EP2534271A1 - A steel sheet suitable for enamelling and method for producing such a sheet - Google Patents

A steel sheet suitable for enamelling and method for producing such a sheet

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Publication number
EP2534271A1
EP2534271A1 EP11713766A EP11713766A EP2534271A1 EP 2534271 A1 EP2534271 A1 EP 2534271A1 EP 11713766 A EP11713766 A EP 11713766A EP 11713766 A EP11713766 A EP 11713766A EP 2534271 A1 EP2534271 A1 EP 2534271A1
Authority
EP
European Patent Office
Prior art keywords
steel sheet
level
sheet
steel
enamelling
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.)
Granted
Application number
EP11713766A
Other languages
German (de)
French (fr)
Other versions
EP2534271B1 (en
Inventor
Nele Van Steenberge
Marc Leveaux
Lode Duprez
Philippe Gousselot
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.)
ArcelorMittal SA
Original Assignee
ArcelorMittal Investigacion y Desarrollo SL
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
Application filed by ArcelorMittal Investigacion y Desarrollo SL filed Critical ArcelorMittal Investigacion y Desarrollo SL
Priority to RS20150565A priority Critical patent/RS54209B1/en
Priority to PL11713766T priority patent/PL2534271T3/en
Priority to SI201130570T priority patent/SI2534271T1/en
Publication of EP2534271A1 publication Critical patent/EP2534271A1/en
Application granted granted Critical
Publication of EP2534271B1 publication Critical patent/EP2534271B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0257—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • C21D3/04—Decarburising
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • 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
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper

Definitions

  • the present invention is related to a steel sheet suitable for enamelling, and to a method for the superficial decarburization of a steel sheet, as a preparation for enamelling the steel. State of the art.
  • the carbon level of a steel sheet has an important influence on the results in terms of surface quality of an enamel layer applied on the surface of the sheet.
  • a high carbon level at the steel surface may give rise to CO-gas bubble formation, which shows up as black spots and craters in the enamel surface.
  • this carbon forms coarse cementite during hot rolling which cracks upon cold rolling. These cracks are capable of capturing hydrogen which enters the steel during the enamelling process.
  • pressure will rise at the steel/enamel surface which gives rise to the so-called x fish-scale' deformation of the enamel.
  • Document JP-A- 2282421 describes such a method, wherein a continuously cast and annealed non-aging steel sheet for enamelling is produced, characterized in that a continuous-cast steel slab containing C between 0.0025 and 0.0050wt ⁇ 6 # Si max . 0.03wt%, Mn between 0.1 and 0.6wt%, P between 0.005 and 0.03wt%, S between 0.005 and 0.03wt%, Al max. 0.01wt%, N max.
  • JP-A-6116634 describes a similar method, but wherein the starting material has no vanadium and the initial C level is up to 0.015wt% and B is added instead of V for H-trapping.
  • the prior art decarburized sheets have rather low formability as testified by the values of the Lankford coefficient (r m ) . These values do not exceed 1.8 which is a concern when deep-drawing is foreseen.
  • figure 1 of JP6116634 shows that r m values between 1.6 and 1.8 are only achieved for a very narrow range of carbon level before decarburizing annealing. Below 0.0050wt%C and above 0.0150wt%C, the r m value is deteriorated. Aims of the invention
  • the present invention aims to provide a partially decarburized steel sheet suitable for enamelling which do not suffer from the drawbacks of the above cited prior art.
  • the invention is related to steel sheets and products and to a production method as disclosed in the appended claims.
  • the invention is thus related to a rolled steel sheet suitable for enamelling, said sheet having a carbon profile, defined by a gradient in the C- level from a level C surface at at least one surface of the sheet, to a level C bu i k in the bulk of the sheet, C bu i k being higher than C surface , and with :
  • the steel sheet of the invention has an r m value between 1.8 and 2.1.
  • C surface is between 0.005wt% and 0.015wt%, or between 0 and 0.005wt%.
  • C bu i k is between 0.02wt% and 0.08wt%, or between 0.025wt% and 0.08wt% or between 0.025wt% and 0.06wt%.
  • the Al-level is between 0.02wt% and 0.06wt%.
  • said depth is between 130 ⁇ and 200 ⁇ .
  • the invention is equally related to an enamelled steel sheet consisting of a steel sheet according to any of the above paragraphs, provided with an enamel layer.
  • the invention is further related to a steel product produced from a sheet according to the invention, and to an enamelled steel product consisting of a such a product, provided with an enamel layer.
  • the invention is also related to a method for producing a rolled steel sheet for enamelling, comprising the steps of :
  • said continuous annealing takes place at an anneal temperature between 760°C and 850°C, and during a decarburizing time between 45s and 300s.
  • the anneal temperature is between 800°C and 850°C.
  • the initial C-level is between 0.025wt% and 0.08wt% or between 0.025wt% and 0.06wt%.
  • the initial Al-level is between 0.02wt% and 0.06wt%.
  • the ratio pH 2 0/pH 2 is between 0.04 and 0.25.
  • the method of the invention may further comprise an over-ageing step at a temperature between 350 °C and 450°C during a timespan between 100s and 500s.
  • the method may further comprise a skinpass step with a reduction of between 0.3% and 1.5%.
  • Figure 1 illustrates the carbon profile in a steel sheet according to the invention.
  • Figure 2 illustrates an example of an annealing step usable in the method of the invention.
  • the steel sheet of the invention has a C- profile, defined by a gradient in the C-level from a lower value C sur f aC e at the surface to a higher value C bu ik in the bulk.
  • the sheet is obtainable by a method which includes a continuous decarburi zat ion step, as will be described further in this text.
  • Figure 1 illustrates the carbon- distribution across the thickness of two sheets according to the invention, with a thickness of 0.7mm.
  • Curve 10 illustrates a sheet which comprises a bulk portion 11, where the C-level Cbuik is substantially constant, and two surface portions 12 (one on each side of the sheet) , each surface portion exhibiting the C-profile.
  • the surface level is defined as the minimum value of the C-profile, measured by a suitable measurement technique (e.g. Glow Discharge Optical Emission Spectroscopy (GD-OES) , which allows composition measurement as depth analysis) .
  • a suitable measurement technique e.g. Glow Discharge Optical Emission Spectroscopy (GD-OES) , which allows composition measurement as depth analysis.
  • the C-level at the surface is maximum 0.015wt%, whereas C uik is higher than zero and lower than or equal to 0.08wt%.
  • Cbuik is higher than C sur face-
  • C S urface is between 0.005wt% and 0.015wt%.
  • Csurface is between 0 and 0.005wt%.
  • Curve 10 is an example of a sheet where the de c a rbu r i z a t i on has not taken place over the entire thickness of the sheet.
  • the level Cbuik is equal to the initial C-level applied in the production method (described further in more detail) .
  • C u i k is then between 0.02wt% and 0.08wt%, or between 0.025wt% and 0.08wt, or between 0.025wt% and 0.06wt% or between 0.025wt% and 0.05wt%.
  • Curve 13 illustrates the case where decarburization has continued until the middle plane of the sheet. In this case, C u i k is smaller than the initial C- level of the method, and the C-profile extends over each half-width of the sheet.
  • the decarburized sheet according to the invention further comprises Al, Mn and possibly S, Cu and Ca.
  • the oxygen level is to be kept lower than 0.01wt%.
  • oxygen is not added deliberately to the composition, but is allowed only at impurity levels. Fish scaling resistance is ensured by the higher initial C-level, so no oxide formation is required for this purpose. This means that no special alloying elements such as V are included. Also, N is kept as low as possible.
  • the Al-level in the sheet of the invention is between 0.012wt% and 0.07wt%, which is higher than the allowed Al-level in the prior art references cited above.
  • Al needs to be limited to avoid deoxidation, so as to ensure the formation of the oxides that will work against fish-scaling.
  • Al is mandatory for deoxidation and binding of free N to avoid the ageing of the mechanical properties.
  • Adding Al at levels higher than 0.07wt% means an increase in cost of the process, and a deterioration of the enamelling quality.
  • a more preferred range for the Al-level, related to more optimized conditions in terms of deoxidation and cost/enamelling quality is between 0.02wt% and 0.06wt%.
  • Mn is present between 0.12wt% and 0.45wt%. This element is added to control the strength properties of the steel and to avoid the formation of free sulphur.
  • Copper, Sulphur and Calcium may optionally be added above the impurity level, more precisely in the ranges 0.025wt% to 0.1wt%, 0.008wt% to 0.04wt% and 0.0005wt% to 0.005wt% respectively. These elements improve the enamelling quality.
  • the balance of the composition of the steel sheet according to the invention consists of Fe and incidental impurities.
  • the following elements may be present as impurities at levels which are preferably lower than the values (in wt%) given in table 1 :
  • the depth of the C-profile being defined as the depth where the C- level reaches (C bu i k + C surface )/2, is higher than 75 ⁇ , to ensure good enamelling capability. According to an embodiment, said depth is between 130 ⁇ and 200 ⁇ .
  • Steel sheets according to the invention i.e. with a C-level at the surface between 0 and 0.015wt% are suitable for 2C/1F enamelling, i.e. enamelling by applying a ground coat enamel, followed by an outer enamel coating, both coatings being subjected to one firing step, and for 1C/1F enamelling, i.e. enamelling by applying one enamel layer subjected to one firing step.
  • Steel sheets with low C-levels (i.e. 0.005wt% and less) at the surface may be suitable also for Direct White Enamelling (DWE) .
  • DWE Direct White Enamelling
  • the r m value of a steel sheet according to the invention is between 1.8 and 2.1. This means that the steel sheet has better formability than the prior art steel sheets referred to above.
  • the x r' value refers to the plastic strain ratio (also known as the anisotropy factor) , being the ratio of the true strain in the width direction to the true strain in the thickness direction when a sheet material is pulled in uniaxial tension beyond its elastic limit.
  • the ⁇ r m ' value is defined as 1 ⁇ 4(r 90 + 2*r 45 + r 0 ) , with r 90 , r 45 and r 0 the r- values as defined above, measured on samples oriented respectively at 90°, 45° and 0° with respect to the rolling direction.
  • fish scaling resistance is ensured by the higher initial C- level applied in the method (see further) .
  • the steel sheet of the invention can be produced by subjecting a steel slab with a specific initial steel composition to hot rolling, coiling and cold rolling, and by subjecting the cold-rolled sheet to continuous superficial decarburization .
  • the initial composition is mainly characterized by a higher C-level compared to the prior art, and by a higher Al-level and a lower oxygen level. No deliberate addition of elements like V, Nb or B is done, while still allowing to produce enamelled steel sheets with a high fish scale resistance and good enamel surface quality.
  • the initial C-level is between 0.02wt% and 0.08wt%, more preferably between 0.025wt% and 0.08wt%. This is higher than the initial C-levels disclosed in the prior art references referred to above.
  • the method of the invention allows to obtain steel sheets with improved formability characteristics compared to the prior art.
  • JP6116634 indicates that above 0.015wt% of initial carbon, it is not possible to obtain acceptable decarburization and good formability, the starting composition of the invention does not encounter these problems. Decarburization is possible down to an acceptable level, while formability is excellent.
  • the initial C-level is lower than 0.02wt%, insufficient cementite formation occurs which deteriorates fish scale resistance.
  • C-levels above 0.08wt% lead to too high strength levels and thus reduced formability.
  • Specific ranges for the initial C-level, related to more optimized characteristics in terms of fish scale resistance and strength/formability are between 0.025wt% and 0.06wt% and between 0.025wt% and 0.05wt%.
  • the initial steel composition according to the method of the invention further comprises Al, Mn and possibly 0, S, Cu and Ca in the same ranges as the decarburized sheet described above, the balance being Fe and the incidental impurities listed in Table 1.
  • a more preferred range for the initial Al-level, related to more optimized conditions in terms of deoxidation and cost/enamelling quality is between 0.02wt% and 0.06wt%.
  • oxygen is not added deliberately to the composition, but is allowed only at impurity levels.
  • the method of the invention comprises standard steps of hot rolling and cold rolling a steel slab of the above composition.
  • the slab is (re) heated at a temperature above 1050°C, subjected to hot rolling with a finishing temperature between 850°C and 950°C, and coiling at coiling temperature between 620°C and 770°C.
  • cold rolling is performed with a reduction of minimum 50%.
  • the final thickness of the cold rolled sheet is preferably between 0.2 and 2mm.
  • the decarburi zat ion anneal is done in an annealing furnace for continuous annealing (i.e. annealing while the cold-rolled sheet moves through the furnace at a given speed, said speed determining the anneal time, i.e. the time spent at the annealing temperature) as known in the art, possibly provided with a vapour injection device for applying a given annealing atmosphere.
  • Figure 2 shows an example of a lay-out of an annealing furnace usable in the method of the invention, starting with heating phase 1 wherein the temperature rises to the annealing temperature.
  • Phase 2 represents the actual annealing (soaking) phase.
  • Phase 3 is an overageing step.
  • Phase 2 can consist of one or more periods with a different (constant or average) annealing temperature and a different annealing atmosphere in each period. Practically speaking, the different periods at different conditions can be obtained by dividing the annealing zone in subsections and by injecting 3 ⁇ 40 vapour into an atmosphere comprising 3 ⁇ 4, at various points along the annealing line (see example further in this description) .
  • the superficial decarburization is done under a decarburizing atmosphere comprising water vapour and hydrogen gas, the remainder being essentially nitrogen gas, with the 3 ⁇ 4 content between lvoll and 95vol%, the 3 ⁇ 40 content between 0.04vol% and 33vol%, the ratio of partial pressures p3 ⁇ 40/pH 2 being between 0.04 and 0.5, more preferably between 0.04 and 0.25.
  • a decarburizing atmosphere comprising water vapour and hydrogen gas, the remainder being essentially nitrogen gas, with the 3 ⁇ 4 content between lvoll and 95vol%, the 3 ⁇ 40 content between 0.04vol% and 33vol%, the ratio of partial pressures p3 ⁇ 40/pH 2 being between 0.04 and 0.5, more preferably between 0.04 and 0.25.
  • the above composition describes the atmosphere at the start of the decarbur i z ing time. It is clear that during decarburization, the atmosphere composition will change, primarily due to the decarburization reaction taking place (formation of 3 ⁇ 4 and CO) .
  • the total pressure under which the superficial decarburization anneal takes place may be atmospheric pressure, or a pressure different from atmospheric but within generally known boundaries applied in this type of annealing process.
  • the decarburizing atmosphere can be prepared with a mixture of 3 ⁇ 4 and 2 with between 1,5 and 5% 3 ⁇ 4 in which 3 ⁇ 40 vapour is injected so that pH 2 0/pH 2 is between 0.04 and 0.5.
  • the minimum value of this ratio ensures that sufficient 3 ⁇ 40 is present to obtain decarburization according to the formula C + H 2 O CO + 3 ⁇ 4 .
  • the maximum of said range ensures that oxidation of Fe and of the furnace is avoided.
  • a more preferred range for p3 ⁇ 40/pH 2 related to more optimized conditions in terms of sufficient decarburization and avoiding the occurrence of Fe-oxidation is between 0.04 and 0.25.
  • the decarburizing atmosphere is applied during at least one of said periods with a different (constant or average) annealing temperature and a different annealing atmosphere in each period, preferably during the totality of phase 2.
  • the ecarburi zing time' refers to the time spent under the conditions of the decarburizing atmosphere .
  • the decarburizing time and the anneal temperature are chosen so as to obtain a steel sheet according to the invention. It is within the skilled person' s knowledge to find suitable combinations of decarburizing time and anneal temperature based on the examples given further in this description. According to a preferred embodiment, the decarburizing time is between 45s and 300s and the anneal temperature between 760°C and 850°C. When the ratio p3 ⁇ 40/pH 2 is lower than about 0.1, the decarburizing time is preferably higher than 70s. A more preferred range of the anneal temperature, applicable in combination with any decarburizing time between 45s and 300s is between 800°C and 850°C. The temperature is not necessarily constant during the decarburizing time.
  • Fluctuations of the temperature may occur due to variations in the line speed for example.
  • An over-ageing step may be applied at a temperature between 350°C and 450°C during a timespan between 100s and 500s.
  • a skinpass may further be applied with a reduction of between 0.3% and 1.5%.
  • Results from industrial trials performed by the applicant will be described hereafter, as well as a number of laboratory trials. All tested samples were produced from starting compositions according to the invention.
  • the coiling temperature was 725 ° C .
  • Two industrial trials were conducted.
  • the thickness of the cold rolled sheet subjected to decarburization annealing in industrial trial 1 was 0.6mm; in the second industrial trial the thickness was 1mm.
  • the continuous annealing line in which the industrial trials were conducted consists of a heating section, two soaking areas, a cooling and an overaging part.
  • the annealing atmosphere consisted mainly of a mixture of 3 ⁇ 4 and 2 , with 3 ⁇ 40 vapour being injected in the first and/or the second soaking area.
  • phase 2 as shown in figure 1 comprises a first period wherein the conditions of the present invention are not met, and a second period wherein these conditions are met. Such a process falls within the scope of the present invention .
  • Table 2 summarizes the results after decarburization in terms of the C-level at the surface (i.e. minimum level of the C-profile, measured by GD-OES), the depth of the C-profile, and the quality of an enamel layer produced on the surface of the samples.
  • Samples 25 to 35 yielded a bad enamelling aspect, which can be ascribed to either an insufficient depth of the C-profile (as determined by the depth where the C-level reaches (Csurface+Cbuik/2 ) , and/or a C level at the surface which is too high.
  • the reason for these negative results can be ascribed to the test conditions, either the anneal temperature which is too low, the decarburizing time too short, or the p3 ⁇ 40/pH 2 ratio too low, or a combination of these factors.
  • Table 4 shows the mechanical properties of a number of samples taken from the sheets of the industrial trials 1 and 2. Importantly, the formability in terms of the r m value is excellent, despite the initial C-level which is higher than in the prior art : r m is between 1.8 and 2.1. These results prove that the method of the invention allows to produce steel sheets suitable for enamelling, starting from an initial C-level higher than 0.02wt%, the resulting sheets allowing good enamelling quality and fish scale resistance, and having very good formability characteristics.
  • the depth-values given in table 1 are values of the depth where the C-level reaches ( C sur f ace +Cbuik) /2.
  • the depth measurements indicated with ⁇ *' show the maximum depth which could be measured with the applied equipment. The real value is thus higher than this value.
  • Table 3 composition of samples (C-level in table 1, remaining elements are beneath impurity level, the remainder is Fe)

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

Abstract

The present invention is related to a rolled steel sheet suitable for enamelling, said sheet having a carbon profile, defined by a gradient in the C-level from a level Csurface at least one surface of the sheet, to a level Cbulk in the bulk of the sheet, Cbulk being higher than Csurface, and With I - Cbulk higher than 0 and lower than or equal to 0.08wt%, - CsurfaCe between 0 and 0.015wt%, - A1 between 0.012wt% and 0.07wt%, Mn between 0.12wt% and 0.45wt%, 0 lower than 0.01wt% and optionally : - Cu between 0.025wt% and 0.1wt%, - S between 0.008wt% and 0.04wt%, - Ca between 0.0005wt% and 0.005wt%, the balance being Fe and incidental impurities, and wherein the depth where the C-level reaches (Cbulk+Csurface) 12, is higher than 75μm. The invention is equally related to a method for producing said steel sheet.

Description

A STEEL SHEET SUITABLE FOR ENAMELLING AND METHOD FOR
PRODUCING SUCH A SHEET
Field of the Invention
[0001] The present invention is related to a steel sheet suitable for enamelling, and to a method for the superficial decarburization of a steel sheet, as a preparation for enamelling the steel. State of the art.
[0002] The carbon level of a steel sheet has an important influence on the results in terms of surface quality of an enamel layer applied on the surface of the sheet. A high carbon level at the steel surface may give rise to CO-gas bubble formation, which shows up as black spots and craters in the enamel surface. On the other hand, when a sufficiently high carbon level is present initially in the bulk, this carbon forms coarse cementite during hot rolling which cracks upon cold rolling. These cracks are capable of capturing hydrogen which enters the steel during the enamelling process. When hydrogen is insufficiently captured, pressure will rise at the steel/enamel surface which gives rise to the so-called xfish-scale' deformation of the enamel.
[0003] It is therefore advantageous to decarburize the steel only in a layer at the surface of the steel, i.e. to conduct a superficial decarburization. Document JP-A- 2282421 describes such a method, wherein a continuously cast and annealed non-aging steel sheet for enamelling is produced, characterized in that a continuous-cast steel slab containing C between 0.0025 and 0.0050wt~6 # Si max . 0.03wt%, Mn between 0.1 and 0.6wt%, P between 0.005 and 0.03wt%, S between 0.005 and 0.03wt%, Al max. 0.01wt%, N max. 0.004wt%, Cu between 0.01 and 0.06wt%, 0 between 0.02 and 0.06wt%, V between 0.01 and 0.06wt%, the balance Fe and inevitable impurities, is hot-rolled with a finishing temperature higher than or equal to 800°C, and a coiling temperature of 600-800°C, cold-rolled with a reduction ratio higher than or equal to 60% and subjected to a decarburization annealing at 700-900°C for 30sec-3min, carried out in a continuous annealing furnace having a decarburizing atmosphere composed of 1-20% water vapour, gaseous hydrogen in an amount higher than or equal to twice the water vapour amount, and the balance being mainly gaseous nitrogen, so as to reduce the C-level to be less than or equal to 0.002wt%. JP-A-6116634 describes a similar method, but wherein the starting material has no vanadium and the initial C level is up to 0.015wt% and B is added instead of V for H-trapping.
[0004] Both prior art methods result in fully or superficially decarburized steel sheets which are suitable for enamelling by Direct White Enamelling (DWE) , wherein one white enamel coating is applied on the surface, followed by one firing step. As the initial carbon level is quite low, fish-scale resistance due to cementite formation is not achieved. To compensate for this, a steel with a high oxygen level and a limited Al-level is used in the prior art together with specific alloying elements such as B, V. Thanks to the limited Al-content, oxides of Si and Mn and nitrides of B and V are formed within the bulk of the steel which are beneficial against fish-scaling. However, this alloying involves extra costs and leads to some technical difficulties, e.g. involving casting with V. Furthermore, the prior art decarburized sheets have rather low formability as testified by the values of the Lankford coefficient (rm) . These values do not exceed 1.8 which is a concern when deep-drawing is foreseen. In particular, figure 1 of JP6116634 shows that rm values between 1.6 and 1.8 are only achieved for a very narrow range of carbon level before decarburizing annealing. Below 0.0050wt%C and above 0.0150wt%C, the rm value is deteriorated. Aims of the invention
[0005] The present invention aims to provide a partially decarburized steel sheet suitable for enamelling which do not suffer from the drawbacks of the above cited prior art.
Summary of the invention
[0006] The invention is related to steel sheets and products and to a production method as disclosed in the appended claims. The invention is thus related to a rolled steel sheet suitable for enamelling, said sheet having a carbon profile, defined by a gradient in the C- level from a level Csurface at at least one surface of the sheet, to a level Cbuik in the bulk of the sheet, Cbuik being higher than Csurface, and with :
- Cbuik higher than 0 and lower than or equal to
0.08wt%,
- CsurfaCe between 0 and 0.015wt%,
Al between 0.012wt% and 0.07wt%,
Mn between 0.12wt% and 0.45wt%,
- 0 lower than 0.01wt%
and optionally :
- Cu between 0.025wt% and 0.1wt%,
- S between 0.008wt% and 0.04wt%, Ca between 0.0005wt% and 0.005wt% the balance being Fe and incidental impurities,
and wherein the depth where the C-level reaches (Cbuik+Csurface) 12, is higher than 75μιη.
[0007] According to a preferred embodiment, the steel sheet of the invention has an rm value between 1.8 and 2.1.
[0008] According to specific embodiments, Csurface is between 0.005wt% and 0.015wt%, or between 0 and 0.005wt%.
[0009] According to other specific embodiments, Cbuik is between 0.02wt% and 0.08wt%, or between 0.025wt% and 0.08wt% or between 0.025wt% and 0.06wt%.
[0010] According to another embodiment, the Al-level is between 0.02wt% and 0.06wt%.
[0011] According to a further embodiment, said depth is between 130μη and 200μιη.
[0012] The invention is equally related to an enamelled steel sheet consisting of a steel sheet according to any of the above paragraphs, provided with an enamel layer.
[0013] The invention is further related to a steel product produced from a sheet according to the invention, and to an enamelled steel product consisting of a such a product, provided with an enamel layer.
[0014] The invention is also related to a method for producing a rolled steel sheet for enamelling, comprising the steps of :
- subjecting a steel slab to hot rolling followed by coiling, and cold rolling, so as to obtain a cold-rolled steel sheet, said slab comprising the following initial composition :
- C between 0.02wt% and 0.08wt%,
- Al between 0.012wt% and 0.07wt%, - Mn between 0.12wt% and 0.45wt%,
- 0 lower than 0.01wt%
and optionally :
- Cu between 0.025wt% and 0.1wt%,
- S between 0.008wt% and 0.04wt%,
- Ca between 0.0005wt% and 0.005wt%,
- the balance being Fe and incidental impurities,
- subjecting said cold-rolled sheet to continuous annealing step, wherein said sheet is exposed during a decarbur i z ing time to a de c a rbu r i z i ng atmosphere comprising water vapour and hydrogen gas, wherein the ¾ content is between lvol% and 95vol%, the ¾0 content between 0.04vol% and 33vol%, the remainder being mainly nitrogen gas, the ratio p¾0/pH2 being between 0.04 and 0.5.
[0015] According to a preferred embodiment, said continuous annealing takes place at an anneal temperature between 760°C and 850°C, and during a decarburizing time between 45s and 300s.
[0016] According to a specific embodiment, the anneal temperature is between 800°C and 850°C.
[0017] According to specific embodiments of the method of the invention, the initial C-level is between 0.025wt% and 0.08wt% or between 0.025wt% and 0.06wt%.
[0018] According to a further embodiment, the initial Al-level is between 0.02wt% and 0.06wt%.
[0019] According to a specific embodiment, the ratio pH20/pH2 is between 0.04 and 0.25.
[0020] The method of the invention may further comprise an over-ageing step at a temperature between 350 °C and 450°C during a timespan between 100s and 500s. The method may further comprise a skinpass step with a reduction of between 0.3% and 1.5%. Brief description of the figures
[0021] Figure 1 illustrates the carbon profile in a steel sheet according to the invention.
[0022] Figure 2 illustrates an example of an annealing step usable in the method of the invention.
Detailed description of the invention
[0023] The steel sheet of the invention has a C- profile, defined by a gradient in the C-level from a lower value CsurfaCe at the surface to a higher value Cbuik in the bulk. The sheet is obtainable by a method which includes a continuous decarburi zat ion step, as will be described further in this text. Figure 1 illustrates the carbon- distribution across the thickness of two sheets according to the invention, with a thickness of 0.7mm. Curve 10 illustrates a sheet which comprises a bulk portion 11, where the C-level Cbuik is substantially constant, and two surface portions 12 (one on each side of the sheet) , each surface portion exhibiting the C-profile. The surface level is defined as the minimum value of the C-profile, measured by a suitable measurement technique (e.g. Glow Discharge Optical Emission Spectroscopy (GD-OES) , which allows composition measurement as depth analysis) . In a steel sheet according to the invention, the C-level at the surface is maximum 0.015wt%, whereas C uik is higher than zero and lower than or equal to 0.08wt%. At the same time, Cbuik is higher than Csurface- According to an embodiment, CSurface is between 0.005wt% and 0.015wt%. According to another embodiment, Csurface is between 0 and 0.005wt%.
[0024] Curve 10 is an example of a sheet where the de c a rbu r i z a t i on has not taken place over the entire thickness of the sheet. This means that the level Cbuik is equal to the initial C-level applied in the production method (described further in more detail) . According to embodiments which correspond to embodiments of the method of the invention (see further), C uik is then between 0.02wt% and 0.08wt%, or between 0.025wt% and 0.08wt, or between 0.025wt% and 0.06wt% or between 0.025wt% and 0.05wt%. Curve 13 illustrates the case where decarburization has continued until the middle plane of the sheet. In this case, C uik is smaller than the initial C- level of the method, and the C-profile extends over each half-width of the sheet.
[ 0025 ] The decarburized sheet according to the invention further comprises Al, Mn and possibly S, Cu and Ca. Contrary to the prior art references, the oxygen level is to be kept lower than 0.01wt%. According to a preferred embodiment of the steel sheet of the invention, oxygen is not added deliberately to the composition, but is allowed only at impurity levels. Fish scaling resistance is ensured by the higher initial C-level, so no oxide formation is required for this purpose. This means that no special alloying elements such as V are included. Also, N is kept as low as possible.
[ 0026 ] The Al-level in the sheet of the invention is between 0.012wt% and 0.07wt%, which is higher than the allowed Al-level in the prior art references cited above. In the cited prior art documents Al needs to be limited to avoid deoxidation, so as to ensure the formation of the oxides that will work against fish-scaling. In the method of the invention (see further), Al is mandatory for deoxidation and binding of free N to avoid the ageing of the mechanical properties. When the Al-level is lower than 0.012wt%, insufficient deoxidation takes place, and binding of N is required through other means. Adding Al at levels higher than 0.07wt% means an increase in cost of the process, and a deterioration of the enamelling quality. A more preferred range for the Al-level, related to more optimized conditions in terms of deoxidation and cost/enamelling quality is between 0.02wt% and 0.06wt%.
[0027] Mn is present between 0.12wt% and 0.45wt%. This element is added to control the strength properties of the steel and to avoid the formation of free sulphur.
[0028] Copper, Sulphur and Calcium may optionally be added above the impurity level, more precisely in the ranges 0.025wt% to 0.1wt%, 0.008wt% to 0.04wt% and 0.0005wt% to 0.005wt% respectively. These elements improve the enamelling quality.
[0029] The balance of the composition of the steel sheet according to the invention consists of Fe and incidental impurities. The following elements may be present as impurities at levels which are preferably lower than the values (in wt%) given in table 1 :
Table 1 : impurity levels
[0030] In a steel sheet of the invention, the depth of the C-profile, being defined as the depth where the C- level reaches (Cbuik + Csurface)/2, is higher than 75μιη, to ensure good enamelling capability. According to an embodiment, said depth is between 130 μιη and 200 μη.
[0031] Steel sheets according to the invention, i.e. with a C-level at the surface between 0 and 0.015wt% are suitable for 2C/1F enamelling, i.e. enamelling by applying a ground coat enamel, followed by an outer enamel coating, both coatings being subjected to one firing step, and for 1C/1F enamelling, i.e. enamelling by applying one enamel layer subjected to one firing step. Steel sheets with low C-levels (i.e. 0.005wt% and less) at the surface may be suitable also for Direct White Enamelling (DWE) .
[0032] According to a preferred embodiment, the rm value of a steel sheet according to the invention is between 1.8 and 2.1. This means that the steel sheet has better formability than the prior art steel sheets referred to above. In the present description, the xr' value refers to the plastic strain ratio (also known as the anisotropy factor) , being the ratio of the true strain in the width direction to the true strain in the thickness direction when a sheet material is pulled in uniaxial tension beyond its elastic limit. The λ rm' value is defined as ¼(r90 + 2*r45 + r0) , with r90, r45 and r0 the r- values as defined above, measured on samples oriented respectively at 90°, 45° and 0° with respect to the rolling direction. In a steel sheet according to the invention, fish scaling resistance is ensured by the higher initial C- level applied in the method (see further) .
[0033] The steel sheet of the invention can be produced by subjecting a steel slab with a specific initial steel composition to hot rolling, coiling and cold rolling, and by subjecting the cold-rolled sheet to continuous superficial decarburization . The initial composition is mainly characterized by a higher C-level compared to the prior art, and by a higher Al-level and a lower oxygen level. No deliberate addition of elements like V, Nb or B is done, while still allowing to produce enamelled steel sheets with a high fish scale resistance and good enamel surface quality. The initial C-level is between 0.02wt% and 0.08wt%, more preferably between 0.025wt% and 0.08wt%. This is higher than the initial C-levels disclosed in the prior art references referred to above. Despite such higher initial C-levels, the method of the invention allows to obtain steel sheets with improved formability characteristics compared to the prior art. Whereas JP6116634 indicates that above 0.015wt% of initial carbon, it is not possible to obtain acceptable decarburization and good formability, the starting composition of the invention does not encounter these problems. Decarburization is possible down to an acceptable level, while formability is excellent. When the initial C-level is lower than 0.02wt%, insufficient cementite formation occurs which deteriorates fish scale resistance. C-levels above 0.08wt% lead to too high strength levels and thus reduced formability. Specific ranges for the initial C-level, related to more optimized characteristics in terms of fish scale resistance and strength/formability are between 0.025wt% and 0.06wt% and between 0.025wt% and 0.05wt%.
[0034] The initial steel composition according to the method of the invention further comprises Al, Mn and possibly 0, S, Cu and Ca in the same ranges as the decarburized sheet described above, the balance being Fe and the incidental impurities listed in Table 1. A more preferred range for the initial Al-level, related to more optimized conditions in terms of deoxidation and cost/enamelling quality is between 0.02wt% and 0.06wt%. According to a preferred embodiment of the method of the invention, oxygen is not added deliberately to the composition, but is allowed only at impurity levels.
[0035] The method of the invention comprises standard steps of hot rolling and cold rolling a steel slab of the above composition. According to the preferred embodiment, the slab is (re) heated at a temperature above 1050°C, subjected to hot rolling with a finishing temperature between 850°C and 950°C, and coiling at coiling temperature between 620°C and 770°C. Still according to the preferred embodiment, cold rolling is performed with a reduction of minimum 50%. The final thickness of the cold rolled sheet is preferably between 0.2 and 2mm.
[0036] The decarburi zat ion anneal is done in an annealing furnace for continuous annealing (i.e. annealing while the cold-rolled sheet moves through the furnace at a given speed, said speed determining the anneal time, i.e. the time spent at the annealing temperature) as known in the art, possibly provided with a vapour injection device for applying a given annealing atmosphere.
[0037] Figure 2 shows an example of a lay-out of an annealing furnace usable in the method of the invention, starting with heating phase 1 wherein the temperature rises to the annealing temperature. Phase 2 represents the actual annealing (soaking) phase. Phase 3 is an overageing step. Phase 2 can consist of one or more periods with a different (constant or average) annealing temperature and a different annealing atmosphere in each period. Practically speaking, the different periods at different conditions can be obtained by dividing the annealing zone in subsections and by injecting ¾0 vapour into an atmosphere comprising ¾, at various points along the annealing line (see example further in this description) .
[0038] According to the invention, the superficial decarburization is done under a decarburizing atmosphere comprising water vapour and hydrogen gas, the remainder being essentially nitrogen gas, with the ¾ content between lvoll and 95vol%, the ¾0 content between 0.04vol% and 33vol%, the ratio of partial pressures p¾0/pH2 being between 0.04 and 0.5, more preferably between 0.04 and 0.25. The above composition describes the atmosphere at the start of the decarbur i z ing time. It is clear that during decarburization, the atmosphere composition will change, primarily due to the decarburization reaction taking place (formation of ¾ and CO) . Also at the start of the decarburizing time, small amounts of other gases may already have formed or may be present as impurities in the atmosphere. The total pressure under which the superficial decarburization anneal takes place may be atmospheric pressure, or a pressure different from atmospheric but within generally known boundaries applied in this type of annealing process.
[0039] According to one embodiment, the decarburizing atmosphere can be prepared with a mixture of ¾ and 2 with between 1,5 and 5% ¾ in which ¾0 vapour is injected so that pH20/pH2 is between 0.04 and 0.5. The minimum value of this ratio ensures that sufficient ¾0 is present to obtain decarburization according to the formula C + H2O CO + ¾ . The maximum of said range ensures that oxidation of Fe and of the furnace is avoided. A more preferred range for p¾0/pH2, related to more optimized conditions in terms of sufficient decarburization and avoiding the occurrence of Fe-oxidation is between 0.04 and 0.25.
[0040] In the method of the invention, the decarburizing atmosphere is applied during at least one of said periods with a different (constant or average) annealing temperature and a different annealing atmosphere in each period, preferably during the totality of phase 2. In the following, the ecarburi zing time' refers to the time spent under the conditions of the decarburizing atmosphere .
[0041] The decarburizing time and the anneal temperature are chosen so as to obtain a steel sheet according to the invention. It is within the skilled person' s knowledge to find suitable combinations of decarburizing time and anneal temperature based on the examples given further in this description. According to a preferred embodiment, the decarburizing time is between 45s and 300s and the anneal temperature between 760°C and 850°C. When the ratio p¾0/pH2 is lower than about 0.1, the decarburizing time is preferably higher than 70s. A more preferred range of the anneal temperature, applicable in combination with any decarburizing time between 45s and 300s is between 800°C and 850°C. The temperature is not necessarily constant during the decarburizing time. Fluctuations of the temperature may occur due to variations in the line speed for example. An over-ageing step may be applied at a temperature between 350°C and 450°C during a timespan between 100s and 500s. A skinpass may further be applied with a reduction of between 0.3% and 1.5%.
Examples
[0042] Results from industrial trials performed by the applicant will be described hereafter, as well as a number of laboratory trials. All tested samples were produced from starting compositions according to the invention. The coiling temperature was 725 ° C . Two industrial trials were conducted. The thickness of the cold rolled sheet subjected to decarburization annealing in industrial trial 1 was 0.6mm; in the second industrial trial the thickness was 1mm. [0043] The continuous annealing line in which the industrial trials were conducted consists of a heating section, two soaking areas, a cooling and an overaging part. The annealing atmosphere consisted mainly of a mixture of ¾ and 2 , with ¾0 vapour being injected in the first and/or the second soaking area. In the first trial, H2O vapour was injected only in the second soaking area. In the second trial, ¾0 was injected in the first and the second soaking area. Overageing was performed in both trials at 400°C. The overageing time depended on the line speed, e.g. at 180m/min line speed, the overageing time was 232s. Table 2 shows the annealing conditions for both trials (numbered trial 1 and trial 2) . Table 3 shows the composition besides C, for a number of the samples shown in table 1.
[0044] In industrial trial 1, the p¾0/pH2 ratio is below the range of 0.04-0.5 in the first soaking area (due to the fact that no ¾0 injection is done) . The decarburizing time in this trial is the time spent in the second soaking area, where the p¾0/pH2 is within said range. This is an example therefore of a process wherein phase 2 as shown in figure 1 comprises a first period wherein the conditions of the present invention are not met, and a second period wherein these conditions are met. Such a process falls within the scope of the present invention .
[0045] In industrial trial 2, ¾0-inj ection was performed in both soaking areas. The decarburizing time indicated here is the time spent in soaking areas 1 and 2. The anneal temperature is the average of the temperatures in soaking areas 1 and 2. The p¾0/pH2 values indicated in table 1 are the average values in soaking area 1 in which more ¾0 was injected. However, the p¾0/pH2 in soaking area 2 is estimated to be also within the range of 0.04- 0.5. In industrial trial 2, longer decarburizing times could be achieved as compared to the first trial, for similar line velocities, leading to stronger decarburization .
[0046] The laboratory trials (marked xtrial 3' in table 2), were conducted on samples which were subjected to a simulation of the continuous annealing step, at the conditions shown in table 2. These trials were conducted in an atmosphere of HNX with 5% ¾, with ¾0 added to obtain pH20/pH2 in the range [0.04-0.5].
[0047] Samples from all three trials were subjected to an enamelling process wherein a ground coat enamel is deposited, this enamel being designed especially to determine the role of C in the enamel characteristics. It was found that the adhesion of the enamelling layer was good for all tested samples. The enamelling aspect was good for C-levels at the surface of maximum 0.015wt%, and for profile depths of 75μη up to 250μιη, as shown in table
1. There is no reason to conclude from the results however that the enamelling quality deteriorates at higher depth values than 250μιη. Such higher depth values are therefore not excluded from the scope of the invention. All tested samples showed a good fish scale resistance.
[0048] Table 2 summarizes the results after decarburization in terms of the C-level at the surface (i.e. minimum level of the C-profile, measured by GD-OES), the depth of the C-profile, and the quality of an enamel layer produced on the surface of the samples. Samples 25 to 35 yielded a bad enamelling aspect, which can be ascribed to either an insufficient depth of the C-profile (as determined by the depth where the C-level reaches (Csurface+Cbuik/2 ) , and/or a C level at the surface which is too high. The reason for these negative results can be ascribed to the test conditions, either the anneal temperature which is too low, the decarburizing time too short, or the p¾0/pH2 ratio too low, or a combination of these factors.
[0049] Table 4 shows the mechanical properties of a number of samples taken from the sheets of the industrial trials 1 and 2. Importantly, the formability in terms of the rm value is excellent, despite the initial C-level which is higher than in the prior art : rm is between 1.8 and 2.1. These results prove that the method of the invention allows to produce steel sheets suitable for enamelling, starting from an initial C-level higher than 0.02wt%, the resulting sheets allowing good enamelling quality and fish scale resistance, and having very good formability characteristics.
decarb
initial urizing anneal Acc. to
SamTrial C time temp. pH20/ C_surf depth enameling invention ple N nr (ppm1) (s) (°C) pH2 (-) (ppm) (Mm) aspect ?
1 1 362 45 807 0, 12 126 90 good y
2 3 330 70 770 0,05 123 92 good y
3 3 330 70 770 0, 12 108 100 good y
4 3 330 70 770 0,24 47 94* good y
5 1 367 90 782 0, 16 132 123 good y
6 1 367 90 785 0, 16 133 130 good y
7 2 330 90 810 0, 13 87 130* good y
8 2 346 90 817 0,09 89 1 16* good y
9 2 386 105 801 0, 12 106 130 good y
10 2 348 105 809 0, 1 1 88 145* good y
1 1 2 316 105 817 0, 12 78 180 good y
12 2 346 105 824 0,09 81 142* good y
13 2 360 126 799 0,09 106 138* good y
14 2 348 126 814 0,09 78 124* good y
15 2 375 126 824 0,09 76 140* good y
16 3 330 155 840 0,05 51 94* good y
17 3 330 155 840 0, 12 61 94* good y
18 3 330 155 840 0,24 35 94* good y
19 2 391 209 815 0,08 68 121* good y
20 2 437 209 817 0,08 70 145* good y
21 2 340 209 821 0,07 71 222 good y
22 1 500 45 795 0,08 211 40 bad n
23 1 491 45 796 0,09 164 75 bad n
24 1 490 45 800 0,09 177 49 bad n
25 1 360 45 793 0,09 150 70 bad n
26 1 360 45 794 0,09 167 75 bad n
27 1 360 45 795 0,09 176 68 bad n
28 3 330 70 770 0,01 198 57 bad n
29 2 363 105 743 0, 17 187 135 bad n
30 2 370 105 752 0, 16 165 120 bad n
31 3 330 155 840 0,01 192 89 bad n
Table 2 : Overview of experimental conditions and results
1 : lwt% = 104 ppm
The depth-values given in table 1 are values of the depth where the C-level reaches ( Csurface+Cbuik) /2. The depth measurements indicated with λ*' show the maximum depth which could be measured with the applied equipment. The real value is thus higher than this value. Sample
n° Al(wt%) Mn(wt%) Cu (wt%) S (wt%)
1 0.024 0.18 0.022 0.0049
5 0.03 0.18 0.028 0.0046
6 0.028 0.19 0.041 0.0052
9 0.035 0.18 0.029 0.0088
1 1 0.034 0.17 0.028 0.0077
Table 3 : composition of samples (C-level in table 1, remaining elements are beneath impurity level, the remainder is Fe)
Table 4 : mechanical properties

Claims

1. A rolled steel sheet suitable for enamelling, said sheet having a carbon profile, defined by a gradient in the C-level from a level Csurface at at least one surface of the sheet, to a level Cbuik in the bulk of the sheet, Cbuik being higher than Csurface, and with :
- Cbuik higher than 0 and lower than or equal to 0.08wt%,
- Csurface between 0 and 0.015wt%,
Al between 0.012wt% and 0.07wt%,
Mn between 0.12wt% and 0.45wt%,
0 lower than 0.01wt%
and optionally :
- Cu between 0.025wt% and 0.1wt%,
- S between 0.008wt% and 0.04wt%,
- Ca between 0.0005wt% and 0.005wt%,
the balance being Fe and incidental impurities,
and wherein the depth where the C-level reaches (Cbuik+Csurface) /2, is higher than 75μιη.
2. Steel sheet according to claim 1, having an rm value between 1.8 and 2.1.
3. Steel sheet according to claim 1 or 2, wherein Csurface is between 0.005wt% and 0.015wt%.
4. Steel sheet according to claim 1 or 2, wherein Csurface is between 0 and 0.005wt%.
5. Steel sheet according to any one of claims 1 to 4, wherein Cbuik is between 0.02wt% and 0.08wt%.
6. Steel sheet according to claim 5, wherein Cbuik is between 0.025wt% and 0.08wt%.
7. Steel sheet according to claim 5, wherein Cbuik is between 0.025wt% and 0.06wt%.
8. Steel sheet according to any one of claims 1 to 7, wherein the Al-level is between 0.02wt% and 0.06wt% .
9. Steel sheet according to any one of claims 1 to 8, wherein said depth is between 130μη and 200μιη.
10. Enamelled steel sheet consisting of a steel sheet according to any one of claims 1 to 9 provided with an enamel layer.
11. Steel product produced from a sheet according to any one of claims 1 to 9.
12. Enamelled steel product consisting of a product according to claim 11, provided with an enamel layer .
13. A method for producing a rolled steel sheet for enamelling, comprising the steps of :
- subjecting a steel slab to hot rolling followed by coiling, and cold rolling, so as to obtain a cold-rolled steel sheet, said slab comprising the following initial composition :
- C between 0.02wt% and 0.08wt%,
- Al between 0.012wt% and 0.07wt%,
- Mn between 0.12wt% and 0.45wt%,
- 0 lower than 0.01wt%
and optionally :
- Cu between 0.025wt% and 0.1wt%,
- S between 0.008wt% and 0.04wt%,
- Ca between 0.0005wt% and 0.005wt%,
- the balance being Fe and incidental impurities,
- subjecting said cold-rolled sheet to continuous annealing step, wherein said sheet is exposed during a decarburizing time to a decarburizing atmosphere comprising water vapour and hydrogen gas, wherein the ¾ content is between lvoll and 95vol%, the ¾0 content between 0.04vol% and 33vol%, the remainder being mainly nitrogen gas, the ratio p¾0/pH2 being between 0.04 and 0.5.
14. Method according to claim 13, wherein said continuous annealing takes place at an anneal temperature between 760°C and 850°C, and during a decarburizing time between 45s and 300s.
15. Method according to claim 14, wherein the anneal temperature is between 800°C and 850°C.
16. Method according to any one of claims 13 to 15, wherein the initial C-level is between 0.025wt% and 0.08wt% .
17. Method according to claim 16, wherein the initial C-level is between 0.025wt% and 0.06wt%.
18. Method according to any one of claims 13 to 17, wherein the initial Al-level is between 0.02wt% and 0.06wt% .
19. Method according to any one of claims 13 to 18, wherein the ratio ρ¾0/ρΗ2 is between 0.04 and 0.25.
20. Method according to any one of claims 13 to 19, further comprising an over-ageing step at a temperature between 350°C and 450°C during a timespan between 100s and 500s.
21. Method according to claim 20, further comprising a skinpass step with a reduction of between 0.3% and 1.5%.
EP11713766.1A 2011-04-08 2011-04-08 A steel sheet suitable for enamelling and method for producing such a sheet Active EP2534271B1 (en)

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PCT/EP2011/055477 WO2012136270A1 (en) 2011-04-08 2011-04-08 A steel sheet suitable for enamelling and method for producing such a sheet

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CN117305714A (en) * 2023-10-31 2023-12-29 东北大学 A kind of hot-rolled enamel steel with excellent scale explosion resistance and preparation method thereof

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US11236427B2 (en) 2017-12-06 2022-02-01 Polyvision Corporation Systems and methods for in-line thermal flattening and enameling of steel sheets
JP6806128B2 (en) * 2018-01-09 2021-01-06 Ｊｆｅスチール株式会社 Judgment method of cold-rolled steel sheet and manufacturing method of cold-rolled steel sheet
KR102305878B1 (en) * 2019-12-20 2021-09-27 주식회사 포스코 Steel sheet for enamel and method of manufacturing the same
KR102405223B1 (en) * 2020-11-05 2022-06-02 주식회사 포스코 Steel sheet for enamel and method of manufacturing the same
KR102469876B1 (en) * 2020-12-18 2022-11-23 주식회사 포스코 High strength cold-rolled enamel steel sheet with excellent adhesion, and method of manufacturing the same
CN113913699A (en) * 2021-10-26 2022-01-11 攀钢集团攀枝花钢铁研究院有限公司 Production method of cold-rolled enamel steel with yield strength of 300MPa

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ZA201307344B (en) 2014-11-26
CA2832357A1 (en) 2012-10-11
SI2534271T1 (en) 2015-10-30
BR112013025885A2 (en) 2016-12-20
US20190112684A1 (en) 2019-04-18
BR112013025885B1 (en) 2022-05-24
US20140065434A1 (en) 2014-03-06
CN103476955A (en) 2013-12-25
WO2012136270A1 (en) 2012-10-11
CN103476955B (en) 2016-03-30
US20190112683A1 (en) 2019-04-18
DK2534271T3 (en) 2015-08-24
EP2534271B1 (en) 2015-06-03
HUE027485T2 (en) 2016-09-28
PL2534271T3 (en) 2015-10-30
RS54209B1 (en) 2015-12-31
KR20140014248A (en) 2014-02-05
MX2013011685A (en) 2014-01-31
ES2545746T3 (en) 2015-09-15
PT2534271E (en) 2015-10-09
UA111195C2 (en) 2016-04-11
MX348721B (en) 2017-06-26
CA2832357C (en) 2016-06-07
KR101645786B1 (en) 2016-08-04
EA024029B1 (en) 2016-08-31

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