A golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating and a preparation method thereof

Abstract

The present invention discloses a golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating and a preparation method thereof. The golf club head includes a golf club head substrate with a diamond-like carbon coating formed on its surface and having a nano-hardness exceeding 15 GPa. The diamond-like carbon coating includes a transition layer with a thickness of 0.5 - 0.9 microns and a hydrogen-containing carbon-based coating with a thickness of 2.0 - 4.0 microns, which are distributed in sequence from the inside to the outside. The transition layer includes a metal layer covering the surface of the golf club head substrate and a metal / C composite layer with carbon gradiently distributed on the metal layer. The thickness of the metal layer is 300 - 500 nm, and the thickness of the metal / C composite layer is 200 - 400 nm. By using the preparation method of the present invention, a golf club head with a diamond-like carbon coating can be deposited and prepared quickly and efficiently. The obtained golf club head has excellent wear-resistant and corrosion-resistant properties, strong coating film-substrate adhesion, and a bright gloss appearance visual effect on the surface.

Description

Technical Field

[0001] The present invention relates to the technical field of golf club head preparation, and particularly to a golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating and a preparation method thereof. Background Art

[0002] Due to good processing performance, metal material products are widely used in industries such as sports equipment and watches. Golf club heads are mostly made of iron-based materials and titanium alloys. The surface hardness of these materials is relatively low, usually lower than HRC50, and the wear resistance of golf club heads during use is poor. In addition, for some golf club heads, due to the extensive use of non-austenitic iron-based materials such as 17-4 alloy, etc., it is necessary to improve the corrosion resistance level of these club heads. In addition, as a decorative requirement, it is also necessary to perform surface treatment on golf club heads to achieve the appearance effect of a black and bright color.

[0003] Currently, various advanced surface modification technologies are constantly being tried and applied in the field of golf club head preparation. Among them, diamond-like carbon coatings (DLC coatings) have attracted wide attention in the field of golf club head manufacturing due to their excellent wear-resistant and corrosion-resistant properties. However, the current efficiency of preparing DLC coatings is low, and the preparation cost is high, which will seriously limit the wide application of DLC coatings in the field of golf club head manufacturing. Summary of the Invention

[0004] The purpose of the present invention is to provide a golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating and a preparation method thereof, which solves the problems of slow deposition rate and weak coating-substrate bonding force when preparing DLC coatings on the surface of golf club heads in the prior art.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating, including a golf club head substrate. A diamond-like carbon coating with a nano-hardness exceeding 15 GPa is formed on the surface of the golf club head substrate. The diamond-like carbon coating includes a transition layer and a hydrogenated carbon-based coating that are distributed in sequence from the inside to the outside. The transition layer includes a metal layer covering the surface of the golf club head substrate and a metal / C composite layer in which carbon is distributed in a gradient on the metal layer; the thickness of the hydrogenated carbon-based coating is 2.0 - 4.0 microns, the thickness of the metal layer is 300 - 500 nm, the thickness of the metal / C composite layer is 200 - 400 nm, and the total thickness of the transition layer is 0.5 - 0.9 microns.

[0007] Further, the volume content of sp 3 C in the hydrogenated carbon-based coating exceeds 45%.

[0008] Further, the metal layer in the transition layer is any one of a titanium layer, a chromium layer, a tungsten layer, a titanium-aluminum alloy layer or a chromium-aluminum alloy layer.

[0009] Further, the material of the golf club head base body is a soft metal material with a hardness lower than HRC50.

[0010] Further, the material of the golf club head base body is an iron-based alloy or a titanium alloy.

[0011] In a second aspect, the present invention provides a method for preparing any one of the above-mentioned golf club heads with a wear-resistant and corrosion-resistant diamond-like carbon coating, comprising the following steps:

[0012] S1. Pretreatment: Ultrasonically clean the surface of the golf club head base body and dry it with oil-free compressed air for later use;

[0013] S2. Etching activation: Place the golf club head base body treated in step S1 in the vacuum chamber of a vacuum coating device. The pressure in the vacuum chamber is 0.05 - 0.15 Pa. There are 2 magnetron target cathodes and 4 ionization source electrodes installed in the vacuum chamber. Apply a pulsed bias voltage of -150 V to -250 V to the golf club head base body, turn on the ion source, and use argon plasma to etch and activate the surface of the golf club head base body. During this period, maintain the DC arc current at 60 - 100 A, and the etching activation time is 30 - 60 min. The surface temperature of the etched golf club head base body reaches 83°C - 150°C;

[0014] S3. Preparation of the transition layer: Introduce argon gas into the vacuum chamber and maintain the pressure at 0.05 - 0.15 Pa. Then start the 2 magnetron target cathodes, adjust the power of the magnetron target cathodes to be maintained at 4 - 5 kW and deposit a metal layer with a thickness of 300 - 500 nm on the golf club head base body; then maintain the inflow rate of argon gas and linearly reduce the power of the magnetron target cathodes from 4 - 5 kW to 1 kW, while linearly increasing the inflow rate of methane working gas until the pressure in the vacuum chamber reaches 1.0 - 2.0 Pa. Start the 2 ionization source electrodes, linearly adjust the power of the ionization source electrodes from 1.5 kW to 4.0 - 5.0 kW for magnetron sputtering, apply a pulsed bias voltage of -150 V to -250 V to the golf club head base body to deposit a metal / C composite layer. When the thickness of the deposited metal / C composite layer reaches 200 - 400 nm, turn off the 2 magnetron target cathodes;

[0015] S4. Preparation of high sp 3Hydrogen-containing carbon-based coating with C content: Maintain the flow rate of argon in step S3 and adjust the inflow rate of methane working gas to keep the pressure in the vacuum chamber at 1.3 - 2.0 Pa. Turn off the magnetron target cathode, and at the same time start the operation of 4 ionization source electrodes with a power adjusted to 4.0 - 5.0 kW. Apply a pulsed bias voltage of -300 to -500 V to the golf club head substrate and deposit for 40 - 60 min to prepare a hydrogen-containing carbon-based coating, thus obtaining a golf club head with a wear-resistant and corrosion-resistant diamond-like coating.

[0016] Furthermore, the surface of the ionization source electrode is covered with an a-C:H coating, the thickness of the a-C:H coating is ≥ 1 micron, and the surface resistance of the a-C:H coating is ≥ 1 MΩ.

[0017] Furthermore, a closed magnetic field is formed in a ring perpendicular to the electrode axis on the surface of the ionization source electrode, and the magnetic field intensity of the closed magnetic field in the direction perpendicular to the electrode axis on the surface of the ionization source electrode is 4000 - 8000 gauss.

[0018] Furthermore, the materials of the magnetron target cathode and the ionization source electrode are metal or alloy.

[0019] Furthermore, the materials of the magnetron target cathode and the ionization source electrode are selected from any one of titanium, chromium, tungsten, titanium-aluminum, chromium-aluminum, or tungsten carbide.

[0020] Compared with the prior art, the present invention provides a golf club head with a wear-resistant and corrosion-resistant diamond-like coating and its preparation method, having the following beneficial effects:

[0021] The present invention uses a special columnar ionization source electrode and a magnetron target cathode with a traditional structure in combination to perform vacuum vapor deposition on the surface of the golf club head to prepare a wear-resistant and corrosion-resistant high-sp 3 Hydrogen-containing diamond-like coating with C content, the total thickness of the transition layer is controlled at 0.5 - 0.9 microns, and the thickness of the hydrogen-containing carbon-based coating is controlled at 2.0 - 4.0 microns; the growth rate of the prepared diamond-like coating reaches 100 - 150 nm / min, the sp 3 C volume content of the coating exceeds 45%, the surface nano-hardness of the coating exceeds 15 GPa, and the 5.5% salt spray corrosion resistance exceeds 96 hours.

[0022] Using the preparation method of the present invention can quickly and efficiently deposit and prepare a golf club head with a diamond-like coating. The obtained golf club head has excellent wear-resistant and corrosion-resistant properties, strong coating-substrate bonding force, and a bright gloss appearance visual effect on the surface. Description of the Drawings

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can be obtained based on these drawings.

[0024] Figure 1 It is a schematic structural diagram of a golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to the present invention.

[0025] Reference numerals: 1, golf ball head substrate; 2, transition layer; 3, hydrogen-containing carbon-based coating. Detailed implementation manners

[0026] The following will clearly and completely describe the technical solutions of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0027] The present invention will be further described in detail below through detailed embodiments in combination with the accompanying drawings.

[0028] The vacuum coating device used in the following embodiments is a conventional device, which has 6 magnetrons, an ion source and a bipolar pulse bias power supply, and can be obtained through commercial channels. In the present invention, 2 magnetrons are modified to be ionization source electrodes for decomposing surrounding hydrocarbon gases; the remaining 4 unmodified magnetrons are used as magnetron cathodes for sputtering the surface substances of the targets. 2 magnetron cathodes share 1 intermediate frequency twin power supply, and every 2 ionization source electrodes share 1 intermediate frequency twin power supply. The surfaces of the 2 ionization source electrodes are covered with an a-C:H coating, the thickness of the a-C:H coating is 1 micron, and the surface resistance of the a-C:H coating exceeds 1 MΩ; a closed magnetic field is formed in the ring perpendicular to the electrode axis on the surface of the ionization source electrode, and the magnetic field intensity of the closed magnetic field in the direction perpendicular to the electrode axis on the surface of the ionization source electrode is 4000 - 8000 gauss.

[0029] Embodiment 1

[0030] This embodiment provides a golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating, which is obtained by using a golf ball head substrate made of 17-4 iron-based alloy material according to the following preparation method:

[0031] S1. Pretreatment: The golf ball head substrate 1 made of 17-4 iron-based alloy material is ultrasonically cleaned on the GT-Cleaningsystem cleaning line and dried with oil-free compressed air for later use.

[0032] S2. Etching activation: Place the golf ball head substrate 1 that has been cleaned in step S1 on the sample workbench in the vacuum chamber of the vacuum coating device. In the vacuum chamber, 2 magnetron target cathodes made of titanium metal, 4 ionization source electrodes made of WC, and coils for forming a closed magnetic field are installed. Close the vacuum chamber and pump the background vacuum to below 5×10 -3 Pa. Introduce argon gas through the ion source to maintain the pressure in the vacuum chamber at 0.15 Pa. Turn on the ion source and use argon plasma to perform Ar + ion bombardment etching and cleaning on the surface of the golf ball head substrate 1 to obtain a clean workpiece surface. During this process, maintain the DC arc current at 100 A, apply a pulsed bias voltage of -250 V to the golf ball head substrate 1. After 60 minutes of etching activation, the surface temperature of the golf ball head substrate 1 reaches 150 °C, and then turn off the ion source.

[0033] S3. Preparation of the transition layer 2: Introduce argon gas into the vacuum chamber and maintain the pressure at 0.15 Pa. Then start the 2 magnetron target cathodes, adjust the power of the magnetron target cathodes to be maintained at 5.0 kW and deposit a 500-nm-thick titanium layer on the golf ball head substrate 1. Then maintain the argon gas flow rate and linearly reduce the power of the magnetron target cathodes from 5.0 kW to 1 kW, while linearly increasing the inflow rate of methane working gas until the pressure in the vacuum chamber reaches 2.0 Pa. Start the 2 ionization source electrodes and linearly adjust the power of the ionization source electrodes from 1.5 kW to 5.0 kW for magnetron sputtering. Apply a pulsed bias voltage of -200 V to the golf ball head substrate 1 to deposit a Ti / C composite layer. When the thickness of the deposited Ti / C composite layer reaches 400 nm, turn off the 2 magnetron target cathodes.

[0034] S4. Preparation of the hydrogen-containing carbon-based coating 3 with a high sp 3 C content: Maintain the argon gas flow rate in step S3 and adjust the inflow rate of methane working gas to keep the pressure in the vacuum chamber maintained at 2.0 Pa. Turn off the magnetron target cathodes, and at the same time start the 4 ionization source electrodes with a power adjusted to 5.0 kW to work. Apply a pulsed bias voltage of -500 V to the golf ball head substrate 1 and deposit for 60 minutes to prepare the hydrogen-containing carbon-based coating 3, that is, a golf ball head with a wear-resistant and corrosion-resistant diamond-like coating is obtained.

[0035] The golf ball head with a wear-resistant and corrosion-resistant diamond-like coating prepared in this embodiment has a structure as Figure 1As shown in the figure, it includes a golf ball head substrate 1 made of 17-4 iron-based alloy. A diamond-like carbon coating is formed on the surface of the golf ball head substrate 1. The diamond-like carbon coating includes a transition layer 2 with a total thickness of 0.8 μm and a hydrogen-containing carbon-based coating 3 with a thickness of 4.0 μm, which are distributed in sequence from the inside to the outside. Among them, the transition layer 2 includes a 400-nm-thick titanium layer covering the surface of the golf ball head substrate 1 and a 400-nm-thick Ti / C composite layer with carbon gradiently distributed on the titanium layer.

[0036] The hardness was tested using a nanoindenter (Anton Paar TTX-NHT3, Switzerland) with a load of 5 mN, a loading rate of 10 mN / min, and a holding time of 10 s. An X-ray photoelectron spectrometer (XPS, Thermo K-Alpha +, USA) with an incident photon energy of 1486.6 eV was used to analyze the sp 3 C volume content ratio in the coating. After testing, the nano-hardness of the golf ball head in this example is 18 GPa, and the volume content of sp 3 C in the coating is 55%. After the golf ball head was rubbed 50,000 times with a 1100 g load on a Tabler, the substrate was not exposed; after 96 hours of 5.5% NaCl neutral salt spray test, no rust spots were seen.

[0037] Example 2

[0038] This example provides a golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating, which is obtained by the following preparation method using a golf ball head substrate made of titanium alloy:

[0039] S1. Pretreatment: The golf ball head substrate 1 made of titanium alloy is ultrasonically cleaned on the GT-Cleaning system cleaning line and dried with oil-free compressed air for standby.

[0040] S2. Etching activation: The golf ball head substrate 1 treated in step S1 is placed on the sample workbench in the vacuum chamber of the vacuum coating device. In the vacuum chamber, 2 magnetron target cathodes made of Ti50Al50 alloy, 4 ionization source electrodes made of WC, and a coil for forming a closed magnetic field are installed. The vacuum chamber is closed and the background vacuum is pumped down to 5×10 -3 Pa or less. Argon is introduced through the ion source to maintain the pressure in the vacuum chamber at 0.05 Pa. The ion source is turned on to use argon plasma to perform Ar + ion bombardment etching cleaning on the surface of the golf ball head substrate 1 to obtain a clean workpiece surface. During this period, the DC arc current is maintained at 60 A, and a pulse bias voltage of -150 V is applied to the golf ball head substrate 1. After 30 minutes of etching activation, the surface temperature of the golf ball head substrate 1 reaches 83 °C, and the ion source is turned off.

[0041] S3. Preparation of the transition layer 2: Introduce argon gas into the vacuum chamber and maintain the pressure at 0.05 Pa. Then start 2 magnetron target cathodes, adjust the power of the magnetron target cathodes to be maintained at 4.0 kW, and deposit a Ti50Al50 alloy layer with a thickness of 300 nm on the golf club head substrate 1. Then maintain the inflow rate of argon gas and linearly reduce the power of the magnetron target cathodes from 4.0 kW to 1.0 kW, while linearly increasing the inflow rate of methane working gas until the pressure in the vacuum chamber reaches 1.0 Pa. Start 2 ionization source electrodes, linearly adjust the power of the ionization source electrodes from 1.5 kW to 4.0 kW for magnetron sputtering, apply a pulsed bias voltage of -100 V to the golf club head substrate 1 to deposit a (Ti + Al) / C composite layer. When the thickness of the deposited (Ti + Al) / C composite layer reaches 200 nm, turn off the 2 magnetron target cathodes.

[0042] S4. Preparation of the hydrogen-containing carbon-based coating 3 with a high sp 3 C content: Maintain the inflow rate of argon gas in step S3 and adjust the inflow rate of methane working gas to keep the pressure in the vacuum chamber at 1.3 Pa. Turn off the magnetron target cathodes, and at the same time start 4 ionization source electrodes with a power adjusted to 4.0 kW to work. Apply a pulsed bias voltage of -300 V to the golf club head substrate 1 and deposit for 60 min to prepare the hydrogen-containing carbon-based coating 3, that is, a golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating is obtained.

[0043] The golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating prepared in this embodiment has a structure as Figure 1 shown, including a golf club head substrate 1 made of titanium alloy. A diamond-like carbon coating is formed on the surface of the golf club head substrate 1. The diamond-like carbon coating includes a transition layer 2 with a total thickness of 0.5 μm and a hydrogen-containing carbon-based coating 3 with a thickness of 2.0 μm, which are distributed in sequence from the inside to the outside. Among them, the transition layer 2 includes a 300-nm-thick titanium-aluminum layer covering the surface of the golf club head substrate 1 and a 200-nm-thick (Ti + Al) / C composite layer with carbon gradiently distributed on the titanium-aluminum layer.

[0044] The hardness was tested using a nanoindentation instrument (Anton Paar TTX-NHT3, Switzerland), with a load of 5 mN, a loading rate of 10 mN / min, and a holding time of 10 s. An X-ray photoelectron spectrometer (XPS, Thermo K-Alpha +, USA) with an incident photon energy of 1486.6 eV was used to analyze the sp 3 C volume content ratio in the coating. After testing, the nano-hardness of the golf club head in this embodiment is 16 GPa, and the volume content of sp 3 C in the coating is 49%. After the golf club head was rubbed 50,000 times with a load of 1100 g on a Tabler, the substrate was not exposed; after a 96-hour 5.5% NaCl neutral salt spray test, no rust spots were seen.

[0045] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

[0046] In addition, it should be understood that although this specification is described in accordance with the embodiments, not every embodiment only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating, comprising a golf club head substrate, characterized in that, The surface of the golf club head substrate is formed with a diamond-like carbon coating having a nano-hardness exceeding 15 GPa. The diamond-like carbon coating includes a transition layer and a hydrogenated carbon-based coating that are sequentially distributed from the inside out. The transition layer includes a metal layer covering the surface of the golf club head substrate and a metal / C composite layer in which carbon is gradiently distributed on the metal layer; the thickness of the hydrogenated carbon-based coating is 2.0 to 4.0 micrometers and the volume content of sp 3 C exceeds 45%, the thickness of the metal layer is 300 to 500 nm, the thickness of the metal / C composite layer is 200 to 400 nm, and the total thickness of the transition layer is 0.5 to 0.9 micrometers; The preparation method of a golf club head with a wear-resistant and corrosion-resistant diamond-like carbon coating comprises the following steps: S1. Pretreatment: ultrasonically clean the surface of the golf club head substrate and dry it with oil-free compressed air for standby; S2. Etching activation: place the golf club head substrate treated in step S1 in the vacuum chamber of a vacuum coating device. The pressure in the vacuum chamber is 0.05 - 0.15 Pa. There are 2 magnetron target cathodes and 4 ionization source electrodes installed in the vacuum chamber. Apply a pulsed bias voltage of -150 V to -250 V to the golf club head substrate, turn on the ion source, and use argon plasma to etch and activate the surface of the golf club head substrate. During this period, maintain the DC arc current at 60 - 100 A, and the etching activation time is 30 - 60 min. The surface temperature of the etched golf club head substrate reaches 83°C - 150°C; S3. Preparation of the transition layer: introduce argon into the vacuum chamber and maintain the pressure at 0.05 - 0.15 Pa. Then start the 2 magnetron target cathodes, adjust the power of the magnetron target cathodes to be maintained at 4 - 5 kW and deposit a metal layer with a thickness of 300 - 500 nm on the golf club head substrate. Then maintain the inflow of argon and linearly reduce the power of the magnetron target cathodes from 4 - 5 kW until 1 kW, and at the same time linearly increase the inflow of methane working gas until the pressure in the vacuum chamber reaches 1.0 - 2.0 Pa. Start the 2 ionization source electrodes, linearly adjust the power of the ionization source electrodes from 1.5 kW to 4.0 - 5.0 kW for magnetron sputtering, apply a pulsed bias voltage of -150 V to -250 V to the golf club head substrate to deposit a metal / C composite layer. When the thickness of the deposited metal / C composite layer reaches 200 - 400 nm, turn off the 2 magnetron target cathodes; S4. Preparation of hydrogen-containing carbon-based coating with high sp 3 C content: Maintain the flow rate of argon in step S3 and adjust the inflow rate of methane working gas to keep the pressure in the vacuum chamber at 1.3 - 2.0 Pa. Turn off the magnetron target cathode, and at the same time start the operation of 4 ionization source electrodes with a power adjusted to 4.0 - 5.0 kW. Apply a pulsed bias voltage of -300~-500 V to the golf ball head substrate and deposit for 40 - 60 min to prepare a hydrogen-containing carbon-based coating, thus obtaining a golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating; Among them, the surface of the ionization source electrode is covered with an a-C:H coating, the thickness of the a-C:H coating is ≥ 1 μm, and the surface resistance of the a-C:H coating is ≥ 1 MΩ; a closed magnetic field is formed in a ring perpendicular to the electrode axis on the surface of the ionization source electrode, and the magnetic field intensity of the closed magnetic field in the direction perpendicular to the electrode axis on the surface of the ionization source electrode is 4000 - 8000 gauss.

2. The golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to claim 1, characterized in that, The metal layer in the transition layer is any one of a titanium layer, a chromium layer, a tungsten layer, a titanium-aluminum alloy layer, or a chromium-aluminum alloy layer.

3. The golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to claim 1, wherein The material of the golf club head substrate is a soft metal material with a hardness lower than HRC50.

4. The golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to claim 3, wherein, The material of the golf club head substrate is an iron-based alloy or a titanium alloy.

5. The golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to claim 1, characterized in that, The materials of the magnetron target cathode and the ionization source electrode are metals or alloys.

6. The golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to claim 5, characterized in that, The materials of the magnetron target cathode and the ionization source electrode are selected from any one of titanium, chromium, tungsten, titanium-aluminum, and chromium-aluminum.

7. The golf ball head with a wear-resistant and corrosion-resistant diamond-like carbon coating according to claim 1, characterized in that, The materials of the magnetron target cathode and the ionization source electrode are tungsten carbide.

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