1. Introduction
Over the years, copper and its alloys have played a critical role in the industrial and metallurgical sectors since properties such as ductility and conductivity ensure extensive involvement in many fields [
1,
2], even under wear conditions [
3]. However, unsatisfactory mechanical properties such as hardness strength and wear resistance limit the application of copper and its alloys, especially under high-temperature operating conditions [
4,
5,
6]; hence, improving wear resistance to increase the service life of copper-based components is an urgent need [
3].
At present, surface treatment technologies such as thermal spraying, electroplating, laser cladding, magnetron co-sputtering, and plasma cladding are widely exploited to coat a protective layer on copper substrates and increase friction wear performance and service life [
6,
7,
8,
9,
10,
11,
12,
13,
14]. Copper-based nanocomposites produced through these methods have shown a growing trend in copper surface protection due to their improved mechanical properties, leaving the physical performance of both the substrate and the matrix unaffected, thus enhancing the wear resistance through improved lubricating capability [
15,
16,
17]. In fact, Cu composite coatings with reinforcing phases (such as ceramic or carbonaceous) benefit from both metals and fillers and demonstrate outstanding wear resistance and improved electrical and thermal conductivity and self-lubricating properties, which has led to themattracting increasing interest in industrial fields [
18,
19,
20,
21,
22].
Among all of the fillers, graphene is an ideal reinforcement due to its superior properties (mechanical, electrical/thermal, and lubricating properties) and relatively inexpensive production cost [
23,
24,
25]. Supposed state-of-the-art methods include powder metallurgy, vapour deposition, electro-spark deposition, laser cladding, and thermal spraying; however, those methods require high-temperature and high-pressure conditions [
26], and the layer produced is not free from defects such as low bonding strength between the coating and the corresponding substrate. Furthermore, vapour deposition methods are complicated to manage and require demanding and costly devices that can release toxic gaseous products [
27]. These critical aspects hinder the application of these strengthening methods in manufacturing Cu components for harsh service conditions; thus, a more cost-effective process of increasing copper surface performance needs to be identified [
28,
29].
Electrophoretic deposition (EPD) processes represent a valuable alternative to vapour phase deposition processes for nanostructured coatings and nanoscale films with enhanced properties [
30]. In Electrophoretic deposition (EPD) processes, charged colloidal particles are dispersed in a liquid medium to migrate, under the influence of an electric field, towards oppositely charged electrodes by applying a voltage [
31]. EPD is a versatile, fast, and cost-effective technique that isadjustable for specific applications due to its easy deposition rate and thickness control, which ensure coating uniformity. The advantages of EPD processes include fast deposition rates and a lack of restrictionsregarding the shape of deposition substrates, which makes the process effective in producing well-adhered coatings in a cost-effective and non-dangerous way using a simple and economical apparatus [
30,
32]. Also, the use of the aqueous system as the suspending medium requires lower voltages and costs, reducing the environmental impact compared to the hazardous organic liquids that are usually used [
31]. Several papers have investigated the utility of the EPD techniquefor producing graphene coatings for used on copper substrates, although the majority of these studiesdiscussed the use of the EPD technique in the context of corrosion prevention [
33,
34,
35,
36,
37,
38,
39,
40].
Surface textures have also been proven to lower the coefficient of friction (COF); however, it is gradually modified by plastic deformation, especially with high local contact pressures [
41,
42].
A combination of surface texturing and lubricants has been applied to improve wear behaviour; the geometry printed on the surface acted as lubricant reservoirs and pits to catch the debris produced during the dry sliding conditions [
43,
44,
45,
46,
47]. To the best of the authors’ knowledge, there is no work on using the EPD process and laser texturing to apply graphene over copper substrates; therefore, this work aims to fill this gap. Different types of texturing on copper substrates were developed as substrate treatments for the electrophoresis process.
Wear tests were carried out to determine the friction coefficient and the graphene coating’s durability and evaluate the laser treatment performance. The experimental results show low friction coefficients for all deposited films; however, the durability of the films was strongly influenced by the type of texturing that precedes deposition.
2. Materials and Methods
Samples of pure copper (99.9% wt.; 20 × 40 × 2 mm
3) were adopted as substrates for the EPD process. The study was divided into two steps: in the first step (pre-tests), to detect the most promising pretreatment technology, five different surface preparations were investigated (electropolishing, sandblasting, pickling and degreasing, laser cleaning, and laser dots).In the second step, based on the results of the first step, a full factorial plan was developed and tested. For the sandblasting treatment (SB), the sample was blasted with aluminium oxide at 4 bars for 30 s, removing the oxide and obtaining a clean, irregular surface, and this was carried out according to previous experience [
48]. The powder exploited was provided by Smyris Abrasivi S.r.l. (Pero, Mi, Italy)and characterised by a mesh of 16 with 1.2 µm average diameter and a shape factor of 0.67. The sandblasting treatment was performed at an angle of about 60° to the normal surface.
For the electropolishing (EP) pretreatment, the sample was electrochemically treated with the bath described in
Table 1.The substrate was attached to the anode of a current generator, and a potential difference of 10 V was applied, resulting in an oxide-free and highly polished surface, as previously obtained in the literature [
49,
50]. In the degreasing and pickling (DP) treatment, the sample was first subjected to electrochemical cathodic degreasing at 8 Ampere for 3 min and subsequently immersed in a commercial degreaser (Condorine 156, Condoroil Chemical S.r.l., Casale Litta, Italy). After being rinsed in water, the sample was then dipped into a commercial chemical degreaser (744P, CondoroilChemical) for 2 min and subsequently rinsed in water.The degreasing solution was purchased from Condoroil Chemical S.r.l.
The laser texturing treatment was performed by using a pulsed 30 Wfibre source (Yb:YAG) (model YLP-RA30-1-50-20-20 by IPG Photonics, Oxford, MA, USA) equipped with a galvanometric scanning head (supplied by LASIT SpA, Naples, Italy). The laser beam was moved via two galvanometric mirrors and focused by a flat lens (F-Theta by LINOS, Göttingen, Germany) 160 mm in focal length. The laser spot at the focusing point was about 80 μm. In
Table 2, the laser system characteristics are reported.
The system was controlled via a software programme that enables the management of the laser power (P), pulse frequency (F), number of repetitions (R), scanning speed (Ss), and scanning strategy. The average power can be changed by varying the power supply provided to the pumping diodes.
Figure 1 depicts a schematic of the laser treatment; the scanning direction and the hatch distance (Hd), i.e., the distance between two successive scanning lines, are highlighted. By changing the pulse frequency and the scanning speed, it is possible to change the pulse overlap, i.e., the distance between two consecutive laser footprints. The laser parameters were selected based on previous experience [
51,
52]. The values for the two laser treatments performed—laser cleaning (LC) and laser dots (LD)— are shown in
Table 3. It is worth noting that by adopting a high scanning speed (4300 mm/s), laser footprints were created without overlap.
For the electrophoretic deposition technique, the component was placed at the anode of a DC generator (PSW250-4.5, GW Instek, New Taipei City, Taiwan) while the cathode consisted of an AISI 304 stainless steel foil. For all samples, the deposition time was set at 10 min, after which the sample was rinsed in distilled water and dried with compressed air. For the factorial plan, three different voltages were chosen: 30, 45, and 60 V. The deposition bath used consisted of a 1 g/L dispersion of GNPs (ACS Material, Pasadena, USA, whose characteristics are reported in
Table 4) in distilled water. Prior to deposition, the bath was subjected to 10 min of sonication to facilitate the dispersion of the graphene using a Sonics Materials VCX 750 (Thermo Fisher Scientific Inc., Waltham, MA, USA) instrument.
In order to reduce the number of trial tests and to assess the effects of the treatments, a 3
2 full factorial plan was developed and tested. The control factors were the treatment type and the voltage adopted during electrophoretic deposition. The control factors and their levels are reported in
Table 5. As response variables, the following wear parameters were selected: the maximum depth (d [µm]) and maximum wear width (w [µm]) of the wear tracks, their combination (w × d [µm
2]), and the coating break distance (CBD). Coating failure was declared when the coating showed a 5% increase in COF from the average plateau value. CBD was computed as the distance in which the failure happened.
After being subjected to the different pretreatments, the morphological characterisation of the samples was performed by using a 3D Surface Profiling System (Talysurf CLI 2000, Taylor Hobson, Leicester, UK) to collect 3D maps and roughness profiles. The 3D map dimensions were 1 × 1 mm2,with a 1 µm resolution; the Arithmetical Mean Height of the scanned area (Sa) was also collected. The roughness of the treated samples was studied while considering the most important roughness parameters: Roughness Average (Ra) and Ten Point Height of Irregularities (Rz). For each sample, 30 profiles with 12.5 mm length, an interspace of 100 µm, and a resolution of 1 µm were collected. The profiles were then elaborated through the use of surface analysis software (Talymap Universal 3.1.4), which collected Ra and Rz using a 0.8 mm Gaussian Filter.
Tribological tests were carried out using a standard tribometer (CSM Instruments, Needham, MA, USA) in the ball-on-flat configuration with a half-amplitude of 2.5 mm and a maximum speed of 5 cm/s. The tests were carried out with a normal load of 1 N using a 100Cr6 steel ball with a diameter of 6 mm. The test distance was set at 100 m. Three different samples were produced and tested for each condition to ensure the repeatability of the process.
For the samples that did not exhibit coating failure during the test, an additional 500 m test was conducted to evaluate the CBD. The maximum depth, d [µm], and the maximum wear width, w [µm], were measured via the use of a 3D digital video microscopy system (KH-8700 by Hirox, Hackensack, NJ, USA) using the MXG-2500 REZ “revolver” optics with 350× magnification and adopting the “3D tiling” function. This function allows for the system to move along 3 axes, acquiring the surface. Then, after the surface is rebuilt, the function is able to measure the profiles extracted by the 3D surface.
Figure 2 depicts a schematic of wear track measurement; wear depth and the width of the tracks were calculated by extracting the profile in the middle of the tracks.
The effect of the control factors (i.e., treatment type and deposition voltage) on wear behaviour was evaluated via ANOVA. For the test, Minitab R18 software was used. The analysis was conducted at a confidence level of 95%, i.e., a control factor or a combination of more control factors is statistically significant if the p-value is less than 0.05. Before the analysis, our hypotheses were checked by graphically analysing the residues. The main effect plots were adopted to show the effect of a control factor on the response variables. In addition, in order to detect the effectsattributable to a combination of multiple control factors, interaction plots were generated.
4. Conclusions
This article presented an analysis of different types of surface preparation treatments on copper substrates, investigating how these affect the deposition of graphene by electrophoresis as a function of the applied process potential. Preliminary analyses have shown that the excessively smooth substrates and highly rough surfaces typical of electropolished and sandblasted samples, respectively, are not conducive to graphene film creation. In fact, although all deposits present a similar coefficient of friction (close to about 0.1), they exhibit a very low CBD.
For the laser and degreasing and pickling treatments, the influence on the electrophoretic process was evaluated, and we also investigated how the potential varies the deposition. A larger dot size favours the adhesion of graphene, which acts as a lubricant reservoir during sliding. However, due to the more pronounced depressions, the process is more sensitive to the applied potential due to the Faraday Cage effect. In general, the lower the roughness of the sample, the lower the sensitivity of the process to this factor, as demonstrated by ANOVA.