Patent Description:
It is known to weld steel substrates by laser arc hybrid welding. This welding technique combines the principles of laser beam welding and arc welding. There are four main types of laser arc hybrid welding process, depending on the setup used: Tungsten Inert Gas (TIG) also known as Gas Tungsten Arc (GTA), Gas Metal Arc (GMA), sometimes referred to by its subtypes Metal Inert Gas (MIG) or Metal Active Gas (MAG), Plasma Arc and Submerged Arc (SA).

The combination of the laser process and the arc process results in an increase in both weld penetration depth and welding speed (as compared to each process alone). Nevertheless, despite these improvements, there is still room for limiting the crack occurrence in the welds and improving the process stability and consequently the weld penetration.

<CIT> discloses a method for the manufacture of a welded joint comprising the following successive steps:
The provision of at least two metallic substrates wherein at least one metallic substrate is a steel substrate being at least partially coated with a pre-coating comprising a titanate and a nanoparticulate oxide selected from the group consisting of TiO2 , SiO2, Y2O3, ZrO2 and mixtures thereof, and II. The welding of the at least two metallic substrates. It is also known from <CIT> to coat a metal strip with an aqueous dispersion containing in addition to water: a) at least one organic film former containing at least one water-soluble or water-dispersed polymer; b) a quantity of cations and/or hexa- or tetrafluoro complexes of cations chosen from a group consisting of titanium, zirconium, hafnium, silicon, aluminium and boron; and c) at least one inorganic compound in particle form with an average particle diameter measured on a scanning electron microscope of <NUM> to <NUM>.

There is thus a need for improving the quality of the weld made by laser arc hybrid welding and therefore the mechanical properties of welded steel substrates. There is also a need for increasing the deposition rate and productivity of the laser arc hybrid welding.

To this end, the invention relates to a method for the manufacture of a welded joint comprising the following successive steps:.

Advantageous embodiments of the invention are laid down in the dependent claims.

The method may also have the optional features listed below, considered individually or in combination.

According to another non-claimed variant, the precoating further comprises microparticulate compounds selected from the list consisting of CeO<NUM>, Na<NUM>O, Na<NUM>O<NUM>, NaBiO<NUM>, NaF, CaF<NUM>, cryolite (Na<NUM>AlF<NUM>) and mixtures thereof.

The invention also relates to a method for the manufacture of a pre-coated steel substrate comprising the successive following steps:.

The method for the manufacture of a pre-coated steel substrate may also have the optional features listed below, considered individually or in combination.

The invention also relates to a steel substrate having a thickness of at least <NUM> and being delimited by at least one beveled edge with a bevel angle comprised between <NUM> and <NUM>°, wherein said beveled edge is at least partially coated with a pre-coating comprising a titanate and a nanoparticulate oxide selected from the group consisting of TiO<NUM>, SiO<NUM>, ZrO<NUM>, Y<NUM>O<NUM>, Al<NUM>O<NUM>, MoO<NUM>, CrO<NUM>, CeO<NUM>, La<NUM>O<NUM> and mixtures thereof.

Without willing to be bound by any theory, it is believed that the pre-coating mainly modifies the melt pool physics during welding. It seems that, in the present invention, not only the nature of the compounds, but also the size of the oxide particles being equal to or below <NUM> modifies the arc and melt pool physics.

Indeed, the arc, which is going first, melts and incorporates the pre-coating in the molten metal in the form of dissolved species and in the arc in the form of ionized species. Thanks to the presence of titanate and nanoparticles in the arc, the arc is constricted and the temperature of the molten metal pool increases. Consequently, the keyhole, i.e. a literal hole in the steel substrate caused by its vaporization, is formed more easily by the laser impacting the molten metal pool. This improves the process efficiency.

Moreover, the pre-coating dissolved in the molten metal modifies the Marangoni flow, which is the mass transfer at the liquid-gas interface due to the surface tension gradient. In particular, the components of the pre-coating modify the gradient of surface tension along the interface. This modification of surface tension results in an inversion of the fluid flow towards the center of the weld pool. Without willing to be bound by any theory, it is believed that the nanoparticles dissolve at lower temperature than microparticles and therefore more oxygen is dissolved in the melt pool, which activates the reverse Marangoni flow. The latter contributes to the retention of a proper keyhole shape, which, in turn, prevents gas entrapment and thus pores in the weld.

Moreover, the titanate mixed with the nanoparticulate oxide modifies the plasma plume interaction with the laser beam. In particular, the increase in oxygen due to the dissolution of the pre-coating reduces the scattering of the laser beam. Consequently, the laser spot diameter is reduced while the keyhole effect is enhanced. This allows the energy beam to penetrate even more deeply and to be delivered very efficiently into the join. This increases the weld penetration and minimizes the heat affected zone, which in turn limits part distortion.

Moreover, as the components of the pre-coating make the surface tension increase with temperature, the wettability of the weld material increases along the bevel which is colder than the center of the melt pool, which prevents slag entrapment.

Additionally, it has been observed that the nanoparticles improve the homogeneity of the applied pre-coating by filling the gaps between the microparticles and covering the surface of the microparticles. It helps stabilizing the welding arc, thus improving the weld penetration and quality.

The invention will be better understood by reading the following description, which is provided purely for purposes of explanation and is in no way intended to be restrictive with reference to <FIG>, which illustrates a substrate with a beveled edge in double Y.

The pre-coating comprises a titanate and a nanoparticulate oxide selected from the group consisting of TiO<NUM>, SiO<NUM>, ZrO<NUM>, Y<NUM>O<NUM>, Al<NUM>O<NUM>, MoOs, CrOs, CeO<NUM>, La<NUM>O<NUM> and mixtures thereof. In other words, the pre-coating comprises a titanate and at least one nanoparticulate oxide, wherein the at least one nanoparticulate oxide is selected from the group consisting of TiO<NUM>, SiO<NUM>, ZrO<NUM>, Y<NUM>O<NUM>, Al<NUM>O<NUM>, MoO<NUM>, CrOs, CeO<NUM>, La<NUM>O<NUM> and mixtures thereof. This means that the pre-coating doesn't comprise any other nanoparticulate oxide that the ones listed.

The titanate is selected from the group of titanates consisting of alkali metal titanates, alkaline-earth titanates, transition metal titanates, metal titanates and mixtures thereof. The titanate is more preferably chosen from among: Na<NUM>Ti<NUM>O<NUM>, NaTiOs, K<NUM>TiO<NUM>, K<NUM>Ti<NUM>O<NUM>, MgTiOs, SrTiOs, BaTiOs, CaTiOs, FeTiOs and ZnTiO<NUM> and mixtures thereof. It is believed that these titanates further increase the penetration depth based on the effect of the reverse Marangoni flow. It is the inventors understanding that all titanates behave, in some measure, similarly and increase the penetration depth. All titanates are thus part of the invention. The man skilled in the art will know which one has to be selected depending on the specific case. To do so, he will take into account how easily the titanates melt and dissolve, how much they increase the dissolved oxygen content, how the additional element of the titanate affects the melt pool physics and the microstructure of the final weld. For example, NaTiO<NUM> is favored due to the presence of Na that improves the slag formation and detachment.

Preferably, the titanate has a diameter between <NUM> and <NUM>, more preferably between <NUM> and <NUM> and advantageously between <NUM> and <NUM>. It is believed that this titanate diameter further improves the arc constriction and the reverse Marangoni effect. Moreover, having small micrometric titanate particles increases the specific surface area available for the mix with the nanoparticulate oxides and have the latter further adhere to the titanate particles. It also makes the particles easier to spray.

Preferably, the percentage in weight of the titanate in dry weight of pre-coating is above or equal to <NUM>%, more preferably between <NUM>% and <NUM>% and even more preferably between <NUM>% and <NUM>%.

The nanoparticulate oxide is chosen from TiO<NUM>, SiO<NUM>, ZrO<NUM>, Y<NUM>O<NUM>, Al<NUM>O<NUM>, MoOs, CrOs, CeO<NUM>, La<NUM>O<NUM> and mixtures thereof. These nanoparticles dissolve easily in the melt pool, provide oxygen to the melt pool and, consequently, increase the penetration depth and stabilize the keyhole which prevent defects. Contrary to other oxides, such as CaO, MgO, B<NUM>O<NUM>, Co<NUM>O<NUM> or Cr<NUM>O<NUM>, they do not tend to form brittle phases, they do not have a high refractory effect that would prevent the heat from correctly melting the steel and their metal ions do not tend to recombine with oxygen in the melt pool.

Preferably, the nanoparticles are SiO<NUM> and/or TiO<NUM>, and more preferably a mixture of SiO<NUM> and TiO<NUM>. It is believed that SiO<NUM> mainly increases the penetration depth and eases the slag removal while TiO<NUM> mainly increases the penetration depth and forms Ti-based inclusions which improve the mechanical properties.

Other examples of mixtures of nanoparticulate oxides are:.

Preferably, the nanoparticles have a size comprised between <NUM> and <NUM>. it is believed that this nanoparticles diameter further improves the homogeneous distribution of the coating.

Preferably, the percentage in weight of the nanoparticulate oxide in dry weight of pre-coating is below or equal to <NUM>%, preferably above or equal to <NUM>%, more preferably between <NUM> and <NUM>%, even more preferably between <NUM> and <NUM>%. In some cases, the percentage of nanoparticles may have to be limited to avoid a too high refractory effect. The man skilled in the art who knows the refractory effect of each kind of nanoparticles will adapt the percentage case by case.

According to one variant of the invention, once the pre-coating is applied on the steel substrate and dried, it consists of a titanate and a nanoparticulate oxide.

According to another variant of the invention, the pre-coating further comprises at least one binder embedding the titanate and the nanoparticulate oxide and improving the adhesion of the pre-coating on the steel substrate. This improved adhesion further prevents the particles of the pre-coating from being blown away by the flow of the shielding gas when such a gas is used. Preferably, the binder is purely inorganic, notably to avoid fumes that an organic binder could possibly generate during welding. Examples of inorganic binders are sol-gels of organofunctional silanes or siloxanes. Examples of organofunctional silanes are silanes functionalized with groups notably of the families of amines, diamines, alkyls, amino-alkyls, aryls, epoxys, methacryls, fluoroalkyls, alkoxys, vinyls, mercaptos and aryls. Amino-alkyl silanes are particularly preferred as they are greatly promoting the adhesion and have a long shelf life. Preferably, the binder is added in an amount of <NUM> to <NUM> wt% of the dried pre-coating.

According to another non-claimed variant, the pre-coating further comprises microparticulate compounds, such as microparticulate oxides and/or microparticulate fluorides, such as, for example, CeOz, Na<NUM>O, Na<NUM>O<NUM>, NaBiO<NUM>, NaF, CaF<NUM>, cryolite (Na<NUM>AlF<NUM>). Moving from nanoparticles to microparticles for some of the nanoparticulate oxides listed above alleviate the health and safety concerns related to the use of some of these oxides. NazO, Na<NUM>O<NUM>, NaBiOs, NaF, CaF<NUM>, cryolite can be added to improve the slag formation so that slag entrapment is further prevented. They also help forming an easily detachable slag. The pre-coating can comprise from <NUM> to <NUM> wt%, in dry weight of pre-coating, of NazO, NazOz, NaBiOs, NaF, CaF<NUM>, cryolite or mixtures thereof.

Preferably the thickness of the pre-coating is between <NUM> to <NUM> more preferably between <NUM> to <NUM>.

The pre-coating covers at least partially one beveled edge of a steel substrate. The latter can have any shape compatible with the laser arc hybrid welding. For the purpose of the invention, it is simply defined by a thickness of at least <NUM>, so that it is compatible with laser arc hybrid welding, and by a beveled edge to be at least partially welded to another metallic substrate. The bevel can have the shape of a single Y or a double Y, depending on the thickness of the sample. The bevel angle is preferably comprised between <NUM> and <NUM>°. Lower angles may promote the lack of edge fusion and higher angles would require more welding passes to fill the material. When the bevel has the shape of a double Y, the bevel angle refers to the angle of each Y.

Preferably, the beveled edge is milled so that the roughness Rz is higher than <NUM> more preferably comprised between <NUM> and <NUM>. Such roughness improves the adhesion of the pre-coating on the beveled edge.

Preferably, the steel substrate is carbon steel.

The steel substrate can be optionally coated on at least part of one of its sides by an anti-corrosion coating. Preferably, the anti-corrosion coating comprises a metal selected from the group consisting of zinc, aluminium, copper, silicon, iron, magnesium, titanium, nickel, chromium, manganese and their alloys.

In a preferred embodiment, the anti-corrosion coating is an aluminium-based coating comprising less than <NUM> wt. % Si, less than <NUM> wt. % Fe, optionally <NUM> to <NUM> wt. % Mg and optionally <NUM> to <NUM> wt. % Zn, the remainder being Al and the unavoidable impurities resulting from the manufacturing process. In another preferred embodiment, the anti-corrosion coating is a zinc-based coating comprising <NUM>-<NUM> wt. % Al, optionally <NUM>-<NUM> wt. % Mg, the remainder being Zn and the unavoidable impurities resulting from the manufacturing process.

The anti-corrosion coating is preferably applied on both sides of the steel substrate.

In term of process, once a steel substrate has been provided, a pre-coating solution is applied at least partially on the substrate beveled edge so as to form the pre-coating.

The pre-coating solution comprises a titanate and a nanoparticulate oxide, as described above for the pre-coating. In particular, it comprises from <NUM> to <NUM>/L of titanate, more preferably between <NUM> and <NUM>. In particular, it comprises from <NUM> to <NUM>. L-<NUM> of nanoparticulate oxide, more preferably between <NUM> and <NUM>. Thanks to these concentrations in titanate and nanoparticulate oxide, the quality of the weld obtained with the help of the corresponding pre-coating is further improved.

Advantageously, the pre-coating solution further comprises a solvent. It allows for a well dispersed pre-coating. Preferably, the solvent is volatile at ambient temperature. For example, the solvent is chosen from among: water, volatile organic solvents such as acetone, methanol, isopropanol, ethanol, ethyl acetate, diethyl ether and non-volatile organic solvents such as ethylene glycol.

According to one variant of the invention, the pre-coating solution further comprises a binder precursor to embed the titanate and the nanoparticulate oxide and to improve the adhesion of the pre-coating on the steel substrate. Preferably, the binder precursor is a sol of at least one organofunctional silane. Examples of organofunctional silanes are silanes functionalized with groups notably of the families of amines, diamines, alkyls, amino-alkyls, aryls, epoxys, methacryls, fluoroalkyls, alkoxys, vinyls, mercaptos and aryls. Preferably, the binder precursor is added in an amount of <NUM> to <NUM>. L-<NUM> of the pre-coating solution.

The pre-coating solution can be obtained by first mixing titanate and nanoparticulate oxide. It can be done either in wet conditions with a solvent such as acetone or in dry conditions for example in a 3D powder shaker mixer. The mixing favors the aggregation of the nanoparticles on the titanate particles which prevents the unintentional release of nanoparticles in the air, which would be a health and safety issue.

The deposition of the pre-coating solution can be notably done by spin coating, spray coating, dip coating or brush coating.

Preferably, the pre-coating solution is deposited locally only. In particular, the pre-coating solution is applied in the area of the beveled edge where the steel substrate will be welded.

Once the pre-coating solution has been applied on the steel substrate, it can optionally be dried. The drying can be performed by blowing air or inert gases at ambient or hot temperature. When the pre-coating comprises a binder, the drying step is preferably also a curing step during which the binder is cured. The curing can be performed by Infra-Red (IR), Near Infra-Red (NIR), conventional oven.

Preferably, the drying step is not performed when the organic solvent is volatile at ambient temperature. In that case, the organic solvent evaporates leading to a dried pre-coating on the metallic substrate.

Once the pre-coating has been formed on a part of the beveled edge of the steel substrate, this part can be welded to another metallic substrate by laser arc hybrid welding.

The arc of the laser arc hybrid welding can be selected among submerged arc, gas metal arc, gas tungsten arc and plasma arc. All these arcs can benefit from the present invention.

The average electric current is preferably between <NUM> and 1000A. The voltage is preferably between <NUM> and 40V.

The laser of the laser arc hybrid welding can be selected among solid state lasers, such as Nd:YAG, Nd:glass, Ruby, Nd:YLF, Yb:YAG, Yb:fibre, Tksapphire. Preferably, it is a Nd:YAG laser whose most common emission wavelength is <NUM> or an Yb:YAG laser (at <NUM>).

Any combination of arc and laser can benefit from the present invention since the pre-coating has similar effects on the different arcs and different lasers.

The welding is operated in leading arc configuration. This means that the arc is ahead of the laser beam. The arc hits first the steel substrate and melts it so as to form a molten pool. The laser then impacts the molten pool.

The other metallic substrate can be a steel substrate of the same composition or of a different composition than the pre-coated steel substrate. It can also be made of another metal, such as for example, aluminium. More preferably, the other metallic substrate is a pre-coated steel substrate according to the present invention. The other metallic substrate is positioned along the pre-coated beveled edge of the steel substrate. The two substrates are then welded by laser arc hybrid welding.

Depending on the welding technique, there can be a consumable electrode in the form of a wire (SAW, GMAW) or, if the electrode is not consumable, a material to fill the joint can be fed from the side in the form of a wire (GTAW, Plasma). In both cases, the wire is for example made of Fe, Si, C, Mn, Mo and/or Ni.

Depending on the welding technique, the beveled edge can be at least locally covered by a shielding flux. The shielding flux protects the welded zone from oxidation during welding.

With the method according to the present invention, it is possible to obtain a welded joint of at least a first metallic substrate in the form of a steel substrate and a second metallic substrate, the first and second metallic substrates being at least partially welded together by laser arc hybrid welding wherein the welded zone comprises a dissolved and/or precipitated pre-coating comprising a titanate and a nanoparticulate oxide.

The titanate is selected from the group of titanates consisting of alkali metal titanates, alkaline-earth titanates, transition metal titanates, metal titanates and mixtures thereof. The titanate is more preferably chosen from among: Na<NUM>Ti<NUM>O<NUM>, NaTiOs, K<NUM>TiO<NUM>, K<NUM>Ti<NUM>O<NUM> MgTiOs, SrTiOs, BaTiO<NUM>, CaTiOs, FeTiOs and ZnTiO<NUM> and mixtures thereof.

The nanoparticulate oxide is chosen from TiOz, SiOz, ZrO<NUM>, Y<NUM>O<NUM>, Al<NUM>O<NUM>, MoO<NUM>, CrOs, CeO<NUM>, La<NUM>O<NUM> and mixtures thereof.

By "dissolved and/or precipitated pre-coating", it is meant that components of the pre-coating can be dragged towards the center of the liquid-gas interface of the melt pool because of the reverse Marangoni flow and can be even dragged inside the molten metal. Some components dissolve in the melt pool which leads to an enrichment in the corresponding elements in the weld. Other components precipitate and are part of the complex oxides forming precipitates in the weld.

In particular, when the Al amount of the steel substrate is above 50ppm, the welded zone comprises inclusions comprising notably Al-Ti oxides or Si-Al-Ti oxides or other oxides depending on the nature of the added nanoparticles. These precipitates of mixed elements are smaller than <NUM>. Consequently, they do not compromise the toughness of the welded zone. The inclusions can be observed by Electron Probe Micro-Analysis (EPMA). Without willing to be bound by any theory, it is believed that the nanoparticulate oxides promote the formation of inclusions of limited size so that the toughness of the welded zone is not compromised.

Finally, a welded joint can be prepared by the method according to the present invention for the manufacture of components for oil&gas and offshore industries, shipbuilding, construction and transportation (rail and automotive).

The steel substrate having the chemical composition in weight percent disclosed in Table <NUM> was selected:.

The steel substrate was <NUM> thick. It had a tensile strength of <NUM>-<NUM> MPa and a yield strength of <NUM> MPa.

As illustrated on <FIG>, samples <NUM> of 100x150mm were prepared with beveled edges in double Y, each bevel being tilted at an angle α of <NUM>° and the upper and lower bevel being separated by a gap <NUM> of <NUM>. The beveled edges were milled so that the bevel has a roughness Rz of <NUM>-<NUM> and the <NUM> gap has a roughness Rz of <NUM>-<NUM>. The beveled edge to be welded was cleaned from oil and dirt with acetone.

Sample <NUM> was not coated with a pre-coating.

For sample <NUM>, an acetone solution comprising MgTiO<NUM> (diameter: <NUM>), SiO<NUM> (diameter: <NUM>) and TiO<NUM> (diameter: <NUM>) was prepared by mixing acetone with said elements. In the acetone solution, the concentration of MgTiO<NUM> was of <NUM>. The concentration of SiO<NUM> was of <NUM>. The concentration of TiO<NUM> was of <NUM>. Then, the cleaned sidewall of sample <NUM> was coated with the acetone solution by spraying. The acetone evaporated. The percentage of MgTiO<NUM> in the dried pre-coating was of 70wt. %, the percentage of SiO<NUM> was of <NUM>0wt. % and the percentage of TiO<NUM> was of 20wt. The pre-coating was <NUM> thick.

Samples <NUM> and <NUM> were each positioned side by side with a bare sample of the selected steel substrate spaced by a <NUM> gap and welded by laser arc hybrid welding in leading arc configuration without preheating by conducting weld passes until the bevel was filled and the joint was complete. The laser was a 16kW Yb:YAG laser with a <NUM> spot. The arc equipment was a gas metal arc welding torch with an Argon/CO<NUM> <NUM>/<NUM> shielding gas. The feeding wire comprised maximum <NUM>. 06wt% C, <NUM>. 8wt% Si et <NUM>. The welding parameters are in the following Table <NUM>:.

As it is apparent from Table <NUM>, Sample <NUM> needed two welding passes to be fully welded while Sample <NUM> needed only one welding pass with the same welding parameters. This first result already shows that the pre-coating according to the invention increases the penetration depth and productivity of the laser arc hybrid welding in leading arc configuration.

After welding, the weld of both welded assemblies was inspected visually and by X-ray imaging and a cross-section was analyzed micrographically.

The pre-coating improved the arc penetration by <NUM>% and the laser penetration by <NUM>%.

The X-ray imaging analysis revealed cracks along the weldment of Sample <NUM> and the cross-section analysis revealed cracks in Sample <NUM>. These results show that the pre-coating improves the wettability.

Tensile tests, Charpy-V tests and hardness characterization also confirmed that the pre-coating on the beveled edge of the steel substrate improves the laser arc hybrid welding in leading arc configuration without degrading the mechanical properties of the joint.

Sample <NUM> was prepared as Sample <NUM> (with pre-coating).

It was then welded with an increased travel speed (<NUM>/s, i.e. an increase of <NUM>%) and a reduced gap (<NUM>), with and without preheating the samples at <NUM> before welding, all other conditions being the same as in Example <NUM>.

The results obtained confirmed that, thanks to the pre-coating, it is possible to increase the travel speed and thus the productivity of the laser arc hybrid welding. Moreover, this productivity improvements comes without degradation of the mechanical properties of the joint and even with improvement of some mechanical properties of the joint as shown in Table <NUM>, where the results obtained with pre-heated Sample <NUM> are compared to the ones obtained with pre-heated Sample <NUM> (detailed in Example <NUM>):.

Charpy V-test was done according to ISO <NUM>:<NUM> at T= -20ºC.

"OK" in column "Fracture in base material" means that the fracture of the sample at the end of the tensile test was on the base metal, which is sought for welded samples.

"OK" in column "hardness" means that the hardness of the tested sample complies with the ISO <NUM>-<NUM> :<NUM> standard.

The effect of different pre-coatings on the welding of steel substrates was assessed by Finite Element Method (FEM) simulations. In the simulations, the pre-coatings comprise nanoparticulate oxides having a diameter of <NUM>-<NUM> and optionally MgTiO<NUM> (diameter: <NUM>). The thickness of the coating was of <NUM>. Arc welding was simulated with each pre-coating and the results are in the following Table <NUM>:.

Results show that the pre-coatings according to the present invention improve the penetration and the quality of the welds compared to comparative examples.

For sample <NUM>, a water solution comprising the following components was prepared: <NUM>. L-<NUM> of MgTiO<NUM> (diameter: <NUM>), <NUM>. L-<NUM> of SiO<NUM> (diameter range: <NUM>-<NUM>), <NUM>. L-<NUM> of TiO<NUM> (diameter range: <NUM>-<NUM>) and <NUM>. L-<NUM> of <NUM>-aminopropyltriethoxysilane (Dynasylan® AMEO produced by Evonik®). The solution was applied on the beveled edge of the steel substrate and dried by <NUM>) IR and <NUM>) NIR. The dried pre-coating was <NUM> thick and contained <NUM> wt% of MgTiOs, <NUM> wt% of SiO<NUM>, <NUM> wt% of TiO<NUM> and <NUM> wt% of the binder obtained from <NUM>-aminopropyltriethoxysilane.

For sample <NUM>, a water solution comprising the following components was prepared: <NUM>. L-<NUM> of MgTiO<NUM> (diameter: <NUM>), <NUM>. L-<NUM> of SiO<NUM> (diameter range: <NUM>-<NUM>), <NUM>. L-<NUM> of TiO<NUM> (diameter range: <NUM>-<NUM>), <NUM>. L-<NUM> of <NUM>-aminopropyltriethoxysilane (Dynasylan® AMEO produced by Evonik®) and <NUM>. L-<NUM> of a composition of organofunctional silanes and functionalized nanoscale SiO<NUM> particles (Dynasylan® Sivo <NUM> produced by Evonik). The solution was applied on the beveled edge of the steel substrate and dried by <NUM>) IR and <NUM>) NIR. The dried pre-coating was <NUM> thick and contained <NUM> wt% of MgTiOs, <NUM> wt% of SiO<NUM>, <NUM> wt% of TiO<NUM> and <NUM> wt% of the binder obtained from <NUM>-aminopropyltriethoxysilane and the organofunctional silanes.

In all cases, the adhesion of the pre-coating on the beveled edge was greatly improved.

Claim 1:
Method for the manufacture of a welded joint comprising the following successive steps:
I. The provision of at least two metallic substrates wherein at least one metallic substrate is a steel substrate having a thickness of at least <NUM> and being delimited by at least one beveled edge, wherein said beveled edge is at least partially coated with a pre-coating comprising a titanate and a nanoparticulate oxide selected from the group consisting of TiO<NUM>, SiO<NUM>, ZrO<NUM>, Y<NUM>O<NUM>, Al<NUM>O<NUM>, MoO<NUM>, CrO<NUM>, CeO<NUM>, La<NUM>O<NUM> and mixtures thereof, and
II. The welding of the at least two metallic substrates along the at least partially coated beveled edge by laser arc hybrid welding in leading arc configuration.