Method for (pre)treatment of the surface of carbon nanocomposite materials, and timepiece governor with a flexible component comprising a modified nanocomposite

Abstract

This invention relates to a method for (pre)treating the carbon surface of a carbon nanocomposite material configured to form a flexible component of a watch movement regulating mechanism. The method can be performed before or without subsequent functionalization of the (pre)treated surface. In the (pre)treatment method according to the invention, the carbon nanocomposite material (90) to be (pre)treated has open pores and comprises a forest of carbon nanotubes impregnated with pyrolytic carbon (70); and the method includes exposing the carbon nanocomposite material (90) to a gaseous reagent comprising a hydrocarbon carbon source and a reagent inhibiting carbon deposition reaction in a chemical vapor deposition reactor at a temperature of 500°C–1200°C to controllably deposit a carbon coating (100) with an average thickness of 50 nm–500 nm covering the carbon surface.

Description

Technical Field

[0001] This invention relates to: a method for functionalizing and passivating the carbon surface of a carbon nanocomposite material (i.e., nanostructured carbon), said carbon nanocomposite material being configured to form a flexible component of a watch movement regulating mechanism; the flexible component; the regulating mechanism comprising the flexible component and a balance wheel cooperating therewith; and the use of a composite for functionalizing and passivating the carbon surface of the carbon nanocomposite material. The invention also relates to a method for (pre)treating the carbon surface of a carbon nanocomposite material, the surface optionally being functionalized and passivated (after pre) by the functionalization and passivation method. It should be understood that the invention may relate to this treatment method alone, without dependence on any subsequent functionalization and passivation methods. The invention is particularly applicable to flexible components of the hairspring type, such as those used in mechanical watches, which may be based on a forest of carbon nanotubes impregnated with pyrolytic carbon, but this is only by way of non-limiting example. Background Technology

[0002] Typically, a watch movement includes a regulator, a mechanical oscillator that determines the time base of the watch movement. This regulator has a hairspring, which is coupled to an oscillating mass called the balance wheel. The hairspring requires extremely high dimensional accuracy because it determines the timekeeping precision of the watch movement.

[0003] The time reference of a clock depends on an oscillator that operates at a specific frequency; its oscillation must remain stable. Known oscillators include pendulums (relying on gravity), quartz crystals (relying on the piezoelectric effect), tuning forks (relying on elastic deformation), and springs of various shapes (also relying on elastic deformation to generate restoring force), depending on the magnitude of their designed oscillation amplitude.

[0004] Specifically, in most mechanical watches, the regulating mechanism includes a balance wheel-hairspring assembly—specifically, this assembly comprises a balance wheel (which acts as a flywheel) and a spiral spring (also called a hairspring, balance wheel hairspring, or spiral hairspring). One end of the hairspring is attached to the balance wheel's shaft, and the other end is attached to the balance wheel bridge; the balance wheel shaft pivots within it. The balance wheel-hairspring assembly oscillates around its equilibrium position at a specific frequency. When the balance wheel deviates from this position, it winds up the hairspring. This generates a restoring torque that pushes the balance wheel back to its equilibrium position when it releases. Since the balance wheel has gained a certain speed, it also gains kinetic energy and will move past the equilibrium position until the reverse torque of the hairspring stops it and causes it to reverse its motion. These oscillations are repeated continuously. Thus, the hairspring regulates the oscillation period of the balance wheel. The hairspring is primarily made of a strip wound around itself, specifically in the form of an Archimedean spiral.

[0005] WO 2017 / 220672 A1 and WO 2020 / 144587 A1 respectively disclose components for watch movements—such as hairsprings—made of composite materials comprising a rigid matrix and a forest of nanotubes embedded in the matrix.

[0006] WO 2013 / 079939 A2 discloses an oscillator spring composed of a spring material made of carbon, ceramic, polymer, polymer precursor, composite material, or a combination thereof; and a barrier material for altering the number of available bonding sites on the surface of the spring material; wherein the barrier material is composed of one or more hydrophobic silicone or hydrophobic silane compounds. The barrier material can prevent the adsorption of water vapor from the ambient atmosphere. Therefore, this barrier layer can adjust the elasticity of the spring.

[0007] A major drawback of the spring disclosed in this document is that it requires the incorporation of crystalline phase change additives (such as silicon dioxide) into the carbon-based material of the spring in order to control the elastic modulus of the spring and to ensure that the silicone or silane barrier layer formed by the carbon material containing the additive can ultimately change the mechanical properties of the resulting spring.

[0008] The applicant has been seeking methods to passivate the surface of carbon nanocomposites (i.e., nanostructured carbon)—such as nanocomposites used to form the balance springs of mechanical watches, which are based on carbon nanotubes impregnated with pyrolytic carbon—to counteract the structural changes observed in current balance springs based on such nanotubes during use, thereby improving the performance of these balance springs. Summary of the Invention

[0009] One object of the present invention is to provide a method for treating the carbon surface of a carbon nanocomposite material (i.e., nanostructured carbon) suitable for forming the hairspring of a watch movement, wherein the nanomaterial to be treated may be mainly or entirely composed of carbon; in particular, the treatment method overcomes the aforementioned disadvantages of the prior art (e.g., no additives other than carbon need to be added to the hairspring) and reduces the hairspring's sensitivity to the environment (especially to ambient humidity, and possibly to other volatile components in the watch (such as mechanical watches) or in the ambient air, such as oils and / or greases used in watches).

[0010] The applicant has demonstrated that this objective is achieved by chemically reacting the carbon surface of such a carbon nanocomposite with a complex comprising a carbon chain and a diazonium salt group located at the reactive carbon end of the chain, thereby covalently grafting the reactive carbon end onto the carbon surface, while simultaneously passivating the surface to make it highly hydrophobic (e.g., with a water contact angle greater than 90°), and significantly reducing its surface energy compared to the same carbon surface that is untreated or not treated with specific reactive groups (e.g., with a halosilane compound or a prior art Epilaame® solution); in particular, this enables efficient and durable passivation (through covalent functionalization) of the carbon surface treated according to the present invention.

[0011] More specifically, the present invention provides a method for functionalizing and passivating the carbon surface of a carbon nanocomposite material configured to form a flexible component of a watch movement regulating mechanism, the method comprising chemically reacting the carbon surface with a composite material comprising: - Carbon chains, which are hydrocarbon chains or fluorocarbon chains; and - A salt of a diazo group at the reactive carbon end of the chain or a precursor of the group; This is used to covalently graft the reactive carbon ends onto a carbon surface and passivate the carbon surface to make it hydrophobic.

[0012] It should be noted that this covalent grafting, combined with the passivation of the carbon surface, ensures the performance of nanocomposites—such as those used in the hairsprings of mechanical watches—by reducing their sensitivity to their environment, particularly to changes in ambient humidity and / or the content of other volatile components (such as oils and / or greases) that may be present in the watch.

[0013] It should also be noted that the carbon chains of the complex can effectively adhere (i.e. attach) to the carbon surface due to their reactive ends, which form a diazonium salt-based "head" for the complex and are grafted onto the carbon surface via covalent C-C bonds.

[0014] Furthermore, it should be noted that the functionalization and passivation methods according to the invention can be advantageously achieved through a purely chemical approach, i.e., without the need for a specific electrochemical approach.

[0015] According to another feature of the invention, the diazonium salt group can be generated in situ from the precursor, such as a fluorocarbon derivative of aniline or triazine, or can be pre-generated before the chemical reaction, wherein the diazonium salt corresponds to the chemical formula [Formula 1]: [Formula 1] Where R is a substituted or unsubstituted hydrocarbon group, preferably an aryl group, such as a substituted phenyl group; And X -It is an inorganic or organic anion, preferably a halide ion or trifluoromethanesulfonate ion, such as chloride ion or fluoride ion; Furthermore, the reactive carbon terminus can be grafted onto the carbon surface via covalent C-C bonds between the R group and the carbon atoms on the carbon surface.

[0016] The anion of the diazonium salt, for example, can be selected from Cl... - BF4 - (Tetrafluoroborate), TFA - (trifluoroacetate), Ts - (p-Toluenesulfonate), Tf - (trifluoromethanesulfonate), PF6 - (hexafluorophosphate), heavy metal anions (e.g., FeCl4) - AuCl4 - SbF6 - And anionic polymer resins (such as resins labeled "Amberlyst" or "sulforesin"), the above being merely non-limiting examples.

[0017] Preferably, the carbon chain of the composite is an aliphatic fluorocarbon chain, and even more preferably a perfluorocarbon chain.

[0018] It should be noted that the fluorocarbon chain (e.g., a partially or fully fluorinated C1-C20 chain) is advantageously a perfluorinated C5-C10 hydrocarbon chain; this can further improve the passivation of the carbon surface compared to hydrocarbon chains (e.g., alkyl chains).

[0019] In addition, it should be noted that fluorocarbon chains containing ether functional groups, such as perfluoroalkoxyalkanes, can also be used.

[0020] Advantageously, the chemical reaction according to the invention forms a functionalized and passivated carbon surface through grafting, which can have: - A water contact angle greater than or equal to 90°, preferably greater than or equal to 100°, and for example 100°-130°, or even 105°-130°, as measured according to the method described in the specification; and / or - The fluorine atom concentration is 5%-70%, preferably 10%-60%, as measured as described in the specification; and / or - The total surface energy is reduced by at least 20%, preferably at least 25%, relative to the total surface energy of the carbon surface (20a) before functionalization and passivation, defined as the sum of dispersion energy and specific energy, expressed in mJ / m 2 Calculate and measure as described in the instructions.

[0021] According to a first aspect of the invention, the chemical reaction can be performed by grafting to form a hydrophobic monolayer film covering a carbon surface, thereby achieving functionalization and passivation of the carbon surface. The hydrophobic monolayer film can be formed simultaneously with the composite or after the composite is formed. The water contact angle of the hydrophobic monolayer film, measured according to the method described in the specification, can be greater than or equal to 90°, preferably greater than or equal to 100°, and for example 100°-130°, or even 105°-130°.

[0022] It should be noted that this obviously hydrophobic monolayer is covalently grafted onto the carbon surface by attaching the reactive carbon ends of the complex chains to the carbon surface.

[0023] It should also be noted that the water contact angle value of the hydrophobic monolayer membrane given above is very high, which proves that in addition to forming covalent bonds with the carbon surface, the membrane can also effectively passivate the carbon surface.

[0024] Water contact angles were measured on a planar substrate (silicon wafer) coated with a carbon layer similar to that constituting the carbon nanocomposite. After passivation, the substrate was ultrasonically cleaned with an organic solvent to ensure covalent bonding of the monolayer. To measure the contact angle, 3 µL of distilled water was dropped onto the surface, and the angle was measured using a KRUSS contact angle analyzer. Droplet analysis was performed using Advance software, applying the Young-Laplace model, and averaging three angle measurements at three different locations on the surface.

[0025] According to a second aspect of the invention, which supplements the first aspect, the total surface energy of the carbon surface coated with the hydrophobic monolayer film can be reduced by at least 20%, preferably by at least 25%, relative to the total surface energy of the carbon surface before deposition of the hydrophobic monolayer film, for example, by at least 50% when measured using the "OWRK" method, wherein the total surface energy is defined as the sum of dispersion energy and specific surface energy, expressed in mJ / m 2 Calculate and measure using reversed-phase gas chromatography (IGC) or the “OWRK” method as described below.

[0026] It should be noted that the total surface energy is significantly reduced after the deposition of the hydrophobic monolayer film, which clearly indicates that the carbon surface has been highly passivated.

[0027] The total surface energy of a hydrophobic monolayer coated carbon surface was measured on a carbon spring using reversed-phase gas chromatography (IGC). The adsorbent under study was placed in the chromatographic column, and a known adsorbate was used in the gas phase. Retention time, as a fundamental measurement parameter, can be converted into retention volume, which is directly related to various physicochemical properties of the solid (adsorbent). This study focuses on the surface energy of the adsorbent. More specifically, an IGC surface energy analyzer was used; a portion of the nanocomposite material was placed in a single IGC silanized glass column, and surface coverage was measured using alkanes and polar probe molecules (adsorbates) to determine the dispersion energy and specific surface energy.

[0028] As further described below, the total surface energy of a carbon surface coated with a hydrophobic monolayer was measured using another method called "OWRK," which involves measuring the contact angle on a planar substrate of the sample.

[0029] According to a third aspect of the invention, which may supplement the first and / or second aspects, the atomic concentration of fluorine in the outermost surface region (a region with a thickness of about 2 nm to 10 nm) of the hydrophobic monolayer film, measured by the method described in this specification, may be 5% to 70%, preferably 10% to 60%.

[0030] It should be noted that this fluorine atom concentration can be used to compare the effectiveness of hydrophobic monolayer deposition reaction conditions and further demonstrates the effectiveness of the accompanying complex (containing a diazo group) in the aforementioned in-situ generation scenario of the complex (a salt containing a diazo group).

[0031] According to a fourth aspect of the invention, which may supplement the first and / or second and / or third aspects, the hydrophobic monolayer may comprise a reaction product between a carbon surface and a diazo functional group, corresponding to chemical formula [Formula 2]: [Equation 2] Where R is a substituted or unsubstituted hydrocarbon group, Preferably: R is an aryl group, such as a substituted phenyl group, and The functional group is an aryl diazonium group, such as a benzene diazonium group, which corresponds to the chemical formula [Formula 3]: [Formula 3] According to a fourth aspect of the invention, the formed monolayer includes a group R, which is functionalized with a carbon chain (preferably a fluorocarbon chain, and even more preferably a perfluorocarbon chain).

[0032] It should be noted that the diazo functional group reacts with the carbon surface to release gaseous nitrogen, thereby forming a monolayer through the covalent bond between the group R and the carbon surface.

[0033] It should also be noted that selecting aryl groups R (e.g., substituted phenyl groups) for the diazonium salt of chemical formula [Formula 1] and the diazonium group of chemical formula [Formula 2] can further improve the functionalization and passivation of the carbon surface.

[0034] According to another feature of the invention, in combination with at least one of the foregoing features and aspects, the carbon surface may optionally be immersed in a reducing solution containing a reducing agent (e.g., ascorbic acid), and then (with or without the reducing solution) a chemical reaction is carried out in a reaction medium containing a complex solution.

[0035] According to another feature of the invention, which may be combined with at least one of the foregoing features and aspects, the carbon nanocomposite material (i.e., nanostructured carbon) may comprise carbon nanotubes and pyrolytic carbon infiltrated into a forest of nanotubes; the carbon surface may be composed of carbon atoms, the carbon nanocomposite material is preferably composed of carbon nanotubes and pyrolytic carbon, and the hydrophobic monolayer preferably directly covers the surfaces of the pyrolytic carbon and carbon nanotubes (or at least covers the accessible nanotube surfaces).

[0036] It should be noted that the carbon composite material is the target of the functionalization and passivation method according to the present invention, which is preferably composed of carbon nanotubes and pyrolytic carbon infiltrated into the nanotube forest (i.e., the nanocomposite material does not contain any non-carbon additives), such that the carbon surface to be treated is mainly or completely composed of carbon atoms (note that a small number of hydrogen atoms and / or oxygen atoms may be present in the surface and / or structure of the carbon nanocomposite material).

[0037] It should be noted that the carbon nanocomposite material and carbon surface to be treated according to the present invention can be mainly or entirely composed of any carbon allotrope, including but not limited to amorphous carbon, tetrahedral carbon, diamond-like carbon (“DLC”), diamond, graphite, graphene, fullerene, and single-walled carbon nanotubes (“SWNT”), double-walled carbon nanotubes (“DWNT”) or multi-walled carbon nanotubes (“MWNT”).

[0038] According to another general feature of the method of the invention, the flexible component is adapted to bend in a plane perpendicular to the Y-axis, and the carbon nanocomposite material is configured to form a filament adapted to oscillate about the Y-axis; the carbon nanocomposite material consists of a matrix formed from pyrolytic carbon and a forest of side-by-side carbon nanotubes impregnated and fixed by the matrix. The nanotubes (e.g., multi-walled nanotubes) may be arranged substantially parallel to the Y-axis or not parallel (e.g., the nanotubes are not straight but wavy and not parallel to the Y-axis).

[0039] Another object of the present invention is to provide a flexible component for the regulating mechanism of a watch movement, which, in particular, is a hairspring (e.g., in the form of an Archimedean spiral), bendable in a plane perpendicular to the Y-axis, and comprises a carbon nanocomposite material (i.e., nanostructured carbon) with a functionalized and passivated carbon surface; this overcomes the aforementioned disadvantages of the prior art, and by passivating the carbon surface of the flexible component, the responsiveness of the flexible component to environmental conditions is reduced, making it unaffected by changes in environmental conditions, particularly changes in ambient humidity and / or the content of other volatile components (such as oils and / or greases) that may be present inside the watch.

[0040] Therefore, the flexible component according to the invention comprises a functionalized and passivated carbon surface containing chemical reaction products between the original carbon surface of the carbon nanocomposite and the composite, the composite comprising: Carbon chains, which can be hydrocarbon chains or fluorocarbon chains, and A salt of a diazo group at the reactive carbon end of the carbon chain or a precursor of the group; The reactive carbon ends of the carbon chain are covalently grafted onto the surface of the original carbon, and Functionalized and passivated carbon surfaces are hydrophobic.

[0041] Generally, it should be noted that the method for functionalizing and passivating the carbon surface of carbon nanocomposites described in this invention can be advantageously used to obtain flexible parts, as described above. This method has the aforementioned advantages and is also applicable to the resulting flexible parts (these advantages include, in particular, the effective passivation of the carbon surface of the nanocomposites, such as the hairspring of a mechanical watch, by reducing the reactivity of the nanocomposites to the environment, especially to changes in ambient humidity and / or the content of other volatile components (such as oils and / or greases) that may be present in the watch).

[0042] Advantageously, the functionalized and passivated carbon surface may optionally form a hydrophobic monolayer film covering the original carbon surface, and the functionalized and passivated carbon surface is capable of exhibiting at least one of the following characteristics: - The water contact angle is greater than or equal to 90°, preferably greater than or equal to 100°, for example 100°-130°, or even 105°-130°, as measured according to the method described in the instruction manual; - The total surface energy is reduced by at least 20%, preferably at least 25%, relative to the original carbon surface energy, for example, by at least 50% as measured by the "OWRK" method. The total surface energy is defined as the sum of the dispersion energy and the specific surface energy, expressed in mJ / m². 2 Calculate and measure by reversed-phase gas chromatography (“IGC”) or “OWRK” method as described in the instructions; - The fluorine atom concentration in the outermost surface region of the hydrophobic monolayer membrane is 5% - 70%, preferably 10% - 60%, as measured according to the method described in the specification; and - A hydrocarbon group R (preferably aryl, for example substituted phenyl), which is functionalized with a carbon chain (preferably a fluorocarbon chain, more preferably a perfluorocarbon chain).

[0043] Advantageously, the original carbon surface can be composed primarily or entirely of carbon atoms, and the nanocomposite material can include a forest of carbon nanotubes and a pyrolytic carbon matrix infiltrated into the nanotube forest, wherein the nanotubes are arranged side by side and fixed by the matrix, typically the nanotubes (e.g., multi-walled nanotubes) are arranged parallel to the Y-axis, or not parallel to the Y-axis (e.g., when the nanotubes are not straight but wavy, they are not parallel to the Y-axis).

[0044] It should also be noted that the nanocomposite material is preferably composed of carbon nanotubes and pyrolytic carbon infiltrated into the nanotube forest (i.e., the nanocomposite material does not contain any non-carbon additives, or the pyrolytic carbon contains trace amounts of hydrogen and / or oxygen); however, the nanocomposite material and its original carbon surface may be mainly or entirely composed of any carbon allotropes, including but not limited to amorphous carbon, tetrahedral carbon, diamond-like carbon (“DLC”), diamond, graphite, graphene, fullerene, and single-walled, double-walled, or multi-walled nanotubes.

[0045] Another object of the present invention is to provide a regulating mechanism for a watch movement, the regulating mechanism comprising: - Flexible components adapted to bend in a plane perpendicular to the Y-axis, particularly suitable for a hairspring oscillating about the Y-axis, and - A balance wheel that mates with the flexible component. It overcomes the aforementioned shortcomings of the prior art and can reduce the responsiveness of the flexible component to environmental conditions by passivating the carbon surface of the flexible component, making it unaffected by changes in environmental conditions, especially changes in ambient humidity and / or the content of other volatile components (such as oil and / or grease) that may be present inside the watch.

[0046] Therefore, this flexible component, as described above, relates to the aforementioned features and aspects of the present invention.

[0047] Another object of the present invention is to provide a use of the complex comprising: - Carbon chains, which are hydrocarbon chains or fluorocarbon chains, and - A salt of a diazo group at the reactive carbon terminus of the chain, or a precursor of the group. The carbon nanocomposite material (i.e., nanostructured carbon) is used to functionalize and passivate the carbon surface through a chemical reaction. The carbon nanocomposite material is configured to form a flexible component of a watch movement regulating mechanism by covalently grafting the reactive ends of the chain onto the carbon surface and passivating the carbon surface to make it hydrophobic.

[0048] Advantageously, this use of the compound according to the invention can be further defined by all or part of the features and aspects of the above-described functionalization and passivation methods.

[0049] According to another aspect of the invention, which relates to a step performed prior to the functionalization and passivation of the carbon surface of the carbon nanocomposite material (this other aspect is referred to below as the "preliminary aspect of the invention" and may optionally be combined with some or all of the features and aspects of the subsequent functionalization and passivation methods defined above), the applicant's objective is also to overcome the disadvantages encountered in the prior art when obtaining carbon nanotube forests infiltrated with pyrolytic carbon using chemical vapor deposition ("CVD"). These disadvantages are particularly: - The carbon nanocomposite material obtained in this way has a relatively high porosity, and its open pores are conducive to the subsequent adsorption of molecules in the pores; and - The free outer surface of carbon nanocomposites with infiltrated nanotubes exhibits both a relatively high specific surface area and a relatively high surface energy.

[0050] This goal is achieved through the applicant's latest discovery: if a sufficiently thin and conformal carbon coating is deposited in a controlled manner on the carbon surface (unfunctionalized and passivated) of carbon nanocomposites by chemical vapor deposition (CVD) under an inert atmosphere, and the deposition time, temperature, and precursor type are controlled to allow pyrolytic carbon to deposit at the pore openings of the carbon surface, while using only gaseous reagents for deposition, then this (pre)treatment of the carbon surface can effectively seal the open pores of carbonaceous materials composed of carbon nanotube forests infiltrated by pyrolytic carbon, while significantly reducing the specific surface area and surface energy of the outer surface of the carbon nanocomposites.

[0051] More specifically, according to this preliminary aspect of the invention, a method for (pre)treating the carbon surface of a carbon nanocomposite material—the nanocomposite material being configured to form a flexible component of a watch movement regulating mechanism, and the (pre)treated carbon surface optionally subsequently being functionalized and passivated by the functionalization and passivation method according to the invention described above—mainly comprises: exposing a carbon nanocomposite material having open pores and containing a forest of carbon nanotubes impregnated with pyrolytic carbon to a gaseous reagent containing a hydrocarbon carbon source and a reagent for inhibiting carbon deposition reaction in a CVD reactor at a temperature of 500°C to 1200°C, to controllably deposit a carbon coating with an average thickness of 50 nm to 500 nm, the carbon coating covering the carbon surface.

[0052] More specifically, the (pre)processing method may include: - A reagent is introduced into a CVD reactor comprising a carbon nanocomposite material with open pores and heated to a temperature of 500°C–1200°C, the reagent comprising: Gas-phase hydrocarbon carbon sources, and The inhibitor, also in gaseous form, can suppress the pyrolytic carbon deposition reaction, thereby reducing the amount (i.e., thickness) of the carbon coating to be deposited on the carbon surface. Optionally, an inert gas containing reagents and reaction products is introduced into the reactor, while simultaneously controlling the volume fraction of the reagent; and reagents are introduced simultaneously, and inert gas is introduced when appropriate. - Carbon nanocomposites were exposed to a reagent at a temperature of 500℃-1200℃ for 1 min-1 h30 min to deposit a carbon coating in a controlled manner.

[0053] It should be noted that when the hydrocarbon carbon source is ethylene, the preferred temperature for exposing the nanocomposite material to the reagent is 800℃-1000℃.

[0054] According to one embodiment of a preliminary aspect of the present invention, the carbon nanocomposite material (i) Before its (pre)processing: - Contains a forest of carbon nanotubes infiltrated with pyrolytic carbon and having open pores, the nanotubes covering a support element deposited on a semiconductor substrate; and - Possessing a carbon surface (i.e., the outer surface of the nanocomposite material, which externally defines the infiltrated nanotube forest), which includes: Top surface; The bottom surface, located at the base of the infiltrated carbon nanotube forest (i.e., the lower surface of the infiltrated forest, in contact with the support element forming a layer covering the substrate), and opposite the top surface; and The side surface connects the top and bottom surfaces; and (ii) After its (pre)processing: This includes carbon coatings deposited on the top, bottom, and side surfaces of the carbon nanocomposite material, which in this exemplary embodiment continuously cover the carbon surface, thereby enabling the reduction or even elimination of open pores in the carbon nanocomposite material.

[0055] According to this exemplary embodiment of the (pre)treatment method of the present invention, after depositing a carbon coating on the top and side surfaces, the nanocomposite material is flipped to deposit the carbon coating on the bottom surface, such that the carbon surface to be (pre)treated can be composed of carbon atoms (the carbon nanocomposite material is preferably composed of carbon nanotubes and pyrolytic carbon). It should be noted that the carbon nanocomposite material and carbon surface to be (pre)treated according to the present invention can therefore be composed primarily or entirely of any allotrope of carbon, including but not limited to amorphous carbon, tetrahedral carbon, diamond-like carbon (“DLC”), diamond, graphite, graphene, fullerene, and single-walled (“SWNT”), double-walled (“DWNT”), or multi-walled (“MWNT”) nanotubes.

[0056] According to the preliminary aspects of the present invention, the (pre)treatment method (including exemplary embodiments involving impregnation nanotubes) allows the controlled deposition of a carbon coating to be carried out under an internal pressure P of a reactor, for example, a pressure less than or equal to atmospheric pressure (i.e., pressure P ≤ about 1.013 × 10⁻⁶). 5 Pa).

[0057] Advantageously, the (pre)treatment method according to the preliminary aspect of the invention (including exemplary embodiments involving impregnation of nanotubes) may use the following substances: - As a hydrocarbon carbon source, an aliphatic or aromatic unsaturated hydrocarbon, such as selected from ethylene, acetylene, or xylene; and / or - As a suppressor of carbon coating thickness, hydrogen-containing gases, such as hydrogen (H2) or ammonia (NH3); and / or - As an inert gas, nitrogen (N2) or argon (Ar).

[0058] Preferably, the (pre)treatment method according to the preliminary aspect of the present invention (including embodiments involving impregnation of nanotubes) uses the following substances: - As a hydrocarbon carbon source, ethylene (C2H4) has a volume fraction X C2H4 It is 0.05-0.50 (i.e., X) C2H4 = 5-50%); and / or - As a reducing agent, hydrogen (H2) has a volume fraction XH2 of 0.30-0.65 (i.e., X... H2 = 30-65%); and / or - As an inert gas, argon (Ar) has a volume fraction X Ar It is 0-0.50 (i.e., X) Ar = 0-50%).

[0059] Note that the volume fraction X of each gaseous species i Defined as the volumetric flow rate Q for each species i The ratio of the sum of the volumetric flow rates of the gaseous species (X)i = Q i / ∑Q i ), flow rate per volume, for example in cm 3 / min or sccm (“standard cubic centimeters per minute”, which is the density defined under standard temperature and pressure conditions) is used to express density.

[0060] Also preferably, the (pre)treatment method according to the preliminary aspect of the invention (including embodiments involving impregnation nanotubes) uses the following conditions for controlled deposition of carbon coatings: - The reaction duration is 10 min - 50 min, and / or - Temperature of 850℃-900℃, and / or - The pressure P inside the reactor is equal to atmospheric pressure (1.013 × 10⁻⁶). 5 Pa), to obtain, for example, an average carbon coating thickness of 90nm-200nm.

[0061] In addition to other features of the (pre)treatment method according to the preliminary aspect of the present invention (including exemplary embodiments involving impregnation of nanotubes), the method may further include the following steps: - Before introducing the reagents and inert gas into the reactor containing the nanocomposite material, and simultaneously exposing the nanocomposite material to the reagents at a temperature of 500℃-1200℃: - Step a) The reactor was purged under an inert atmosphere to remove reagents and reaction products previously used for pyrolytic carbon deposition (e.g., reagents and reaction products associated with nanotube infiltration), and The temperature is adjusted under the inert atmosphere to prepare for controlled deposition (the temperature may be kept constant or varied relative to the temperature used for nanotube infiltration in the exemplary embodiment); - Step b), a carbon coating is deposited in a controlled manner by continuously adding precursors; - Step c) includes purging the reactor under an inert atmosphere (e.g., under argon or nitrogen) and then cooling the reactor; - Step d) Remove the substrate support element and the carbon nanocomposite material above it from the reactor, the composite material comprising at least partially impregnated (pre)treated nanotube forest (i.e. at least partially covered by a carbon coating); - Step e), clean the reactor (e.g., by introducing air at a temperature of 800-1000°C); and - Optionally, in step f), only a portion of the (pre)treated carbon nanocomposite material separated from the substrate support element is reintroduced into the reactor, the nanocomposite material being rotated 180° relative to the axis in the main plane to repeat steps a)-d) and complete the deposition of the carbon coating (in embodiments involving impregnated nanotubes, in order to deposit the coating on the bottom surface of the nanocomposite material).

[0062] According to a preliminary aspect of the present invention relating to the above-described processing method, a flexible component for a regulating mechanism in a watch movement is also disclosed, the flexible component, particularly the hairspring, being adapted to bend in a plane perpendicular to the axis. The flexible component comprises a carbon nanocomposite material having a carbon surface treated as described above, the carbon nanocomposite material comprising a forest of carbon nanotubes impregnated with pyrolytic carbon, and the carbon surface being covered with a carbon coating having an average thickness of 50 nm to 500 nm, for example, 90 nm to 200 nm.

[0063] The flexible component according to the preliminary aspect of the invention allows a carbon coating to cover the top, bottom, and side surfaces of the carbon nanocomposite material.

[0064] Advantageously, the carbon surface treated according to the present invention can exhibit: - Total surface energy – defined as the sum of dispersion energy and specific surface energy, expressed in mJ / m 2 Calculated, and measured by reversed-phase gas chromatography (“IGC”) as described in the specification—a reduction of at least 20%, for example, at least 50%, in the total surface energy relative to the original carbon surface; and / or - Specific surface area less than or equal to 1.5m² 2 / g, measured by reversed-phase gas chromatography (“IGC”) as described in the instructions.

[0065] According to a preliminary aspect of the present invention relating to the above-described processing method, a watch movement regulating mechanism is also disclosed, the regulating mechanism comprising: - Flexible components as defined above, particularly hairsprings suitable for oscillating about the axis, and - A balance wheel that mates with the flexible component.

[0066] In this specification, the term "based on" should be understood to mean that the material or element concerned mainly contains the component concerned, by weight (i.e., mass fraction) greater than 50%, preferably greater than 75%, and up to 100% (if the material is composed of that component). Attached Figure Description

[0067] Other features, details, and advantages of the invention will become apparent from the following description of several embodiments of the invention, taken in conjunction with the accompanying drawings. These embodiments are for illustrative purposes only and are not intended to limit the invention: Figure 1 [ Figure 1 [Illustrated diagram of an embodiment of a watch that can include a flexible component (such as a hairspring) according to the invention.]

[0068] Figure 2 [ Figure 2 This is an exemplary embodiment of the present invention. Figure 1 A top view of the hairspring in a watch's regulating mechanism.

[0069] Figure 3 [ Figure 3 ]Schematic illustration Figure 2 An exemplary composition of the hairspring material is shown in the form of a forest of nanotubes. For clarity, the nanotubes are intentionally enlarged and therefore not drawn to scale.

[0070] Figure 4 [ Figure 4 [A] is a perspective view of an embodiment of a speed regulating mechanism according to the present invention, which includes Figure 2 The gossamer threads.

[0071] Figure 5 [ Figure 5 [Illustrated diagram] is a simplified reaction diagram illustrating the main steps of a functionalization and passivation method according to an embodiment of the present invention, starting from a precursor of a diazonium salt complex (a fluorocarbon derivative of aniline).

[0072] Figure 6 [ Figure 6 This is a graph comparing the water contact angles of distilled water on a monolayer silicon substrate coated with a pyrolytic carbon layer: - Untreated (reference sample) - Surface treatment (silane sample) with a halosilane-containing solution. - Surface treat (Epilame® sample) with Epilame® solution. - According to Embodiment 1 of the present invention, a hydrophobic monolayer membrane is used for functionalization and passivation. - According to Embodiment 4 of the present invention, a hydrophobic monolayer film is used for functionalization and passivation, and - According to Embodiment 6 of the present invention, a hydrophobic monolayer membrane is used for functionalization and passivation.

[0073] Figure 7 [ Figure 7The diagram illustrates a typical result of the initial step in a CVD process for treating a catalyst layer, used to prepare a nanocomposite material based on carbon nanotubes impregnated with pyrolytic carbon. This step is applied to a multi-layered substrate to ultimately form the catalyst layer, on which carbon nanotubes are grown.

[0074] Figure 8 [ Figure 8 The schematic diagram illustrates the process in CVD. Figure 7 Typical results of subsequent steps in growing carbon nanotubes on a catalyst layer treated in the middle.

[0075] Figure 9 [ Figure 9 [Schematic diagram showing the infiltration of pyrolytic carbon in a CVD process] Figure 8 Typical results of subsequent steps within and between carbon nanotubes deposited in the middle.

[0076] Figure 10 [ Figure 10 [Schematic diagram illustrating, according to a preliminary aspect of the present invention, in a CVD process, for] Figure 9 The result of subsequent steps to deposit carbon coatings on the top and side surfaces of the obtained carbon nanocomposite material.

[0077] Figure 11 [ Figure 11 [Schematic diagram illustrating, according to a preliminary aspect of the present invention, in a CVD process, ...] Figure 10 The diagram shows the result of a subsequent step in flipping the coated carbon nanocomposite, with the aim of further depositing the coating onto the bottom surface of the nanocomposite.

[0078] Figure 12 [ Figure 12 [Schematic diagram illustrating, according to a preliminary aspect of the present invention, the deposition of a carbon coating onto the substrate in this CVD process.] Figure 11 The results of subsequent steps on the bottom surface of the flipped carbon nanocomposite are shown. Detailed Implementation

[0079] Figure 1 A clock 1 is shown, such as a mechanical watch, which includes: - Case 2, - The watch movement 3 is contained within the case 2. - Typically, the on-chain mechanism 4, - Dial 5, - The watch crystal 6 covering dial 5, and - The time indicator 7, for example, includes two hands 7a and 7b that indicate the hour and minute respectively, which are positioned between the crystal 6 and the dial 5 and are driven by the watch movement 3.

[0080] Figure 2 The hairspring 20 of the speed regulating mechanism 1a according to the present invention is shown (see Figure 4 The hairspring 20 is arranged to rotate together with the balance wheel 10 about the central axis Y (see also). Figure 4 The hairspring 20 is L in length and includes multiple coils 22, as well as an end portion 23 (“end curve”) that is typically secured to the oscillating clamp by studs. Figure 4 (See reference numeral 40 in the attached figure), wherein the balance wheel 10 is pivotally mounted on the balance clamp.

[0081] The hairspring 20 includes a central portion 21 for attaching it to the balance shaft of the balance wheel 10. Figure 2 In the illustrated embodiment, the central portion 21 is integrally formed with the hairspring 20 and is made of the same material as the hairspring 20. Figure 2 As shown, the thickness of coil 22 is t (in a plane perpendicular to axis Y), for example, about tens of micrometers, such as about 10µm-100µm. It should be noted that the thickness of coil 22 may not be constant.

[0082] like Figure 3 As shown, coil 22 also has a height h (parallel to axis Y), and the hairspring 20 is made of a composite material comprising carbon nanotubes 200 contained within a pyrolytic carbon matrix 202. The nanotubes 200 form a forest of side-by-side nanotubes, which are substantially parallel to each other, advantageously parallel to axis Y, or not parallel (e.g., when the nanotubes are not straight but wavy, not parallel to axis Y). They are generally regularly spaced apart from each other and are present throughout the composite material.

[0083] The diameter d of the nanotube can be 1 nm to 30 nm, optionally 4 nm to 18 nm, and more particularly about 10 nm. The length of the nanotube can be 50 µm to 500 µm, optionally 150 µm to 275 µm, and more particularly about 225 µm. This length can advantageously correspond to the aforementioned height h of the coil 22 of the hairspring 20.

[0084] The matrix 202 can advantageously be composed of pyrolytic carbon, and it advantageously encapsulates the nanotubes 200 through the voids 204 between the nanotubes 200 and within the internal space 206. The matrix 202 serves to provide cohesion for the nanotube forest.

[0085] Figure 4A perspective view of an embodiment of the speed regulating mechanism 1a according to the invention is shown, wherein the balance wheel 10 includes a balance wheel rim 12 and four arms 14; each arm 14 has a generally triangular shape and includes a central opening 17, which in this example has no technical function. In one variation, the number of arms may be different from four. In another variation, the arms are generally linear in shape. In yet another variation, the arms have no openings. Figure 4 Also visible is the regulator-indicator assembly 30, which acts on the effective length of the hairspring 20 to adjust the oscillation frequency.

[0086] For example, such as Figure 2 The hairspring 20 shown is mainly manufactured through the following steps: - A chemical vapor deposition (“CVD”) process performed on a silicon wafer used as a substrate; subsequently - Perform cleaning processes, including: First, use air or nitrogen; then For example, the second step involves ultrasonic treatment in a solvent to clean the surface, followed by the third step, which extracts the physically adsorbed molecules; finally... - Dry at ambient temperature or elevated temperature to remove solvent traces.

[0087] The hairsprings 20 manufactured in this way are then classified into specific categories and stored.

[0088] According to the present invention, the functionalization and passivation of the carbon surface 20a of the hairspring 20 are carried out during its cleaning cycle, preferably between the second and third steps (see...). Figure 5 ).

[0089] In the embodiments presented below, the carbon surface 20a of the same hairspring 20 is formed of a carbon / carbon nanocomposite material, which consists of a forest of carbon nanotubes 200 impregnated with pyrolytic carbon 202 (also referred to as "nanocrystalline carbon" or "amorphous carbon") and is functionalized and passivated. As described below, a hydrophobic monolayer film is deposited on pyrolytic carbon 202 and carbon nanotubes 200 (within the reach of nanotubes 200) using the method of the present invention.

[0090] Therefore, such as Figure 5 As shown, a precursor for the complex was used; this precursor is, for example, composed of a fluorocarbon derivative of aniline (i.e., 4-(heptadecylfluorooctyl)aniline). The expanded structural formula of this derivative is shown below. Figure 5 As shown on the left. This precursor reacts with NaNO2 in a mixture of HCl and DMSO (dimethyl sulfoxide) at, for example, 20°C, to yield a fluorocarbon chain complex terminated with a diazonium salt; the structural formula of this complex is as follows. Figure 5 The intermediate chemical formula is shown, in which the anion X - In this exemplary embodiment, Cl- .

[0091] The hairspring 20 reacts with the composite precursor in situ (note that other precursors, such as triazine, may also be used as variants), or reacts with the resulting composite itself (according to a pre-formulated embodiment), by adding the precursor or the resulting composite to a reaction medium. As detailed in the examples below, a first in-situ scheme using a reducing agent is employed, applied to 50 hairsprings; then, as a variant, a second in-situ scheme without a reducing agent is employed, also applied to 50 hairsprings; and a third scheme using a pre-formed precursor.

[0092] The first experimental scheme uses a reducing agent (Example 1): The hairspring was pre-cleaned by ultrasonic cleaning in 10 mL of isopropanol (IPA) for 10 min. In the first flask, ascorbic acid (18 mg) was dissolved in water (1.25 mL) to prepare a reducing agent solution, and then IPA (3.75 mL) was added to obtain a final concentration of 0.02 mol / L. The hairspring was immersed in the ascorbic acid solution. In the second flask, 64 mg of 4-(heptadecylfluorooctyl)aniline was dissolved in 5 mL of IPA (0.025 mol / L), and 0.25 mL of 1 mol / L HCl aqueous solution was added. Next, 1.25 mL of NaNO2 aqueous solution (0.1 mol / L) was added to the 4-(heptadecylfluorooctyl)aniline solution to induce the formation of diazonium salt. Then, the diazonium salt solution was added to the reducing solution containing the hairspring, making the volume ratio of the two solutions 1:1. The surface reaction was allowed to proceed for 24 hours. Next, remove the hairspring and rinse it, optionally using acetone for ultrasonic cleaning 1-3 times, then water for ultrasonic cleaning 1-3 times, and finally IPA for ultrasonic cleaning 1-3 times. Then, allow the hairspring to air dry at ambient temperature for 1 hour.

[0093] The second experimental scheme does not use a reducing agent (Example 4): The hairspring was pre-cleaned by ultrasonic cleaning in 10 mL of isopropanol (IPA) for 10 min. Next, 128 mg of 4-(heptadecylfluorooctyl)aniline was dissolved in 10 mL of dimethyl sulfoxide (DMSO) (0.025 mol / L), and 0.5 mL of 1 mol / L HCl aqueous solution was added. The hairspring was then added to this solution. Next, 2.5 mL of 0.1 mol / L NaNO₂ in DMSO solution was added. The surface reaction was allowed to proceed for 24 hours. The hairspring was then removed and rinsed, optionally ultrasonically cleaned 1-3 times with acetone, followed by 1-3 times with water, and finally 1-3 times with IPA. The hairspring was then air-dried at ambient temperature for 1 hour.

[0094] The third experimental approach uses a pre-formed complex (Example 6): A solution of t-BuONO (124 mg) and 4-(heptadecylfluorooctyl)aniline (511 mg) in glacial acetic acid (4 mL) was added dropwise to a solution of trifluoromethanesulfonic acid (180 mg) in glacial acetic acid (6 mL). The reaction mixture was stirred for 10–20 min. After the reaction was complete, ether (100–150 mL) was added. The precipitated diazonium salt was collected by filtration, yielding a white powder, which was then dried. This powder (134 mg) was dissolved in DMSO (10 mL) to obtain a 0.02 mol / L solution, which was then added to a pre-cleaned hairspring that had been ultrasonically cleaned for 10 min in 10 mL of isopropanol (IPA). The surface was allowed to react for 24 hours. The hairspring was then removed and rinsed, optionally ultrasonically cleaned 1–3 times with acetone, then 1–3 times with water, and finally 1–3 times with IPA. The hairspring was then allowed to air dry at ambient temperature for 1 hour.

[0095] The "XPS" experimental protocol was used to analyze the hairspring samples obtained through these treatments: X-ray photoelectron spectroscopy (XPS) analysis was performed in a laboratory accredited according to ISO / IEC 17025:2017-11. XPS instruments were calibrated according to ISO 15472:2010-05, and their performance was validated monthly according to ISO 16129:2018-11. Samples were prepared according to ISO 18117:2009-03. Analysis and evaluation were performed according to ISO 10810:2019-08.

[0096] More specifically, XPS measurements are performed by bombarding atoms with X-rays, exciting their electrons and causing them to detach from the atoms and potentially from the surface of each sample. The energy of these photoelectrons is analyzed using a hemispherical analyzer to calculate their binding energy. This allows for the quantitative determination of the chemical composition of each sample surface layer within the 5 nm–10 nm range.

[0097] Specifically, the XPS analysis can assess the fluorine atom concentration in the passivated carbon surface region (i.e., the outermost surface region of each hairspring, with a thickness of approximately 2-10 nm) deposited on each hairspring sample obtained according to the processing according to the present invention, as a function of reaction parameters, as shown in Table 1 below, which compares the efficiency of depositing the film according to the reaction conditions used.

[0098] The fluorine atom concentration on this surface is the percentage of F measured on surface 20a of the hairspring 20, after the hairspring has been functionalized and passivated by depositing a hydrophobic monolayer film. Since fluorine originates solely from this film, this F atom concentration assesses the number of molecules present on the hairspring surface (for an untreated hairspring, the atomic percentage of F = 0).

[0099] According to embodiments 1-6 of the present invention, the hairspring 20 is treated as follows: In Examples 1-5 presented in Table 1 below, in-situ formation of the composite and deposition of the monolayer occurred simultaneously. Therefore, in this case, the atomic concentration of fluorine reflects the efficiency of both composite formation and monolayer deposition.

[0100] In Table 1 below: - "Na Asc" is an abbreviation for sodium ascorbate; - “conc.” indicates the concentration (mmol / L) of the complex in the reaction medium; and - IPA, DMSO and TFA are abbreviations for isopropanol, dimethyl sulfoxide and trifluoroacetic acid, respectively (used in Example 5 to treat the sample instead of HCl in Examples 1-4).

[0101] [Table 1]:

[0102] Scheme for measuring water contact angle: Since the water contact angle cannot be measured directly on the obtained hairspring 20, a planar substrate (silicon wafer) coated with a pyrolytic carbon layer is used as a reference standard sample, similar to the carbon layer that defines the carbon surface 20a of each hairspring 20.

[0103] Sample description: - Reference Standard samples without surface treatment were ultrasonically cleaned in isopropanol (IPA), and then the water contact angle was measured. - silane The standard sample was immersed in a chloroform solution containing 0.01 mol / L 1H,1H,2H,2H-perfluorooctyltrichlorosilane for 24 hours; then, the sample was rinsed with chloroform and then sonicated in pure chloroform to remove chemicals not bound to the carbon surface, and then the water contact angle was measured. - epilame The standard sample was immersed in a commercially available solution, "Moebius FixoDrop ES / BS 8981" (commonly known as "epilame," based on fluorinated polyester), for 24 hours; then, the sample was rinsed with acetone, followed by sonication in pure acetone to remove unbound chemicals, after which the water contact angle was measured; and - Embodiments 1, 4 and 6 of the present invention After rinsing each sample according to the above experimental protocol (Example 1 is the first protocol using a reducing agent; Example 4 is the second protocol without using a reducing agent; Example 6 is the third protocol using a pre-formed complex), the samples were placed in acetone for sonication. Subsequently, the water contact angle of each sample in Examples 1, 4, and 6 was measured, and the detailed results are recorded in Table 1.

[0104] The water contact angle was measured by dropping 3 µL of distilled water droplets onto the surface of each sample to be characterized. More specifically, the contact angle was measured using a contact angle analyzer, and droplet analysis was performed using the Yang-Laplace model. Figure 6 The values ​​shown represent the average of three angular measurements taken at three different locations on the surface to be characterized for each sample.

[0105] like Figure 6 As shown in the graphs, the carbon surfaces of the samples modified according to Examples 1, 4, and 6 of the present invention are indeed hydrophobic, i.e., their water contact angles are significantly greater than 90°. In fact, the angles of the treated samples from Examples 1, 4, and 6 exceed 100°, especially compared to the approximately 90° water contact angles observed in samples treated with silane reagents or epilame reagents. Therefore, these measurements clearly demonstrate that the monolayer film based on diazo functional groups can effectively passivate the carbon surface 20a of the hairspring 20 while simultaneously grafting onto the surface 20a via covalent bonds.

[0106] Scheme for measuring sample surface energy: The dispersive and specific surface energies of the samples to be characterized were determined using the “OWRK” method developed by Owens, Wendt, Rabel, and Kaelble (Owens DK and Wendt RC, 1969, J. Appl. Polym. Sci. 13, 1741). This method utilizes the static contact angles of several liquids. 3 µL droplets were dropped onto the surface of each sample to be characterized (reference sample and Example 4), and the static contact angles of water, diiodomethane, glycerol, and ethylene glycol were measured. Specifically, the contact angles were measured using a contact angle analyzer (Kruss), and droplet analysis was performed using the Yang-Laplace model. The values ​​for each sample listed in Table 2 are the average of three angular measurements taken at three different locations on the surface to be characterized. These values ​​were then used in the “OWRK” model to obtain the specific and dispersive surface energies of each sample.

[0107] Tables 2 and 3 below show the results for the contact angle and the resulting surface energy, respectively.

[0108] [Table 2]:

[0109] [Table 3]:

[0110] Scheme for measuring the surface energy of the hairspring 20: As described in the second aspect of the invention above, reversed-phase gas chromatography (IGC) was employed, and all analyses were performed using an IGC surface energy analyzer (surface measurement system). Data were analyzed using the "SEA" standard and advanced analytical software. Approximately 32 mg–56 mg of the Softspring 20 material was packed into a single IGC silanized glass column.

[0111] Therefore, a series of surface coverage measurements were performed using alkanes and polar probe molecules (adsorbates) to determine the dispersive surface energy and specific surface energy. For this purpose, the sample column was pretreated for 1 hour at 30 °C and 0% relative humidity (RH) with helium carrier gas at a flow rate of 10 mL / min. Experiments were conducted at 30 °C with a total helium flow rate of 10 mL / min, and dead volume correction was performed using methane.

[0112] Table 4 below shows the results obtained before and after applying the treatment according to the invention to the samples of Example 1 in Table 1 at relative humidity (RH) levels of 0%, 30%, and 60% (i.e., the untreated reference sample and the treated sample according to the invention).

[0113] [Table 4]

[0114] Comparing the reference sample (i.e., the undeposited monolayer film) with the sample of Example 1 demonstrates the passivation effect of the carbon surface 20a of the filament 20 in Example 1, showing a significant reduction in total surface energy when the relative humidity varies from 0% to 60%. Therefore, Table 4 demonstrates that the treated surface is insensitive to changes in ambient humidity (total surface energy remains constant), unlike the untreated surface, whose total surface energy decreases with increasing relative humidity.

[0115] Finally, it should be noted that the functionalization and passivation treatments according to the present invention do not change the mechanical properties (i.e., classification) of the hairspring 20 before and after treatment, but rather change the reactivity of the hairspring 20 to its environment. In fact, the applicant has verified that each treated hairspring 20 sample prepared according to Examples 1-6 showed no significant difference in classification before and after treatment according to the present invention. It should be understood that any incidental observation of individual sample classification differences is within the range of instrument measurement error.

[0116] Figure 7This is a cross-sectional view showing a known deposition process in a CVD reactor—on a silicon (Si) substrate 50 covered with a silica (SiO2) layer 51, at a temperature of 650°C–750°C in the presence of inert gases such as argon (Ar) and hydrogen (H2)—depositing a support element 52 (only one shown in the figure) formed from an alumina (Al2O3) layer. The support element 52 is deposited on layer 51, and these elements 52 contain an iron (Fe) 53 layer to promote the growth of carbon nanotubes 61. Figure 8 ).

[0117] Figure 8 This is a cross-sectional view showing that, in the same reactor at a temperature of 650℃-750℃, in the presence of inert gases argon and hydrogen, hydrocarbon gases are introduced as a carbon source into the CVD reactor, causing carbon nanotubes 61 to... Figure 7 The carbon nanotubes 61 are deposited along the axial direction (i.e., mainly perpendicular to the substrate 50) on the treated support element 52, a process known as CVD. This produces a forest 60 of carbon nanotubes 61 with a length, for example, 100µm-500µm.

[0118] Figure 9 This is a cross-sectional view showing a deposition process (also known as CVD deposition) in which, in the same reactor at a temperature of 750°C–850°C, pyrolytic carbon 70 is infiltrated into and between nanotubes 61 and contacts the support element 52, again using hydrocarbon gas as the carbon source and in the presence of argon and hydrogen.

[0119] In addition, Figure 9 The top surface 63 of each nanotube 61 forest 60 is indicated (in Figure 9 (in the middle horizontal display) and the opposite bottom surface 64; these surfaces are generally perpendicular to the side surface 62 (in Figure 9 (Vertical display in the middle) Extends. Surfaces 62, 63, and 64 together constitute the entire external carbon surface 80 of the carbon nanocomposite material 90 to be coated.

[0120] Therefore, the carbon surface 80 of the nanocomposite material 90 should be understood to refer to the surface 80 (pre-treated) according to the present invention, which includes all of the corresponding top surface 63, bottom surface 64 and side surface 62 of the carbon nanotube forest 60 impregnated with pyrolytic carbon.

[0121] Figure 10 This is a cross-sectional view illustrating, according to the present invention, the deposition of a carbon coating 100 onto the top surface 63 and side surface 62 of a nanotube forest 60 by CVD at approximately 850°C, using, for example, ethylene (C2H4) as a carbon source, in the presence of an inert argon gas and a hydrogen reducing agent. Figure 10As shown, the average thickness of the carbon coating 100 is preferably 50 nm-500 nm, for example, 90 nm-200 nm, which continuously covers the top surface 63 and side surface 62 of the carbon surface 80 (surfaces 62 and 63 are visible in...). Figure 9 ).

[0122] An exemplary embodiment of the method for depositing a carbon coating 100 according to the present invention comprises the following steps: - Purge the CVD reactor with argon gas to remove the residue from the previous step ( Figure 9 In this process, pyrolytic carbon is infiltrated into the spaces between and inside the nanotubes 61 of each nanotube forest 60, producing all the reagents and reaction products generated. - Under an inert argon atmosphere, the reactor temperature is adjusted to deposit carbon coating 100. The set temperature can be kept constant (i.e., the permeation temperature is 750-850°C, and the temperature for depositing carbon coating 100 is, for example, 850°C). - At atmospheric pressure and a temperature of 850℃-900℃, apply a carbon coating 100 (see...) Figure 10 ) was deposited on the top surface 63 and side surface 62 of the forest 60 of nanotube 61, with a deposition time of approximately 30 minutes (with Figure 9 Compared to the relatively slow deposition (lasting several hours) of intermediate infiltration, this is rapid deposition. The volume fractions and flow rates of argon, ethylene, and hydrogen in the reactor are as follows: Ar: Volume fraction = 0.38, Volumetric flow rate = 2500 sccm; C2H4: volume fraction = 0.23, volumetric flow rate = 1500 sccm; H2: Volume fraction = 0.38, Volumetric flow rate = 2500 sccm; - Purge, then cool the reactor under an inert argon atmosphere (nitrogen can also be used as an alternative); - Remove the entire substrate 50 from the reactor, including layers 51-52 and the nanocomposite material 90; - Add air at 900°C to clean the reactor; - Separate the nanocomposite material 90 from the layer formed by each support element 52 covering the substrate 50; then - The carbon nanocomposite material 90, which has detached from the support element layer 52, is reintroduced into the reactor individually, rotated 180° relative to the axis in the main plane (see...). Figure 11 Thus, under the same reaction conditions as those for the deposition of the top surface 63 and the side surface 62, the carbon coating 100 is deposited onto the bottom surface 64 (see [reference]). Figure 12 ).

[0123] Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show that, compared with the uncoated carbon nanocomposite 90 with a more porous microstructure, the carbon coating 100 obtained by each carbon nanocomposite 90 pretreated according to the present invention has a dense microstructure (the local thickness of the coating 100 is 95 nm).

[0124] In fact, the top surface 63, bottom surface 64 and side surface 62 of each coated nanocomposite 90 (i.e. the entire coated carbon surface 80 of the (pre)treated nanocomposite 90) have significant closed pores, which makes it possible to reduce or even eliminate molecular adsorption into the pores of the (pre)treated nanocomposite 90 according to the present invention.

[0125] Table 5 below shows the results of the total surface energy measured using the aforementioned IGC technique, for example, as Figure 10-12 As shown, the carbon coating 100 of the present invention was deposited on the nanocomposite material 90 (i.e., the treated sample according to the present invention), and compared with variants that do not conform to the present invention: i.e., no carbon coating, such as Figure 9 As shown (i.e., the untreated reference sample).

[0126] [Table 5]

[0127] Table 6 below shows the results of specific surface area measured by IGC, for example, Figure 10-12 As shown, the carbon coating 100 of the present invention is deposited on the nanocomposite material 90 (i.e., the treated sample according to the present invention), and compared with a variant without carbon coating (i.e., an untreated reference sample, such as...). Figure 9 (As shown) for comparison.

[0128] [Table 6]

Claims

1. A method for treating the carbon surface (80) of a carbon nanocomposite material (90), said carbon nanocomposite material (90) being configured to form a flexible component of a watch movement regulating mechanism, said carbon nanocomposite material (90) having open pores and comprising a forest (60) of carbon nanotubes (61) impregnated with pyrolytic carbon (70), The method includes: In a chemical vapor deposition reactor, at a temperature of 500°C–1200°C, the carbon nanocomposite material (90) was exposed to a gaseous reagent containing a hydrocarbon carbon source and a reagent for inhibiting the carbon deposition reaction. A carbon coating (100) with an average thickness of 50 nm to 500 nm is deposited in a controlled manner, the carbon coating covering the carbon surface (80).

2. The processing method according to claim 1, comprising: - The reagent is introduced into a reactor containing the carbon nanocomposite material (90) and heated to the specified temperature, with or without the introduction of an inert gas carrying the reagent and reaction products into the reactor; and simultaneously - At the stated temperature, the carbon nanocomposite material (90) is exposed to the reagent for a duration of 1 min - 1 h 30 min.

3. The processing method according to any one of the preceding claims, wherein the carbon nanocomposite material (90) (i) Before its processing: - Contains a forest (60) of carbon nanotubes (61) impregnated with pyrolytic carbon (70), the nanotubes (61) covering a support element (52) deposited on a semiconductor substrate (50); and - Having said carbon surface (80), said carbon surface forming the outer surface of said nanocomposite material (90), which externally defines said nanotube (61) forest (60), and includes: The corresponding top surface (63) of the nanotube (61), The bottom surface (64), which is located at the bottom of the nanotube (61) forest (60) and opposite to the top surface (63), and The side surface (62) connecting the top surface (63) and the bottom surface (64); and (ii) After its processing: The carbon coating (100) is deposited on the top surface (63), bottom surface (64) and side surface (62) of the carbon nanocomposite material (90).

4. The processing method according to claim 3, wherein the nanocomposite material (90) is rotated 180° so that after the carbon coating (100) is deposited on the top surface (63) and the side surface (62), the carbon coating (100) is deposited on the bottom surface (64), thereby the carbon coating (100) continuously covers the carbon surface (80) composed of carbon atoms, the carbon nanocomposite material (90) being composed of carbon nanotubes (61) and pyrolytic carbon (70).

5. The processing method according to any one of the preceding claims, wherein an aliphatic or aromatic unsaturated hydrocarbon, such as that selected from ethylene, acetylene and xylene, is used as the hydrocarbon carbon source.

6. The processing method according to claim 5, wherein the hydrocarbon carbon source is ethylene, and the nanocomposite material (90) is exposed to the reagent at a temperature of 800°C - 1000°C.

7. The processing method according to claim 6, wherein ethylene is used as the hydrocarbon carbon source, and its volume fraction X C2H4 It is 0.05-0.

50.

8. The processing method according to any one of the preceding claims, wherein a hydrogen-containing gas, such as hydrogen or ammonia, is used as a suppressing agent.

9. The processing method according to claim 8, wherein hydrogen is used as the suppressant, and its volume fraction X H2 It ranges from 0.30 to 0.

65.

10. The processing method according to any one of the preceding claims, wherein, To deposit the carbon coating (100) in a controlled manner, the following conditions are employed: - The reaction duration is 10 min - 50 min, and / or - Temperature is 850℃ - 900℃.

11. The processing method according to any one of the preceding claims, wherein, Before exposing the carbon nanocomposite material (90) to the reactor for controlled deposition of the carbon coating (100), the method further includes an initial step comprising: - The reactor is purged under an inert atmosphere to remove reagents and reaction products previously used for depositing pyrolytic carbon (70), and - The temperature is adjusted under the inert atmosphere to prepare for the controlled deposition of the carbon coating (100).

12. A flexible component (20) for a regulating mechanism (1a) of a watch movement, said flexible component, particularly a hairspring, adapted to bend in a plane perpendicular to an axis (Y), said flexible component comprising a carbon nanocomposite material (90) having a carbon surface (80) treated by the method according to any one of the preceding claims, said carbon nanocomposite material (90) comprising a forest (60) of carbon nanotubes (61) impregnated with pyrolytic carbon (70), The carbon surface (80) is covered with a carbon coating (100) with an average thickness of 50 nm-500 nm, for example 90 nm-200 nm.

13. The flexible component (20) according to claim 12, wherein the carbon surface (80) exhibits the following characteristics after the treatment: - The total surface energy is reduced by at least 20%, for example, at least 50%, relative to the total surface energy of the original carbon surface; the total surface energy is defined as the sum of dispersion energy and specific surface energy, expressed in mJ / m 2 Calculated, and measured using reversed-phase gas chromatography ("IGC") as described in the instructions, and / or - Specific surface area less than or equal to 1.5 m² 2 / g, which is measured by reversed-phase gas chromatography ("IGC") as described in the instructions.

14. A regulating mechanism (1a) for a watch movement, said regulating mechanism (1a) comprising: - A flexible component (20) adapted to bend in a plane perpendicular to the axis (Y), particularly adapted to a hairspring oscillating about said axis (Y); and - A balance wheel (10) that cooperates with the flexible component (20), The flexible component (20) is as defined in claim 12 or 13.

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