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
  • C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
  • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon

Definitions

• the invention relates to the manufacture of steel sheets or structural parts simultaneously combining a high modulus of elasticity E, a reduced density and a high strength.
• these materials have a much higher modulus of elasticity, ranging from about 250 to 550 GPa, than that of base steels, of the order of 210 GPa, where they are incorporated.
• a hardening is achieved by a charge transfer between the matrix and the ceramic particles under the influence of a stress.
• the refinement of the grain size of the matrix by the ceramic particles further increases this hardening.
• processes are known which are based on powder metallurgy: firstly, the geometrically controlled ceramic powders are prepared. these with steel powders, which corresponds for steel to an exogenous contribution of ceramic particles.
• the invention aims to solve the above problems, in particular the large scale and economical provision of steels with increased modulus of elasticity by the presence of TiB2 particles.
• the invention aims in particular at providing a continuous casting manufacturing method which does not present any particular difficulties when casting steels.
• the invention relates to a steel sheet whose chemical composition comprises, the contents being expressed by weight: 0.010% ⁇ C ⁇ 0.20%, 0.06% ⁇ Mn ⁇ 3%, Si ⁇ 1.5%, 0.005% ⁇ Al ⁇ 1.5%, S ⁇ 0.030%, P ⁇ 0.040%, of titanium and boron in amounts such that: 2.5% ⁇ Ti ⁇ 7.2%, (0, 45 xTi) - 0.35% ⁇ B ⁇ (0.45 xTi) + 0.70%, optionally one or more elements chosen from: Ni ⁇ 1%, Mo ⁇ 1%, Cr ⁇ 3%, Nb ⁇ 0, 1%, V ⁇ 0.1%, the rest of the composition consisting of iron and unavoidable impurities resulting from the preparation.
• the contents of titanium and boron, expressed in% by weight are such that: -0.22 ⁇ B - (0.45x Ti) ⁇ 0.35.
• the contents of titanium and boron, expressed in% by weight are such that: -0.35 ⁇ B - (0.45x Ti) ⁇ - 0.22.
• the titanium content is preferably such that: 4.6% ⁇ Ti ⁇ 6.9%. According to one particular embodiment, the titanium content is such that: 4.6% ⁇ Ti ⁇ 6%.
• the carbon content is preferably such that: C ⁇ 0.080%. According to a preferred mode, the carbon content satisfies: C ⁇ 0.050%.
• the chromium content is preferably such that: Cr ⁇ 0.08%.
• the invention also relates to a steel sheet of the above composition, comprising eutectic precipitates of TiB 2 and possibly Fe 2 B, whose average size is less than or equal to 15 micrometers, and preferably less than or equal to 10 micrometers. Preferably, more than 80% by number of TiB 2 precipitates have a monocrystalline character.
• the invention also relates to a steel sheet according to the above characteristics, whose average grain size is less than or equal to 15 microns, preferably less than or equal to 5 microns, very preferably less than 3.5 microns.
• the invention also relates to a steel sheet according to one of the above characteristics, whose modulus of elasticity measured in the rolling direction is greater than or equal to 230GPa, preferably greater than or equal to 240GPa, or preferentially greater than or equal to 250GPa According to a particular mode, the strength of the steel sheet is greater than or equal to 500 MPa and its uniform elongation is greater than or equal to 8%.
• the subject of the invention is also an article manufactured from a plurality of steel parts, of identical or different composition, of identical or different thickness, at least one of the steel parts being a steel sheet.
• the composition or compositions of the other steel parts comprising by weight: 0.001-0.25% C, 0.05-2 % Mn, Si ⁇ 0.4%, Al ⁇ 0.1%, Ti ⁇ 0.1%, Nb ⁇ 0.1%, V ⁇ 0.1%, Cr ⁇ 3%, Mo ⁇ 1%, Ni ⁇ 1%, B ⁇ 0.003%, the remainder of the composition consisting of iron and unavoidable impurities resulting from the preparation.
• the invention also relates to a method according to which a steel is supplied according to any one of the above compositions, and the steel is cast in the form of a semi-finished product, the casting temperature not exceeding more than 40 ° C the liquidus temperature of the steel.
• the semi-finished product is cast as slabs or thin products between counter-rotating rolls.
• the cooling rate during the solidification of the casting is preferably greater than or equal to 0.1 ° C./s.
• the semi-finished product is heated before hot rolling, the temperature and the duration of the heating being chosen so that that the density of eutectic precipitates of TiB 2 and possibly Fe 2 B, maximum size L ma ⁇ greater than 15 micrometers and form factor f> 5, is less than 400 / mm 2 .
• the semi-finished product is thermally rolled, optionally cold rolling and annealing, the rolling and annealing conditions being adjusted so that a steel sheet whose size is obtained is obtained.
• grain average is less than or equal to 15 microns, preferably less than or equal to 5 microns, very preferably less than 3.5 microns.
• the hot rolling is preferably carried out with an end-of-rolling temperature of less than 820 ° C.
• At least one blank is cut from a steel sheet according to one of the above modes, or manufactured according to one of the above modes, and the blank is deformed in a temperature range from 20 ° to 900 ° C.
• the invention also relates to a manufacturing method according to which one welds at least one steel sheet according to one of the above modes, or a steel sheet manufactured according to one of the modes above.
• the invention also relates to the use of a steel sheet or an object according to one of the above modes, or manufactured according to one of the modes above, for the manufacture of parts of structure or reinforcement elements in the automotive field.
• FIGS. 1 and 2 respectively illustrate the microstructure of two steels according to the invention comprising eutectic Fe-TB2 precipitation, in the raw casting state.
• FIG. 3 illustrates the microstructure of a steel according to the invention in the cold rolled and annealed state.
• FIGS. 4 and 5 illustrate the microstructure of two steels according to the invention comprising eutectic precipitations Fe-TiB 2 and Fe-Fe 2 B, respectively in the raw state of casting and hot rolled.
• FIGS. 6 and 7 illustrate the microstructure of a steel according to the invention, cooled according to two cooling speeds during solidification, in the raw state of casting
• the carbon content is adapted for the purpose of economically attaining a given level of yield strength or resistance.
• the carbon content also makes it possible to control the nature of the microstructure of the matrix of steels according to the invention, which can be partially or totally ferritic, bainitic, austenitic or martensitic or comprise a mixture of these constituents in proportion adapted to satisfy the mechanical properties required.
• a carbon content greater than or equal to 0.010% makes it possible to obtain these various constituents.
• the carbon content is limited because of the weldability: cold cracking resistance and heat-affected zone toughness decrease when the C content is greater than 0.20%.
• the carbon content is less than or equal to 0.050% by weight, the resistance weldability is particularly improved.
• the carbon content is preferably limited so as to avoid a primary precipitation of TiC and / or Ti (C 1 N) in the liquid metal. These precipitates which form in the liquid are detrimental to the flowability in the continuous casting process of the liquid steel. On the other hand, when this precipitation occurs in the solidification or solid phase interval, it has a favorable effect on the structural hardening.
• the maximum carbon content must therefore preferably be limited to 0.080% so as to reveal the TiC and / or Ti (C, N) precipitates, mainly during the eutectic or solid phase solidification.
• manganese increases the quenchability, contributes to hardening in solid solution and thus to obtaining increased strength. It combines with any sulfur present, reducing the risk of hot cracking.
• sulfur present, reducing the risk of hot cracking.
• Silicon effectively contributes to increasing strength through solid solution hardening.
• an excessive addition of silicon causes the formation of adherent oxides that are difficult to remove during a stripping operation, and the possible appearance of surface defects due in particular to a lack of wettability in the dip galvanizing operations.
• the silicon content should not exceed 1.5% by weight.
• aluminum is a very effective element for the deoxidation of steel. Beyond a content of 1, 5% by weight, excessive primary precipitation of alumina occurs, however, causing flowability problems. In excess of 0.030%, sulfur tends to precipitate excessively in the form of manganese sulfides which greatly reduce hot or cold forming ability.
• Phosphorus is a known element to segregate at grain boundaries. Its content must not exceed 0.040% so as to maintain a sufficient hot ductility by avoiding the creasability and to avoid hot cracking during welding.
• nickel or molybdenum can be added to increase the strength of the steel. For economic reasons, these additions are limited to 1% by weight.
• chromium can be added to increase the strength. It also makes it possible to precipitate borides in a larger quantity. However, its content is limited to 3% by weight to make a less expensive steel.
• a chromium content of less than or equal to 0.080% will be chosen.
• an excessive addition of Cr leads to more borides being precipitated, but these are borides of (Fe, Cr)
• niobium and vanadium may be added in an amount less than or equal to 0.1%, so as to obtain a complementary hardening in the form of precipitation of fine carbonitrides.
• Titanium and boron play an important role in the invention:
• the weight contents expressed in percent, titanium and boron of the steel are such that:
• the titanium and boron contents are such that: -0.22 ⁇ B - (0.45 ⁇ Ti) ⁇ 0.35
• the titanium and boron contents are such that: -0.35 ⁇ B - (0.45 ⁇ Ti) - 0.22
• B- (0.45xTi) is greater than or equal to -0.35 and less than -0.22
• the content of titanium dissolved at room temperature in the matrix is between 0.5% and 0 respectively, 8%. This amount is particularly suitable for obtaining a precipitation composed only of TiB 2 .
• the titanium content is such that: 4.6% ⁇ Ti ⁇ 6.9%
• the weight content of titanium is less than or equal to 6.9%, the amount of primary precipitates of TiB 2 is less than 3% by volume.
• the total precipitation of TiB 2 consisting of possible primary precipitates and eutectic precipitates, is then less than 15% by volume.
• the titanium content is such that: 4.6% ⁇ Ti ⁇ 6%: when the weight content of titanium is less than or equal to 6%, flowability is then particularly satisfactory due to the low precipitation of primary TiB 2 in the liquid metal.
• a eutectic Fe-TiB 2 precipitation occurs during solidification.
• the eutectic character of the precipitation confers on the microstructure formed a particular character of fineness and homogeneity that is advantageous for the mechanical properties.
• the modulus of elasticity of the steel measured in the rolling direction may exceed about 220 GPa.
• the module can exceed about 240 GPa, which makes it possible to design structures with notable lightening.
• This amount can be increased to 15% by volume to exceed about 250 GPa, especially in the case of steels comprising alloying elements such as chromium or molybdenum. The presence of these elements indeed increases the maximum amount of TiB2 that can be obtained in the case of eutectic precipitation.
• the boron and titanium contents according to the invention make it possible to avoid a coarse primary precipitation of TiB 2 in the liquid metal.
• the formation of these primary precipitates of sometimes large size (several tens of micrometers) must be avoided because of their harmful role vis-à-vis mechanisms of damage or rupture during subsequent mechanical stresses.
• these precipitates appeared in the liquid metal, when they do not decant, are distributed in a localized manner and reduce the homogeneity of the mechanical properties. This early precipitation must be avoided because it can lead to a plugging of nozzles from the continuous casting of steel following the agglomeration of precipitates.
• titanium must be present in sufficient quantity to lead to the endogenous formation of TiB 2 in the form of eutectic Fe-TiB 2 precipitation.
• the titanium may also be present dissolved at room temperature in the matrix in superstoichiometric proportion relative to boron, calculated from TiB 2 .
• the precipitation takes place in the form of two successive eutectics: Fe-TiB 2 in the first place, then Fe-Fe 2 B, this second endogenous Fe 2 B precipitation intervenes in greater or lesser quantity depending on the boron content of the alloy.
• the amount precipitated as Fe 2 B can be up to 8% by volume. This second precipitation also occurs according to a eutectic scheme to obtain a fine and homogeneous distribution, which ensures a good homogeneity of the mechanical characteristics.
• Fe 2 B completes that of TiB 2 , the maximum amount of which is linked to the eutectic.
• Fe 2 B has a role similar to that of TiB 2 . It increases the modulus of elasticity and decreases the density. It is thus possible to adjust the mechanical properties in a fine way by adjusting the precipitation complement of Fe 2 B with respect to the precipitation of TiB 2 .
• This is a means that can be used in particular to obtain a modulus of elasticity greater than 250 GPa in steel as well as an increase in the mechanical strength of the product.
• the modulus of elasticity increases by more than 5 GPa.
• the elongation at break is then between 14% and 16% and the mechanical strength reaches 590 MPa.
• the amount of Fe 2 B is greater than 7.5% by volume, the modulus of elasticity is increased by more than 10 GPa but the elongation at break is then less than 9%.
• the average size of the eutectic precipitates of TiB 2 or Fe 2 B is less than or equal to 15 microns so as to obtain increased elongation characteristics and good fatigue properties.
• the average size of these eutectic precipitates is less than or equal to 10 microns, the elongation at break may be greater than 20%.
• the inventors have demonstrated that, when more than 80% of the number of TiB 2 eutectic precipitates have a monocrystalline character, the matrix-precipitated damage during a mechanical stress is reduced and the risk of defect formation is lower. because of the greater plasticity of the precipitate and its great cohesion with the matrix.
• larger TiB 2 precipitates have hexagonal crystallization. Without wishing to be bound by theory, it is believed that this crystallographic character confers an increased possibility of deformation by twinning of these precipitates under the effect of a mechanical stress.
• the resistance to cleavage is particularly high: Charpy resilience tests of thickness 3 mm at -60 0 C, reveal that the proportion of ductile zone in the broken test pieces is greater than 90%.
• a steel of composition according to the invention is supplied
• the casting may be carried out in a format allowing the manufacture of products of various geometries, in particular in the form of a billet for the manufacture of long products.
• the fineness of the precipitation of TiB 2 and Fe 2 B increases the strength, ductility, resilience, formability and mechanical behavior in the Heat Affected Zone.
• the fineness of the precipitation is increased by a low casting temperature and a higher cooling rate. In particular, it has been found that a casting temperature limited to 40 ° C beyond the liquidus temperature, led to the obtaining of such fine microstructures.
• the casting conditions will also be chosen so that the cooling rate at the time of solidification is greater than or equal to 0.1 ° C./s so that the size of the precipitates of TiB 2 and Fe 2 B is particularly fine.
• the inventors have also demonstrated that the morphology of the eutectic precipitates of TiB 2 and Fe 2 B plays a role in the damage during a subsequent mechanical solidification. After observing the precipitates by optical microscopy at magnitudes ranging from 500 to 150Ox approximately on a surface which has a statistically representative population, it is determined by means of an image analysis software known per se such as, for example, the image analysis software Scion®., The maximum size L ⁇ 13x and minimum L min of each precipitate. The ratio between the maximum and minimum size characterizes the form of a given precipitate. The inventors have shown that precipitates of large size (L max > 15 micrometers) and elongated (f> 5) reduce the distributed elongation and the coefficient of hardening n.
• the temperature and the reheating time of the semi-finished product are chosen before the subsequent hot rolling so as to cause a globulization of the most harmful precipitates.
• the temperature and the reheating time will be chosen so that the density of eutectic precipitates with a size L m ⁇ > 5 microns and elongated (f> 5) is less than 400 / mm 2 .
• the semi-finished product is then hot-rolled, optionally followed by a winding.
• cold rolling and annealing are carried out to obtain sheets of lesser thickness.
• the conditions of hot rolling, winding, cold rolling and annealing are chosen such that a steel sheet is obtained whose average grain size is less than or equal to 15 micrometers, preferably less than 5 microns. micrometers, very preferably less than 3.5 micrometers.
• a finer grain size is obtained by: - an important work hardening before the end of hot rolling and before the allotropic transformation ( ⁇ - ⁇ ) occurring during cooling
• a low end-of-rolling temperature preferably less than 820 ° C.
• an end-of-hot-rolling temperature below 82 ° C. is an effective means for obtaining a fine grain size.
• the higher deformation field around the precipitates favors the germination of the grains during the restoration / recrystallization which follows the cold rolling, resulting in a refinement of the grain.
• the steel sheet thus obtained thus has a very good formability: without wishing to be bound by theory, it is believed that the eutectic precipitates present within a highly deformable matrix play a role similar to that played by the martensitic or bainitic phases within the ferrite in "Dual-Phase" type steels.
• the steels according to the invention have a ratio (elasticity limit Re / resistance Rm) favorable to various shaping operations.
• hot-rolled or hot-rolled sheets can be obtained.
• cold and annealed having matrices with various microstructures these may be totally or partially ferritic, bainitic, martensitic or austenitic.
• a steel containing 0.04% C, 5.9% Ti, 2.3% B will have, after cooling from 1200 0 C, a hardness ranging from 187 to 327 HV for a cooling rate ranging from at 15O 0 CVs.
• the highest levels of hardness correspond in this case to a totally bainitic matrix composed of slats with low disorientation, without carbides.
• a blank is cut from the sheet and deformation is carried out by means such as stamping, folding in a box.
• temperature range between 20 and 900 ° C. Very good thermal stability of the TiB 2 and Fe 2 B hardening phases is observed up to 1100 ° C.
• pieces of complex geometry with an increased modulus of elasticity can be produced according to the invention.
• the increase of the modulus of elasticity of the steels according to the invention decreases the springback after the shaping operations and thus increases the dimensional accuracy on finished parts.
• Structural elements are also advantageously manufactured by welding steels according to the invention, of identical or different composition or thickness so as to obtain in the final stage parts whose mechanical characteristics vary within them and are adapted locally. to subsequent solicitations.
• the composition by weight of steels that can be welded to the steels according to the invention will comprise, for example: 0.001-0.25% C, 0.05-2% Mn, Si ⁇ O.4%, AI ⁇ 0.1%, Ti ⁇ 0.1%, Nb ⁇ 0.1%, V ⁇ 0.1%, Cr ⁇ 3%, Mo ⁇ 1%, Ni ⁇ 1%, B ⁇ 0.003%, the balance of the composition consisting of iron and unavoidable impurities resulting from the elaboration.
• composition of a reference steel R1 containing no endogenous eutectic precipitates of TiB 2 or Fe 2 B has been indicated for comparison.
• These steels were produced by casting semi-finished products from the liquid state, the additions of titanium and boron being carried out for steels 1-1 and I-2 in the form of ferroalloys.
• the casting temperature is 133O 0 C, an excess of 40 ° C. with respect to the liquidus temperature.
• FIGS. 1 and 2 The microstructure in the raw state of casting, illustrated in FIGS. 1 and 2, relating respectively to steels 1-1 and I-2, shows a fine and homogeneous dispersion of endogenous TiB 2 precipitates within a ferritic matrix. Boron precipitates as a Fe-TiB 2 binary eutectic.
• the volume amounts of precipitates were measured by means of an image analyzer and are respectively 9% and 12.4% for I-1 and I-2 steels.
• the amount of TiB 2 in the form of primary precipitates is less than 2% by volume and promotes good flowability.
• the average sizes of the eutectic precipitates of TiB 2 are respectively 5 and 8 microns for the 1-1 and I-2 steels.
• more than 80% in number have a monocrystalline character.
• hot-rolled sheets were then pickled according to a method known per se and then cold-rolled to a thickness of 1 mm.
• a recrystallization annealing was then carried out at 800 ° C. for 1 minute of maintenance, followed by cooling in air.
• the average grain size of the steel 1-1 is 12 micrometers whereas it is 28 micrometers for the reference steel.
• a low end-of-rolling temperature (810 ° C) leads to a very fine average grain size (3.5 micrometers) after hot rolling.
• Table 3 Mechanical tensile characteristics of cold-rolled and annealed sheets (parallel to rolling)
• the ratio Re / Rm of the hot-rolled or cold-rolled sheets according to the invention is close to 0.5, reflecting a mechanical behavior approaching that of a Dual-Phase steel and a good aptitude for subsequent shaping.
• Spot resistance welding tests were carried out on cold-rolled steel 1-1 sheets: failure in tensile-shear tests occurs systematically by unsticking. It is known that this is a preferred mode of rupture because associated with high energy.
• the presence of eutectic precipitates according to the invention is also observed in welded melted zones, which contributes to a homogeneity of mechanical properties in welded joints. Satisfactory properties are also obtained in LASER welding and arc welding.
• Table 4 below shows the composition of three steels according to the invention.
• the steels were produced by casting semi-finished products, the additions of titanium and boron being carried out in the form of ferroalloys.
• the casting temperature is 40 ° C. above the liquidus temperature.
• the steels I-3 to I-5 have an excess of boron with respect to the stoichiometry of TiB 2 so that eutectic co-precipitation of TiB 2 and Fe 2 B occur.
• the volume amounts of eutectic precipitates are shown in Table 5.
• FIG. 4 illustrates, in the case of steel I-3, the coexistence of TiB 2 and Fe 2 B precipitates.
• the Fe 2 B precipitates appearing in light gray and the darker TiB 2 precipitates are dispersed. within the ferritic matrix.
• Table 6 Mechanical tensile characteristics of hot rolled sheets (direction parallel to rolling) and density.
• Semi-finished products of steel of composition I-2 were cast at a temperature of 1330 ° C. By varying the intensity of the cooling flow of these semi-finished products, and the thickness of the cast semi-finished products, two cooling rates were achieved, ie 0.8 and 12 ° C / s.
• the microstructures shown in FIGS. 6 and 7 illustrate that an increased cooling rate makes it possible to very significantly refine the eutectic Fe-TiB 2 precipitation.
• a 1-2 steel sheet was also welded by LASER without any difficulty in operation with a soft, stampable steel sheet whose composition contains (% by weight): 0.003% C, 0.098% Mn, 0.005% Si, 0.059% AI , 0.051% Ti, 0.0003% B, as well as unavoidable impurities resulting from the elaboration.
• the melted zone still contains Fe-TiB 2 eutectic precipitation, which is naturally less important than in the case of welding. autogenous. In this way, it is possible to manufacture metal structures whose rigidity properties vary locally and whose mechanical characteristics more specifically correspond to the local requirements for implementation or maintenance in service.
• the welding domain expressed in intensity I is between 7 and 8.5 kA.
• the two terminals of this domain correspond on the one hand to obtaining a core diameter greater than 5.2mm (lower limit in intensity) and on the other hand to the appearance of the spark when welding (terminal).
• the steel according to the invention thus has good resistance to spot welding with a sufficiently wide weldability range of 1.5 kA.
• the invention thus enables the manufacture of structural parts or reinforcing elements with an increased level of performance, both in terms of intrinsic lightening and the increase of the modulus of elasticity.
• the easy implementation by welding of the steel sheets according to the invention makes their incorporation possible within more complex structures, in particular by means of connections with pieces of steels of different composition or thickness. We will take particular advantage of these different characteristics in the automotive field.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Heat Treatment Of Sheet Steel (AREA)
• Continuous Casting (AREA)
• Heat Treatment Of Steel (AREA)
• Resistance Welding (AREA)
• Laminated Bodies (AREA)

Priority Applications (2)

Applications Claiming Priority (3)

Publications (2)

Family

ID=37496804

Family Applications (2)

Family Applications Before (1)

Country Status (16)

Cited By (2)

Families Citing this family (21)

Family Cites Families (12)

• 2006
  • 2006-09-06 EP EP06291413A patent/EP1897963A1/de not_active Withdrawn
• 2007
  • 2007-08-27 TR TR2018/02707T patent/TR201802707T4/tr unknown
  • 2007-08-27 BR BRPI0716877A patent/BRPI0716877B1/pt active IP Right Grant
  • 2007-08-27 CA CA2662741A patent/CA2662741C/fr active Active
  • 2007-08-27 HU HUE07823448A patent/HUE036845T2/hu unknown
  • 2007-08-27 JP JP2009527173A patent/JP5298017B2/ja not_active Expired - Fee Related
  • 2007-08-27 RU RU2009108338/02A patent/RU2416671C2/ru active
  • 2007-08-27 ES ES07823448.1T patent/ES2659987T3/es active Active
  • 2007-08-27 PL PL07823448T patent/PL2064360T3/pl unknown
  • 2007-08-27 CN CN2007800330419A patent/CN101563476B/zh active Active
  • 2007-08-27 UA UAA200902135A patent/UA95490C2/ru unknown
  • 2007-08-27 WO PCT/FR2007/001401 patent/WO2008029011A2/fr not_active Ceased
  • 2007-08-27 EP EP07823448.1A patent/EP2064360B1/de active Active
  • 2007-08-27 KR KR1020097004737A patent/KR20090043555A/ko not_active Ceased
  • 2007-08-27 MX MX2009002411A patent/MX2009002411A/es active IP Right Grant
• 2009
  • 2009-02-26 ZA ZA2009/01377A patent/ZA200901377B/en unknown
  • 2009-03-03 MA MA31679A patent/MA30698B1/fr unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events