 1994-12-26 2000-05-08 川崎製鉄株式会社 耐衝撃性に優れる自動車用熱延鋼板および冷延鋼板ならびにそれらの製造方法
JPH08176732A (ja) * 1994-12-27 1996-07-09 Nkk Corp 被削性の優れた窒化用鋼
JP3529178B2 (ja) * 1994-12-28 2004-05-24 Ｊｆｅスチール株式会社 衝撃吸収能に優れた極低炭素鋼板
JP3090421B2 (ja) * 1996-07-22 2000-09-18 新日本製鐵株式会社 耐久疲労性に優れた加工用熱延高強度鋼板

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5123969A (en) † 1991-02-01 1992-06-23 China Steel Corp. Ltd. Bake-hardening cold-rolled steel sheet having dual-phase structure and process for manufacturing it

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G. BÉRANGER ET AL.: "The Book of Steel", vol. 59, 1996, LAVOISIER PUBLISHERS, PARIS, pages: 1208 - 1211 †
O. MAID ET AL.: "Herstellung von Warmband aus Dualphasen-Stahl mit Haspeltemperaturen unterhalb der Martensitstart-Temperatur", THYSSEN TECHNISCHE BERICHTE, no. 1/85, 1985, pages 28 - 33 †
S. MASATOSCHI ET AL.: "Influence of Microstructure on Yielding Behavior in Continuous-Annealed Multi-Phase Sheet Steels", 1985, THE METALLURGICAL SOCIETY OF AIME, PENNSYLVANIA, pages: 341 - 360 †

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2704049C1 (ru) * 2018-10-03 2019-10-23 Общество с ограниченной ответственностью Научно-производственное предприятие "БУРИНТЕХ" (ООО НПП "БУРИНТЕХ") Долотная сталь

Also Published As

Publication number Publication date
CA2283924A1 (fr) 1998-09-24
WO1998041664A1 (fr) 1998-09-24
CA2283924C (fr) 2006-11-28
KR100334949B1 (ko) 2002-05-04
EP0969112A4 (fr) 2003-05-21
EP0969112A1 (fr) 2000-01-05
EP2314729A1 (fr) 2011-04-27
KR20000076372A (ko) 2000-12-26
EP2314729B2 (fr) 2017-03-08
CN1251140A (zh) 2000-04-19
AU717294B2 (en) 2000-03-23
CN1080321C (zh) 2002-03-06
AU6311898A (en) 1998-10-12
TW426742B (en) 2001-03-21
EP2314729B1 (fr) 2012-02-08
EP0969112B1 (fr) 2011-08-17

Similar Documents

Publication Publication Date Title
EP0969112B2 (fr) Procede de preparation des toles d'acier biphasees a haute resistance mécanique et a haute capacité d'absorption d'energie de chock
EP0974677B1 (fr) Procede de fabrication de toles d'acier a haute resistance mecanique ayant une excellente aptitude à la déformation et a haute capacite d'absorption d'energie de chock
EP2314730B1 (fr) Aciers haute résistance ayant d'excellentes propriétés d'absorption d'énergie aux chocs.
US6364968B1 (en) High-strength hot-rolled steel sheet having excellent stretch flangeability, and method of producing the same
JP3793350B2 (ja) 動的変形特性に優れたデュアルフェーズ型高強度冷延鋼板とその製造方法
JP3619357B2 (ja) 高い動的変形抵抗を有する高強度鋼板とその製造方法
US6319338B1 (en) High-strength steel plate having high dynamic deformation resistance and method of manufacturing the same
JP3492176B2 (ja) 高い動的変形抵抗を有する良加工性高強度鋼板とその製造方法
EP3612650B1 (fr) Feuille d'acier à haute résistance présentant une excellente déformabilité de bordage par étirage, procédé de production dudit acier et son utilisation
EP1325966A1 (fr) Plaque en acier ecroui presentant une tres haute resistance a la traction et procede de production
JPH1161326A (ja) 耐衝突安全性及び成形性に優れた自動車用高強度鋼板とその製造方法
JP3936440B2 (ja) 耐衝突安全性と成形性に優れた自動車用高強度鋼板とその製造方法
CN115698362B (zh) 钢板、构件及它们的制造方法
JPH10259448A (ja) 静的吸収エネルギー及び耐衝撃性に優れた高強度鋼板並びにその製造方法
KR102440772B1 (ko) 성형성이 우수한 고강도강판 및 그 제조방법
EP4265781A1 (fr) Tôle d'acier laminée à froid de très forte ténacité, possédant d'excellentes propriétés en termes de limite d'élasticité et de flexion, et son procédé de fabrication
EP3730651A1 (fr) Tôle d'acier à haute résistance de type à rapport de rendement élevé et son procédé de fabrication
JP2000290745A (ja) 疲労特性と衝突安全性に優れた加工用高強度鋼板及びその製造方法
JP4016573B2 (ja) 延性と耐衝撃特性に優れた高張力鋼板およびその製造方法と、耐衝撃特性を有する構造部材の製造方法
JPH10317096A (ja) 耐衝突安全性に優れた自動車用高強度鋼板とその製造方法
KR20240139067A (ko) 강판, 부재, 그들의 제조 방법, 냉연 강판용 열연 강판의 제조 방법 및 냉연 강판의 제조 방법
CN116194609A (zh) 扩孔性优异的高强度钢板及其制造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990929

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

A4 Supplementary search report drawn up and despatched

Effective date: 20030403

17Q First examination report despatched

Effective date: 20080303

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: A METHOD OF PRODUCING DUAL-PHASE HIGH-STRENGTH STEEL SHEETS HAVING HIGH IMPACT ENERGY ABSORPTION PROPERTIES

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NIPPON STEEL CORPORATION

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MABUCHI, HIDESATOC/O NIPPON STEEL CORP. OITA WORKS

Inventor name: WAKITA, JUNICHIC/O NIPPON STEEL CORP. OITA WORKS

Inventor name: KAWANO, OSAMUC/O NIPPON STEEL CORP. OITA WORKS

Inventor name: SAKUMA, YASUHARUC/O NIPPON STEEL CORP. KIMITSU WOR

Inventor name: KURIYAMA, YUKIHISAC/O NIPPON STEEL CORPORATION

Inventor name: TAKAHASHI, MANABUC/O NIPPON STEEL CORPORATION

Inventor name: UENISHI, AKIHIROC/O NIPPON STEEL CORPORATION

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 69842366

Country of ref document: DE

Effective date: 20111027

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: THYSSENKRUPP STEEL EUROPE AG

Effective date: 20120518

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 69842366

Country of ref document: DE

Effective date: 20120518

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: NIPPON STEEL & SUMITOMO METAL CORPORATION

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69842366

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

Effective date: 20130227

Ref country code: DE

Ref legal event code: R082

Ref document number: 69842366

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER, DE

Effective date: 20130227

Ref country code: DE

Ref legal event code: R081

Ref document number: 69842366

Country of ref document: DE

Owner name: NIPPON STEEL & SUMITOMO METAL CORPORATION, JP

Free format text: FORMER OWNER: NIPPON STEEL CORP., TOKIO/TOKYO, JP

Effective date: 20130227

Ref country code: DE

Ref legal event code: R081

Ref document number: 69842366

Country of ref document: DE

Owner name: NIPPON STEEL & SUMITOMO METAL CORPORATION, JP

Free format text: FORMER OWNER: NIPPON STEEL CORP., TOKIO/TOKYO, JP

Effective date: 20110901

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: THYSSENKRUPP STEEL EUROPE AG

Effective date: 20120518

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

27A Patent maintained in amended form

Effective date: 20170308

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 69842366

Country of ref document: DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170307

Year of fee payment: 20

Ref country code: FR

Payment date: 20170213

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20170315

Year of fee payment: 20

Ref country code: NL

Payment date: 20170210

Year of fee payment: 20

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69842366

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20180315

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20180315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20180315