Method for wet-applying metal matrix composite plating to support components

Abstract

This invention provides a method for wet-depositing a metal matrix composite plating onto a support component, thereby improving the tribological properties of the support component. [Solution] A method for depositing a metal matrix composite plating onto a support component, comprising the steps of immersing the support component to be plated in an electrolytic bath containing the metal to be deposited (50), and depositing the metal in layers onto the support component by electrodeposition (60), characterized in that, before immersing the support component to be plated in the electrolytic bath, a predetermined amount of two-dimensional material is added and dispersed in the electrolytic bath (30) so as to uniformly distribute the two-dimensional material over the entire thickness of the metal matrix formed by the layered metal.

Description

[Technical Field]

[0001] This invention relates to wet deposition on support parts or substrates, such as clock components.

[0002] More specifically, the present invention provides a method for depositing a metal matrix composite plating onto a support component, comprising the steps of: immersing the support component to be plated in an electrolytic bath containing the metal to be deposited; and subsequently depositing the metal in layers onto the support component by electrodeposition.

[0003] This method is intended, but not limited to, the plating of horology parts. These horology parts include, but are not limited to, parts that are intended to come into frictional contact with other horology parts, such as escapement wheels, shafts, and gears. [Background technology]

[0004] In a clock mechanism, many moving parts come into contact with each other, generating friction. This friction causes wear on the parts, increases the energy required to move them, slows down the movement, and affects both the accuracy and autonomy of the mechanism. Therefore, minimizing friction as much as possible is essential for a clock mechanism to function properly.

[0005] To reduce this friction, it is common practice to lubricate the watch mechanism by applying an appropriate amount of liquid lubricant (oil) or paste lubricant (grease) to specific zones. A drawback of such lubricants is that they can leak out of the applied zone. Furthermore, their behavior can be significantly affected by environmental conditions such as temperature and humidity, which can influence viscosity. Moreover, this lubrication method is not permanent. The lubricant can dry out or become contaminated with wear-related debris, requiring replacement after several years, making re-lubrication essential.

[0006] To overcome the shortcomings of liquid or paste lubricants, dry lubrication solutions have been developed, particularly through the application of dry lubrication plating. Such dry lubrication plating has the advantage of being able to be applied to the protected component, thereby limiting the risk of loss, while also offering greater resistance to chemical degradation and reduced sensitivity to environmental conditions. Dry lubrication plating includes nickel-based plating, polytetrafluoroethylene (PFTE) plating, and plating based on carbon nanotubes dispersed in a nickel matrix. Such platings are described, for example, in U.S. Patent Application Publication No. 20081323475 and European Patent Application Publication No. 4390556.

[0007] Dry lubrication solutions offer improvements over liquid or paste lubricants, but there is still room for improvement in terms of friction issues and tribological properties. In particular, there is a constant need to reduce dry friction and improve wear resistance.

[0008] The present invention aims to provide a method for depositing plating onto a support component, thereby improving the tribological properties of the plated support component, particularly by providing a low coefficient of friction and improved wear resistance.

[0009] Furthermore, the present invention also aims to provide improved tribological properties to watch components intended to come into frictional contact with other watch components, particularly a lower coefficient of friction and improved wear resistance. [Overview of the project]

[0010] The present invention relates to a method for depositing a metal matrix composite plating onto a support component, comprising the steps of immersing the support component to be plated in an electrolytic bath containing the metal to be deposited, and then depositing the metal in layers onto the support component by electrodeposition. This method is noteworthy in that, before immersing the support component to be plated in the electrolytic bath, a predetermined amount of two-dimensional material is added and dispersed in the electrolytic bath so as to uniformly distribute the two-dimensional material throughout the entire thickness of the metal matrix formed by the layered metal.

[0011] Preferably, the two-dimensional material is a material of general formula M n+1 X n T x Selected from the MXenes family, in the formula, n = 1 to 3, "M" is a transition metal selected from the group consisting of titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, or tungsten. "X" is either carbon or nitrogen. "T" is a surface termination containing oxygen, hydrogen, chlorine, fluorine, or a combination of these compounds, and "X" is an integer variable that depends on the surface termination "T".

[0012] Depending on the selected foil exfoliation method, the surface end T x This can be omitted. In this case, the two-dimensional material is given by the general formula M n+1 X nIt is selected from the MAX phase family having. Adding MAX has the advantage of improving the tribological properties of the support parts due to the effect of its own structure (the layers slide relative to each other and limit friction), and the same is true for the ends of MAX. A tribochemical reaction can occur with lubricants and friction materials and limit wear.

[0013] Advantageously, MAX is added to the electrolytic bath in the form of individual or agglomerated sheets.

[0014] Advantageously, it can include adding at least one surfactant to the electrolytic bath before adding the two-dimensional material to the electrolytic bath.

[0015] Advantageously, the electrolytic bath to which the two-dimensional material is added is ultrasonically treated.

[0016] Advantageously, the support part to which the plating is applied is a watch part.

[0017] Another aspect of the present invention relates to a watch part designed to be in frictional contact with the contact surfaces of other watch parts, characterized in that it includes a plating formed from a composite containing a metal matrix to which a two-dimensional material is added.

[0018] Advantageously, the two-dimensional material has the general formula M n+1 X n T x and is selected from the MAX phase family, where n = 1 to 3, "M" is a transition metal selected from the group consisting of titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten, "X" is carbon or nitrogen, "T" is a surface termination including oxygen, hydrogen, chlorine, fluorine, or a combination of these compounds. "X" is an integer variable depending on the surface termination "T". Depending on the selected foil peeling method, the surface end T x can be omitted. In this case, the two-dimensional material is of the general formula M n+1 X n selected from the MAX family.

[0019] Advantageously, the selected MAX is Ti3C2.

[0020] Advantageously, the metal matrix is a nickel-based matrix.

Brief Description of the Drawings

[0021] Other features and advantages of the present invention will be apparent from the following detailed description of the invention provided by way of example and made with reference to the accompanying drawings. [Figure 1] FIG. 1 shows the steps involved in the deposition of a metal matrix composite plating according to an exemplary embodiment of the deposition method according to the present invention. [Figure 2] FIG. 2 is a graph showing the average dynamic friction coefficient of different samples tested under specific conditions (long amplitude). [Figure 3] FIG. 3 is a graph showing the average dynamic friction coefficient of different samples tested under specific conditions (short amplitude).

Modes for Carrying Out the Invention

[0022] Detailed Description of the Invention FIG. 1 shows a schematic diagram of the steps involved in the deposition of a metal matrix composite plating on a support part according to an exemplary embodiment of the method according to the present invention. <0000​​​​​​​​Formed from a two-dimensional (2D) material selected from the Maxine family having, in the formula, n = 1 to 3, "M" is a transition metal selected from the group including titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, or tungsten. "X" is either carbon or nitrogen. "T" is a surface end containing oxygen, hydrogen, chlorine, fluorine, or a combination of these compounds, and "X" is an integer variable that depends on the surface end "T". Depending on the selected foil stripping method, the surface end T x This can be omitted. In this case, the two-dimensional material is given by the general formula M n+1 X n Selected from the Maxine family, which has the following characteristics.

[0024] Therefore, the maxine contained in the composite consists of n+1 (n=1 to 3) layers of transition metals, represented by "M," which may be one of the aforementioned metals, and these metal layers are separated by carbon or nitrogen in the "n" layer. Here, "T" represents a functional group that allows for the modification of the surface properties of maxine.

[0025] To deposit the metal matrix composite plating, the first step is to prepare an electrolytic bath, preferably galvanic, to reduce the metal (nickel in this case) on the support component (step 10). The electrolytic bath consists of a solution to which Maxine is added, and the solution consists of the metal to be deposited, an electrolyte for conducting the current in the bath, and a solvent (water).

[0026] It is advantageous to add at least one surfactant to the electrolytic bath before adding Maxine (Step 20). The surfactant is used to charge the surface of the Maxine sheets. These surface charges act, on the one hand, to prevent the Maxine sheets from re-aggregating after separation according to the principles of electrostatics and steric repulsion, thus ensuring the stability of the suspension, and on the other hand, to allow these sheets to be added uniformly and sufficiently to the matrix by electrophoresis.

[0027] Once the surfactant is added, the maxine is added to the electrolytic bath in an amount sufficient to ensure a uniform distribution of the sheets throughout the entire thickness of the deposit, either as individual sheets or in aggregates (step 30).

[0028] To add non-aggregated single sheets or aggregated sheets, a sonication phase in the solution (step 40) is required, or at least preferred. Single sheets may aggregate slightly when placed in the solution, but sonication actually allows for complete mechanical separation of grouped sheets into single sheets. Preferably, non-aggregated sheets are incorporated. Once the sheets are separated, surfactants bind to their surfaces, providing the aforementioned advantages of stability and electrophoretic mobility.

[0029] After the Maxine has stabilized, the support parts to be plated are immersed in an electrolytic bath to which Maxine has been added (step 50).

[0030] Subsequently, the metal matrix composite is deposited (step 60). Such deposition can be carried out under the same conditions as deposition in a “conventional” electrolytic bath, in other words, an electrolytic bath without additives, as well as in a bath with a grain refiner or leveling agent added, and can be carried out regardless of the electrodeposition method used (such as direct or pulsating current).

[0031] Comparative tribological tests were conducted on steel samples plated with the nickel / maxine composite prepared using the method described above, and on steel samples plated with nickel similar to that found in watch components such as escapement wheels—in other words, samples without maxine added. The test conditions corresponded to the horological contact of a Swiss pallet escapement in terms of stress and velocity, with no contact lubricant added.

[0032] The tests were performed using a ball-on-disc tribometer. The ball was made from a typical opposing watch component (ruby in this example), and the disc was plated with a nickel deposit similar to those found on the composite deposit or watch component such as an escapement being tested. The tests were divided into long and short amplitudes to preferentially bias either the deposit or the opposing component. The maxine used in these tests was Ti3C2.

[0033] The results are shown in Figure 2 (long amplitude) and Figure 3 (short amplitude).

[0034] Three samples, labeled “Sample 1,” “Sample 2,” and “Sample 3,” plated with a metal matrix composite deposit of nickel and Ti3C2, were prepared using the method described above and tribologically tested with a tribometer. The three samples correspond to increasing deposition time, and therefore increasing thickness. “Sample 1” corresponds to a thickness of 1 μm, “Sample 2” to 5 μm, and “Sample 3” to 10 μm. Contact is made between the ruby ​​beads and the disk plated with the composite nickel / Ti3C2 deposit, as previously described. A comparison was made with a fourth sample of nickel-plated steel without maxine additive, as seen in watch components such as escapements. The fourth sample is labeled “Reference.”

[0035] The vertical lines on each bar indicate the variation in the measured value.

[0036] Regardless of whether long or short amplitudes were applied, the "reference" sample exhibited greater variability than "samples 1" through "sample 3" and had a higher mean coefficient of kinetic friction (CoF) value (approximately 0.25 for long amplitudes and approximately 0.21 for short amplitudes).

[0037] Therefore, the samples containing nickel / Ti3C2 deposits had a lower average coefficient of dynamic friction than the reference, demonstrating better performance of these materials in reducing friction. Sample 2 exhibited the best performance with the lowest average CoF and limited variation.

[0038] Therefore, the results show the gain in the coefficient of friction of the three samples according to the present invention ("Sample 1" to "Sample 3") compared to the "Reference" sample. Furthermore, with respect to wear, a relatively small number of cycles (3,000 cycles), no fragments appeared on the ruby ​​or plating.

[0039] Tribological tests have shown that the addition of maxine, in this case Ti3C2, to a metal matrix, particularly a nickel matrix, improves the dry contact performance of watch components without altering contact wear, while reducing the average dynamic friction coefficient compared to nickel plating without maxine.

[0040] The above description of the present invention is provided as an example. Those skilled in the art will understand that different modifications of the present invention can be arrived at without departing from the scope of the present invention.

[0041] term 10: Preparation of the electrolytic bath 20: Addition of surfactant 30: Addition of two-dimensional materials from the Maxine family 40: Ultrasonic treatment phase 50: Immersion of the support component to be plated into the electrolytic bath. 60: Electrodeposition of metal matrices with maxine added

Claims

1. A method for depositing a metal matrix composite plating onto a support component, comprising the steps of: immersing the support component to be plated in an electrolytic bath containing a metal to be deposited (50); and then depositing the metal in layers onto the support component to be plated by electrodeposition (60), wherein, before immersing the support component to be plated in the electrolytic bath, a predetermined amount of a two-dimensional material is added and dispersed in the electrolytic bath (30) so as to uniformly distribute the two-dimensional material throughout the entire thickness of the metal matrix formed by the layered metal.

2. The two-dimensional material has the general formula M ｎ＋１ X ｎ T ｘ It is characterized by being selected from the Maxine family having, in the formula, n = 1 to 3, "M" is a transition metal selected from the group consisting of titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, or tungsten. "X" is either carbon or nitrogen. "T" is a surface end consisting of oxygen, hydrogen, chlorine, fluorine, or a combination of these compounds. A method for attaching a metal composite plating as described in claim 1.

3. The method for depositing a metal composite plating according to claim 2, characterized in that the maxine is added to the electrolytic bath in the form of individual or aggregated sheets.

4. A method for depositing a metal composite plating according to claim 1, characterized in that at least one surfactant is added to the electrolytic bath before the two-dimensional material is added to the electrolytic bath (20).

5. A method for depositing a metal composite plating according to claim 1, characterized in that the electrolytic bath to which the two-dimensional material is added is subjected to ultrasonic treatment (40).

6. The method for applying metal composite plating according to claim 1, characterized in that the support component to which the plating is applied is a watch component.

7. A watch component designed to make frictional contact with the contact surfaces of other watch components, characterized by including a plating formed from a composite material containing a metal matrix to which a two-dimensional material has been added.

8. The two-dimensional material has the general formula M ｎ＋１ X ｎ T ｘ It is characterized by being selected from the Maxine family having, in the formula, n = 1 to 3, "M" is a transition metal selected from the group including titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, or tungsten. "X" is either carbon or nitrogen. "T" is a surface end containing oxygen, hydrogen, chlorine, fluorine, or a combination of these compounds. The watch component according to claim 7.

9. The selected Maxine is Ti ３ C ２ The watch component according to claim 7 or claim 8, characterized in that it is the same as the watch component according to claim 7 or claim 8.

10. The watch component according to claim 7, characterized in that the metal matrix is ​​a nickel-based matrix.

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