Patent Publication Number: US-2021172048-A1

Title: Method for manufacturing a decorative surface

Description:
CROSS-REFERENCE TO RELATED APPLICATION(S) 
     This application claims the benefit based on Patent Application No. EP19214570.4 filed Dec. 9, 2019, the contents of all of which are incorporated herein by reference in their entirety. 
     TECHNICAL FIELD 
     The invention relates to the field of the manufacture of decorative surfaces for luxury items, such as watches or jewelry. The invention relates more particularly to the use of lanthanum hexaboride (LaB 6 ) for producing these decorative surfaces. 
     TECHNOLOGICAL BACKGROUND 
     Lanthanum hexaboride belongs to the rare earths. In view of the very low work function thereof, i.e. about 2.4 eV, this material is routinely used in the field of electronics. One of the main uses is the manufacture of hot cathodes. 
     The stoichiometry LaB 6  has an intense purple-violet colour, and the adjacent stoichiometries can take on blue or green colours for example. This ceramic has a very high hardness value (about 2500 HV), and a high corrosion resistance. 
     SUMMARY OF THE INVENTION 
     According to the present invention, a layer of lanthanum boride of stoichiometry LaB x  is deposited on a substrate, for example a stainless steel watch dial, and subsequently treated with a laser, so as to modify said stoichiometry of said portion of the layer of LaB x  subjected to the laser treatment to LaB y  and give same a colour, said colour obtained being determined by the laser parameters. The change from LaB x  to LaB y  occurs by adjusting the laser parameters. The laser parameters are particularly the impulse duration, the mean laser beam power, the energy per impulse, the repeat frequency, the spot diameter, the spot overlap in the longitudinal and transversal direction and the fluence per impulse. 
     Advantageously, the LaB x  layer is converted by the laser treatment into LaB y  where y is between 9 and 12. 
     This method makes it possible to produce multicoloured surfaces having a high resistance to corrosion and abrasion. Preferably, the layer of LaB x  is deposited by PVD (Physical Vapour Deposition), and preferentially by cathode sputtering, using a LaB 6  target of purple-violet colour, such that the colour of the deposited layer differs from the colour of the target. The laser treatment at specific powers changes the stoichiometry of the layer in the treatment portions, such that the colour of these portions changes according to the stoichiometry obtained. At higher powers, the laser will essentially remove the layer of LaB x , such that the colour of the treated portions is determined by the material of the substrate. 
     The invention also relates to a decorative object produced using the method of the invention, particularly an object including a substrate provided with a layer, the layer comprising at least two portions of different colours with respect to one another, the portions consisting at least on the surface thereof of lanthanum boride determined by different lanthanum boride stoichiometries in the different portions. Preferably, one of the portions of the surface of said layer comprises a LaB y  where y is between 9 and 12. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     A detailed embodiment of the invention will be described hereinafter. This embodiment does not limit the scope of the invention, but merely serves as an example of use of the method according to the invention. 
     The target is prepared by depositing LaB x  where x=6 in the form of a purple-violet coloured powder on a sole, preferably made of copper. The powder is sintered and brazed on the sole, such that a solid layer, once again of purple-violet colour, is formed on the sole, which can serve as a target for the application of a PVD deposition by cathode sputtering. Typically, the thickness of the solid layer is of the order of 500 nm (0.5 μm). Soles provided with LaB 6  and prepared in advance are available for PVD applications. In the example of the method described hereinafter, the inventors used a sole provided with a circular layer of LaB 6  having a diameter of about 75 mm. 
     A stainless steel substrate of 20 mm×30 mm is introduced into an RF-CCP (Radio-Frequency Capacitively Coupled Plasma) type reactor, and is placed on a platform inside the reactor chamber. The reactor includes a support suitable for holding the target and a standard RF source. The reactor is provided with means for reducing and regulating the pressure inside the chamber, and means for introducing a flow of a gaseous fluid, such as argon, into the chamber. 
     In the current example, the reactor is operated in confocal mode. This implies that the target is placed at an angle preferably of 30° with respect to the central axis and perpendicular to the platform. The platform is rotatably mounted and can rotate about this central axis. 
     A step of cleaning the substrate is first performed, by subjecting it to an etching process, by means for example of an argon plasma created in the reactor chamber, after installing the target. The parameters of this etching step are for example as follows: pressure 1.5 10 −2  mbar; duration 5 min; acceleration voltage 600 V. 
     Then, the target is used in the support so as to act as a cathode during the PVD deposition, and such that the distance between the target and the centre of the substrate is typically 110 mm. The deposition of a layer of lanthanum boride of about 500 mm in thickness by PVD in argon, via cathode sputtering of the target, occurs under the following typical conditions:
         Power applied to the cathode: 250 W (i.e. 404 V for 0.62 A in DC mode)   Ar pressure: 3 μbar.   Deposition temperature: 430° C. (this temperature is a setpoint programmed on the machine, and not the actual temperature measured on the substrate).   Bias applied to the cathode with respect to the substrate: −150V DC   Deposition time: 1500 seconds to obtain 300 nm (0.2 to 0.25 nm/s).   Rotational speed of substrate: about 10 rpm       

     It is observed that the colour of the deposited layer differs from the purple-violet colour of the target. The colour of the deposited layer is slate grey-blue. The explanation of this difference in colouring is provided by the SEM-EDX analysis of the layer. A layer of stoichiometry LaB 6  is no longer the target, but a stoichiometry LaB 9  to LaB 12 , hereinafter referred to as LaBy. Indeed, the sputtering rates of lanthanum and boron are different, which results in a boron-enriched and therefore lanthanum-depleted layer. 
     According to the invention, the local laser treatment of the layer deposited by PVD will once again change the colour of the layer. A marking laser is used operating in the infrared range. The laser is controlled to sweep a spot over a predefined portion of the surface of the layer of LaB x . According to the parameters applied, three different colours can be obtained on adjacent zones of the same substrate: blue, violet and grey-white, so as to obtain a multicoloured pattern on the substrate. The following table discloses the typical parameters applied in the three cases. 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Colours obtained 
                   
                   
                   
               
               
                 
                   
                 
                   
                   
                   
               
               
                 Parameters applied 
                   
                   
                   
               
               
                 
                   
                 
                 blue 
                 Violet 
                 Grey-white 
               
               
                   
               
             
            
               
                 Impulse duration 
                 4 ns 
                 8 ns 
                 4 ns 
               
               
                 Mean power 
                 8 t0 10 W 
                 5.2 W 
                 18 to 20 W 
               
               
                 Energy per impulse 
                 40 to 100 μJ 
                 11.6 μJ 
                 90 to 135 μJ 
               
               
                 Repeat frequency 
                 100 to 200 kHz 
                 400 to 500 kHz 
                 150 to 
               
               
                   
                   
                 preferably 
                 200 kHz 
               
               
                   
                   
                 450 kHz 
                   
               
               
                 Spot diameter 
                 68 μm 
                 68 μm 
                 68 μm 
               
               
                 Spot overlap in 
                 70 &amp; 85% 
                 97 &amp; 98% 
                 80 &amp; 85% 
               
               
                 longitudinal and 
                   
                   
                   
               
               
                 transversal direction 
                   
                   
                   
               
               
                 Fluence per impulse 
                 1.2 to 2.8 J/cm2 
                 0.30 to 
                 2.5 to 3.7 
               
               
                   
                   
                 0.34 J/cm2 
                 J/cm2 
               
               
                   
                   
                 preferably 
                   
               
               
                   
                   
                 0.32 J/cm2 
               
               
                   
               
            
           
         
       
     
     It was observed that the laser power primarily defined the colour obtained. The differences in terms of frequency, overlap and impulse duration have little or no impact on the colour, but can result in different shades of the same colour. 
     An SEM-EDX analysis established that the blue and violet layers consist of specific stoichiometries of lanthanum boride which determine the colours in question. On the other hand, the grey-white colour contains little boron and lanthanum, but the colour thereof is determined by the presence of Fe and Ni of the stainless steel substrate. This means that the layer of LaBy has essentially been removed or partially removed and that the colour is determined primarily by the colour of the substrate. 
     A series of nano-indentations demonstrated that the layer deposited by PVD had a hardness value of about 2500 HV, and that after laser treatment it retained a hardness value of 1500 HV for violet and 1000 HV for blue, which is sufficient for horological applications exposed to abrasion. Furthermore, a “tropical climate” test, i.e. exposure in an chamber to a temperature of 60° C., with a % RH of 90% for 7 days, demonstrated that the coating was in no way affected. 
     Thus, in a non-limiting manner and once the laser spot does not pass through the layer of LaB x , it is possible to decorate, according to this method, a horological component such as a horological dial, hands, a watch case, a clasp element, or a bracelet link. 
     Obviously, the present invention is not limited to the example illustrated but is suitable for various variants and modifications which will be obvious to those skilled in the art. In particular, the invention would not be limited to an external horological part or even to the horological field. Thus, by way of example, there is nothing to prevent using the method according to the invention for an application in the field of tableware, jewelry, leather goods, or indeed writing implements.