Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
  • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
• • 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
  • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
  • C21D8/0236—Cold rolling
• • 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
  • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
  • C21D8/0273—Final recrystallisation annealing
• • 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
  • C22C38/02—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
  • 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
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
• • 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
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
• • 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
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
• • 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
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
  • 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
• • 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
  • 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
  • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
  • C23C2/06—Zinc or cadmium or alloys based thereon
• • 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
  • C23C2/26—After-treatment
  • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath

Definitions

• This disclosure relates to a low-yield-ratio, high-strength galvannealed steel sheet used in application as an automobile steel sheet and a method for producing the same.
• the surfaces of these steel sheets are galvanized for improving rust proofness in practical use.
• galvanized steel sheets galvannealed steel sheets subjected to heat treatment for diffusing Fe of the steel sheets into plating layers after hot-dip galvanization are widely used from the viewpoint of securing press property, spot weldability, coating adhesion.
• various proposals have been made.
• Japanese Unexamined Patent Application Publication No. 2004-115843 there has been proposed a hot-dip galvanized steel sheet in which the amounts of Si, Al, and Mn are balanced, and the steel sheet is maintained at a low temperature for a short time after annealing to form a martensite phase containing a large amount of C, thereby achieving a low yield ratio.
• the proposed technique relates to DP steel which cannot utilize improvement in ductility (TRIP effect) due to strain-induced transformation of residual austenite. Therefore, the steel sheet cannot be recognized as having sufficient ductility.
• high strength means a TS of 340 MPa or more.
• the yield ratio of the galvannealed steel sheet can be significantly decreased by adding Cr, V, and Mo in combination with Al, thereby achieving a yield ratio of about 55% or less.
• the amounts of C, Si, Mn, and Al are appropriately controlled, the amount of residual austenite can be increased without decreasing the alloying hot-dip galvanization properties, achieving excellent ductility.
• C is an element for stabilizing austenite and a necessary element for securing residual austenite.
• the C amount is less than about 0.05%, it is difficult to simultaneously secure the strength of the steel sheet and the amount of residual austenite to achieve high ductility.
• the C amount exceeds about 0.25%, a welded portion and a heat-affected portion are significantly hardened, thereby impairing weldability. Therefore, the C amount is in the range of about 0.05 to about 0.25%.
• Si about 2.0% or less
• Si is an element effective in strengthening steel.
• Si is also a ferrite forming element which promotes the concentration of C in austenite and suppresses the formation of a carbide and thus has the function of promoting the formation of residual austenite.
• the Si amount is preferably about 0.01% or more. However, when the Si amount exceeds about 2.0%, plating properties are degraded. Therefore, the Si amount is about 2.0% or less and preferably about 0.5% or less.
• Mn is an element effective in strengthening steel. Mn is also an element for stabilizing austenite and an element necessary for increasing residual austenite. However, when the Mn amount is less than about 1%, these effects cannot be easily obtained. On the other hand, when the Mn amount exceeds about 3%, a second phase fraction is excessively increased, and the amount of solid-solution strengthening is increased, thereby significantly increasing strength and decreasing ductility. Therefore, the Mn amount is in the range of about 1 to about 3%.
• P is an element effective in strengthening steel. However, when the P amount exceeds about 0.1%, embrittlement is caused by grain boundary segregation to impair impact properties. Therefore, the P amount is about 0.1% or less.
• the S amount is preferably as small as possible. However, from the viewpoint of production cost, the S amount is about 0.01% or less.
• Al effectively functions to purify ferrite and decrease the yield ratio of steel.
• the Al amount is less than about 0.3%, the effect is insufficient.
• the Al amount exceeds about 2%, the amount of the inclusion in a steel sheet is increased to degrade ductility. Therefore, the Al amount is in the range of about 0.3% to about 2%.
• Al is a ferrite forming element which promotes the concentration of C in austenite and suppresses the formation of a carbide and thus has the function of promoting the formation of residual austenite.
• the total of Al and Si is less than about 0.6%, the effect is insufficient, and sufficient ductility cannot be obtained. Therefore, the total of Si+Al is about 0.6% or more and preferably about 3% or less.
• N is an inevitable impurity and forms a nitride.
• the N amount is about 0.005% or more, ductility at high and low temperatures is decreased by the formation of a nitride. Therefore, the N amount is less than about 0.005%.
• the N amount is less than about 0.005%, and the relational expression, N ⁇ 0.007% ⁇ (0.003 ⁇ Al)%, is satisfied.
• Cr, V, and Mo are elements effective in decreasing the yield ratio of steel.
• the effect becomes significant when these elements are added in combination with Al. Even when each of these elements is added in an amount of over 1%, the effect is saturated. In addition, the effect is insufficient when the total of Cr, V, and Mo is less than about 0.1%. Conversely, when the total exceeds about 2%, strength may be excessively increased to decrease ductility and degrade the plating properties. Therefore, the amount of each of Cr, V, and Mo is about 1% or less, and the total is about 0.1 to about 2% and preferably about 0.15 to about 1.3%.
• Ti and Nb precipitate as carbonitrides to strengthen steel.
• such precipitation strengthening increases yield stress and is thus disadvantageous for decreasing the yield ratio.
• the amount of each of the elements added is about 0.005% or more, the yield stress is increased. Therefore, the amount of each of Ti and Nb is less than about 0.005%.
• B is effective in strengthening steel and can thus be added according to demand.
• the B amount exceeds about 0.005%, strength is excessively increased to decrease workability. Therefore, when B is added, the amount is about 0.005% or less.
• Ni about 1% or less
• Ni is an austenite-stabilizing element which causes austenite to remain and is effective in increasing strength, and thus can be added according to demand. However, even when the amount of Ni exceeds about 1%, the effect is saturated, and conversely the cost is increased. Therefore, when Ni is added, the amount is about 1% or less.
• Ca and REM at Least One in Total of about 0.01% or less
• Ca and REM have the function to control the form of a sulfide inclusion and thus have the effect of improving elongation and flange properties of a steel sheet, and thus can be added according to demand.
• the total of these elements exceeds about 0.01%, the effect is saturated. Therefore, when Ca and REM are added, the total of at least one of the elements is about 0.01% or less.
• a residual austenite phase is essential for effectively utilizing strain-induced transformation and obtaining high ductility. Therefore, it is very important to control the volume ratio of the residual austenite. From the viewpoint of securing high ductility, the ratio of the residual austenite phase is preferably at least about 3% or more. On the other hand, when the ratio of the residual austenite phase exceeds about 20%, a large amount of martensite is formed after molding to increase brittleness. Since it may be necessary to suppress brittleness in a permissible range, therefore, the ratio of the residual austenite phase is preferably about 20% or less.
• the metal structure of the steel sheet includes a ferrite main phase and a second phase including a residual austenite phase.
• the volume ratio of the ferrite phase is preferably about 40 to about 90% from the viewpoint of securing high ductility.
• a metal structure other than the residual austenite phase in the second phase include a bainite phase, a martensite phase and a pearlite phase.
• the total volume ratio of these phases is preferably about 7 to about 50%.
• Steel having the above-described composition is melted and continuously cast to form a cast slab, and then the slab is hot-rolled and cold-rolled.
• the conditions for these processes are not particularly limited.
• the steel sheet is annealed in a temperature range of about 730° C. to about 900° C., cooled at about 3 to about 100° C./s, retained in a temperature range of about 350° C. to about 600° C. for about 30 to about 250 seconds, hot-dip galvanized, and then alloyed at about 470° C. to about 600° C.
• Annealing temperature about 730 to about 900° C.
• Annealing is performed in an austenite single-phase zone or a two-phase zone including an austenite phase and a ferrite phase.
• the annealing temperature is lower than about 730° C., in some cases, a carbide is not sufficiently dissolved in the steel sheet, or recrystallization of ferrite is not completed, thereby failing to obtain intended properties.
• the annealing temperature exceeds about 900° C., austenite grains are significantly grown, and the number of ferrite nucleation sites formed from the second phase by subsequent cooling may be decreased. Therefore, the annealing temperature is about 730° C. to about 900° C.
• Cooling Rate about 3 to about 100° C./s
• the cooling rate is less than about 3° C./s, a large amount of pearlite precipitates, the amount of C dissolved in untransformed austenite is significantly decreased, and thus the intended structure cannot be obtained.
• the cooling rate exceeds about 100° C./s, growth of ferrite is suppressed to significantly decrease the volume ratio of ferrite, and thus sufficient ductility cannot be secured. Therefore, the cooling rate is preferably about 3 to about 100° C./s.
• Retention Temperature about 350° C. to about 600° C.
• the retention temperature exceeds about 600° C.
• a carbide precipitates from untransformed austenite.
• the retention temperature is lower than about 350° C., a car-bide precipitates in bainitic ferrite due to lower bainite transformation, thereby failing to sufficiently obtain stable residual austenite. Therefore, the retention temperature is about 350° C. to about 600° C.
• the retention temperature is preferably about 500° C. or less.
• Retention Time about 30 to about 250 seconds
• the retention time pays a very important role for controlling residual austenite. Namely, when the retention time is less than about 30 seconds, stabilization of untransformed austenite does not proceed, and thus the amount of residual austenite cannot be secured, thereby failing to obtain desired properties. On the other hand, when the retention time exceeds about 250 seconds, an austenite phase containing a small amount of dissolved C cannot be obtained, and it becomes difficult to transform to a martensite phase with a small amount of strain and achieve low yield stress by a strain field formed around the martensite phase. Therefore, the retention time is about 30 to about 250 seconds. From the viewpoint of stabilization of untransformed austenite, the retention time preferably exceeds about 60 seconds and more preferably exceeds about 90 seconds. In order to decrease yield stress, the retention time is preferably about 200 seconds or less.
• Alloying Temperature about 470° C. to about 600° C.
• the alloying temperature after the retention and hot-dip galvanization must be higher than the plating bath temperature, and the lower limit is about 470° C.
• the alloying temperature exceeds about 600° C., like in the case where the retention temperature exceeds about 600° C., a carbide precipitates from untransformed austenite, and thus stable residual austenite cannot be obtained. Therefore, the alloying temperature is about 470° C. to about 600° C.
• the specified annealing temperature, retention temperature, and alloying temperature need not be constant as long as they are in the above respective ranges.
• the cooling rate may be changed during cooling as long as it is in the above range.
• the plating conditions may be in a usual operation range, i.e., METSUKE may be about 20 to about 70 g/m 2 , and the amount of Fe in a plating layer may be about 6 to about 15%.
• the resulting slab was heated to 1250° C. and then hot-rolled at a finish rolling temperature of 900° C. to prepare a hot-rolled steel sheet having a thickness of 3.0 mm. After hot-rolling, the hot-rolled steel sheet was pickled and further cold-rolled to prepare a cold-rolled steel sheet having a thickness of 1.2 mm. Then, in a continuous hot-dip galvanization line, each cold-rolled steel sheet was heat-treated under the conditions shown in Table 2, plated at 50/50 g/m 2 , and then alloyed so that the Fe amount in the plating layer was 9%.
• each of the resulting steel sheets was temper-rolled by 0.5% to examine mechanical properties.
• mechanical properties yield stress YS, tensile strength TS, and elongation EL were measured using a JIS No. 5 tensile specimen obtained from each steel sheet in a direction perpendicular to the rolling direction. A tensile test was conducted at a strain rate of 6.7 ⁇ 10 ⁇ 3 s ⁇ 1 .
• the measured values, yield ratios YR, and values of TS ⁇ EL are also shown in Table 2.
• Table 2 indicates that steel sheet Nos. 1, 2, 5 to 8, 11 to 16, 18, 21, 22, 24, and 28 satisfy our composition and production conditions and have yield ratios as low as about 55% or less and satisfactory values of tensile strength TS and elongation EL.
• comparative steel sheet Nos. 3, 4, 9, 10, 17, 19, 20, 23, 25 to 27, and 29 to 38 not satisfying our composition and production conditions are out of the preferred range of at least one of yield ratio YR, tensile strength TS, elongation EL, and balance therebetween.
• Table 1 indicates that among our steel sheets, steel sheet Nos. A to L satisfying N ⁇ 0.007% ⁇ (0.003 ⁇ Al)% caused no cracking in the slabs.

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• 2006
  • 2006-03-03 JP JP2006058458A patent/JP5250938B2/ja active Active
  • 2006-03-31 EP EP06731354A patent/EP1867747B1/fr not_active Revoked
  • 2006-03-31 WO PCT/JP2006/307406 patent/WO2006104282A1/fr active Application Filing
  • 2006-03-31 US US11/885,804 patent/US20080163961A1/en not_active Abandoned
  • 2006-03-31 CA CA2601497A patent/CA2601497C/fr not_active Expired - Fee Related
• 2007
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