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Progress in Organic Coatings 67 (2010) 209219

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Progress in Organic Coatings


journal homepage: www.elsevier.com/locate/porgcoat

Scratch and wear resistance of transparent topcoats on carbon laminates


M. Barletta a, , D. Bellisario b , G. Rubino a , N. Ucciardello a
a b

Universit degli Studi di Roma Tor Vergata, Dipartimento di Ingegneria Meccanica, Via del Politecnico, 1 - 00133 Roma, Italy Universit degli Studi di Roma La Sapienza, Dipartimento di Meccanica e Aeronautica, Via Eudossiana, 18 - 00184 Roma, Italy

a r t i c l e

i n f o

a b s t r a c t
The present investigation deals with the application of low-curable powder paints on epoxycarbon laminates. Carbon laminates were rst peened to corrugate their surface, hence increasing the wettability and allowing a better adhesion of the overlying coatings. Powder coatings were then electrostatically sprayed onto peened and unpeened substrates and baked into a convection oven. Their aesthetic and tribological performance was comparatively evaluated. Powder coated peened carbon laminates exhibited good adhesion and visual appearance as well as noteworthy scratch resistance and tribological performance. 2009 Elsevier B.V. All rights reserved.

Article history: Received 30 June 2009 Received in revised form 17 September 2009 Accepted 8 October 2009 Keywords: Powder paints Epoxycarbon laminates Scratch Wear

1. Introduction Carbon laminates are literally spreading in aeronautic and aerospace applications, in manufacturing of high performance components for cars and motorcycles, in assembling of high added values items, in electronic and medical devices, in sport and tness equipments as well as in all those market shares in which the technological challenge and the exclusivity of the design receive much attention [1,2]. Finishing has always been one of the major concerns for carbon laminates manufacturers and painters [2]. Nowadays, aesthetic and protective nishing is often provided by wet paints (mostly, solventborne [3]), which allow good visual appearance and mechanical properties with a simple deposition process and a spontaneous drying [3]. Increasing environmental concerns and the even more stringent regulations are, however, limiting the emission of volatile organic compounds during the nishing processes, thus demanding alternative technologies, which make use of dry painting formulations [3,4]. Powder coating is a well-known viable and eco-friendly alternative to wet painting [5]. Yet, the applications of powder coatings are generally restricted by several drawbacks as poor levelling, reduced adhesion, high baking temperature and difcult-to-deposit procedure onto complex geometry, heat sensitive and/or electrical insulating substrates [58]. Accordingly, carbon laminates can be extremely difcult to powder coat [9].

Corresponding author. E-mail address: barletta@ing.uniroma2.it (M. Barletta). 0300-9440/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.porgcoat.2009.10.015

They are semi-conductive materials, in which an electrically conductive carbon bre is dispersed inside a non-conductive epoxy matrix with limited wettability to molten painting polymers. Such issues denitely complicate the deposition process, as powder coatings involve the usage of powder paints which must be electrostatically sprayed onto the substrate and, then, oven-baked to allow their melting, levelling and curing. This process requires, at least, a uniformly semi-conductive material characterized by a relatively wettable surface to the molten polymer powders [5,9]. Furthermore, depending on the way in which the carbon laminate is manufactured, it could be more or less heat sensitive [2]. This would push towards an application method requiring a baking procedure at relatively low temperature and, in any case, at temperature well below the 170 C mostly used for the customary applications of the powder coatings [5]. Lastly, carbon laminates are susceptible to the release of a not negligible amount of volatile compounds (i.e., degassing) when baked at moderate or high temperature (>115 C) [9]. If the gas release takes place during the curing process of an overlaying coating, the volatile compound emitted from the bulk of the carbon laminates can remain trapped inside the lm, thus giving rise to the formation of unaesthetic, porous and brittle topcoats [9]. The basic idea should be to preventively treat the surface of the carbon laminates in order to promote the wettability of the surface, induce a corrugated morphology on it and facilitate the rapid release of the volatile compounds during the baking. This is, therefore, the context in which the present work investigates the effect of pre-treating the carbon laminates by a peening process with glass beads to improve the visual appearance, adhesion strength and wear resistance of the overlying organic coatings. In this respect,

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transparent polyester-based powder coatings were rst electrostatically sprayed onto peened and unpeened substrates and then baked at moderate temperature in a convection oven. Their visual appearance, scratch resistance and tribological performance were comparatively evaluated. The experimental ndings revealed that peened and subsequently powder coated carbon laminates exhibit good adhesion, good visual appearance as well as noteworthy scratch resistance and wear response.

2. Experimental Commercially available 2040 mm 1050 mm 1.1 mm carbon laminates were supplied by Carbon-Composite Technology (Waldstetten, Germany). They consist in a standard laminate structure composed of continuous 3K carbon fabric (205245 g/m2 in plain) with a bre alignment bidirectional (50% at 0 and 50% at 90 ). The matrix is epoxy-based with a Tg of 170 C. Custom size cuts were performed by abrasive water jet up to the nal dimension of 6 mm 4 mm. Pre-treatments of the carbon laminates prior to the deposition process were scheduled as follows: (i) peening with glass beads [3]; (ii) cleaning of the carbon laminates by powerwashing and rinsing; (iii) overnight drying and stabilization in convection oven at moderate temperature (60 C). Peening of the as-received carbon laminates was performed by an abrasive jet of glass beads [10]. In this process, the carbon laminates enter the space into which nearly spherical glass particles (factor shape 0.95) with average diameters in the range of 100800 m are injected by means of an air stream issued at moderate or high pressure (4, 6 and 8 bar) and varying operating time (1, 2 and 3 min). Powder particles impacting the carbon laminates release their kinetic energy and are supposed to cause manifold effects: (i) the micro-grooving of the softer epoxy matrix; (ii) the selective removal of the surface contaminants; (iii) a stress-release action benecial to relax the carbon laminates residual stresses. Peening was followed by the cleaning processes, which can remove the residuals of the impacts between the glass beads and the carbon laminates as well as some occasional organic contaminants whose presence could compromise the performance of the whole coating process. Finally, the oven-drying and stabilization process allows the further release of the internal stresses of the pre-treated carbon laminates and the evacuation of most of the volatile organic compounds still retained inside the bulk of the material. The 3D morphology of the carbon laminates before and after peening was measured by using a Taylor Hobson Surface Topography System (TalySurf CLI 2000, Taylor Hobson, Leicester, UK) with the non-contact 300 m Chromatic Aberration Length (CLA) HE gauge. The absence of contact between the gauge and the coating was chosen to prevent any damage to the surface being measured. 200 proles (step 100 m) 20 mm long were recorded for each sample to cover a wide enough area (400 mm2 ) of the entire surface structure. TalyMap software Release 3.1 was then used for analytical examination of the experimental data. Standard amplitude, spacing and hybrid roughness parameters (Gaussian lter) were considered to depict the surface morphology of the carbon laminates. Upon pre-treatments, the carbon laminates were electrostatically sprayed (ESD PC15, Siver Srl, Terni, Italy) with low-curable outdoor resistant polyester-based transparent painting powders (20 m average diameter, 0.80 factor shape, PPG Industries, Bellaria, Italy). Applied voltage, feeding pressure and auxiliary pressure were set at 90 kV, 1.5 bar and 1.0 bar, respectively. Deposition time was set at 6 s. After the deposition, the coated carbon laminates were submitted to the curing process in a convection oven (Naddeo RT11, Naddeo Engineering, Scafati, Italy) at 135 C for 20 min. Coating thickness of about 120 m (ISO 2178 and ISO 2370) could

be achieved with an error of 10%. All the coatings failing to agree with this specication were disregarded. The surface roughness of the coated carbon laminates were measured using a contact probe surface proler (TalySurf CLI 2000, Taylor Hobson, Leicester, UK). Optical (DM IRM, Leika) and stereoscopic microscopy (SMZ-1500, Nikon) were used to catch high resolution images of the surface morphology after the coating process. The adhesion strength of the coatings were analyzed by scratch tests (Micro-Combi Tester, C.S.M. Instruments, Peseaux, Switzerland) equipped with a Rockwell C-type conical indenter (800 m tip radius), and operating in progressive mode (track 3 mm, scratch speed 1 mm/min, load 100 mN30 N) at about 20 C and 40% RH. SEM (SEM Leo Supra 35, Oberkochen, Germany) was used to observe the residual scratch patterns, which were rebuilt using the contact probe surface proler with 2 m lateral resolution. Calculated features of the 3D scratch patterns were the volume of the plastic pile-up formations, VPILE and the scratch ditch, VDITCH [11]. Tribological tests with alternative dry-sliding motion were performed by a standard tribometer (Linear Reciprocating Tribometer, C.S.M. Instruments, Peseaux, Switzerland) at about 20 C and 40% RH. Samples were tested at 3 N load and back-and-forth sliding (stroke length 10 mm, frequency 5 Hz, duration 20, 50, 100, 500 and 2000 s) of the upper SAE52100 steel ball (6 mm diameter). Wear rate of the coatings was assessed by contact probe surface proler, measuring the area involved by the action of the antagonist, the wear volume and the minimum and maximum height of the wear pattern.

3. Results and discussion 3.1. Analysis of the peening process Peening by glass beads was found to be successful in pre-treating the carbon laminates and to make them ready for the painting process. The carbon laminates are exposed to the repeated impacts of glass beads, which, moving at relatively high pressure, can impinge on the substrate and release their kinetic energy. The impacts can modify the surface morphology of the carbon laminates and establish a micro-corrugated topography as already shown by Barletta and Gisario in a previous study on similar substrates [9]. Fig. 1 shows the trends of the amplitude, spacing and hybrid roughness parameters before and after the peening process. Increasing the peening pressure and the exposure time, the surface of the carbon laminates becomes progressively rougher. Average roughness Ra and ISO 10 points height Rz can approach high values as 0.5 m and 5 m, respectively, which are, at least, one order of magnitude more than the corresponding values of the untreated substrates. Corrugation of the surface morphology after peening process is also stated by the increase in the modulus of spacing and hybrid roughness parameters. In particular, skewness Rsk tends to assume negative values. This means that the surface proles become even more anti-symmetrical around the mean line and this is more likely ascribable to the random impacts of the glass beads onto the softer polymer matrix of the carbon laminates. Similarly, Kurtosis Rku increases, thus supporting the basic idea of a rougher and widely micro-grooved morphology being established after the peening process. Peening of the carbon laminates by glass beads at lower pressure or for shorter time was not accounted for as it would lead to irrelevant modication of the substrate morphology. At the same time, peening of the carbon laminates at higher pressure or for longer time were excluded as it would lead to over-peening phenomena. Under such circumstances, the structure of the composite material would be damaged and some local delamination phenomena could occur, thus compromising the overall performance of the laminates.

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Fig. 1. Evolution of carbon laminates morphology vs. peening process parameters.

A typical consequence of the over-peening is the removal of some bres bundles from the polymeric matrix [9], which is extremely detrimental to the visual appearance and functional properties of the composite material. Average roughness of the coated carbon laminates were measured on both unpeened and peened substrates and, whatever the peening parameters, average roughness Ra of 0.05 m was found. Once heated, the polymer powders melt, their viscosity drops down and, accordingly, they were able to level and ll the cavities which can characterize the morphology of the peened samples, particularly those peened under the severest conditions. In any case, a smooth surface nishing is established and, in this respect, the starting morphology of the underlying substrates is irrelevant. Therefore, the build-up of a good surface structure and, consequently, a good visual appearance can also be achieved by polyester coatings deposited onto rougher substrates.

residual depth trend shows rst small jumbling at a normal force of 7.5 N (the rst small saddle) and, again, a bigger jumbling event at 1011 N (the second saddle). The jumbling events could be explained as the result of a sort of stick-slip motion occurring during the scratch test of the coating material. Therefore, the scratching process evolves by recurring jerks instead of a smooth path as observed by Zhang and Valentine for scratching of bulk PMMA [12]. Yet, Zhang et al. observed how in the bulk PMMA the time of the

3.2. Scratch response of polyester coatings onto unpeened carbon laminates Micro-grooving of the carbon laminates is extremely helpful in improving the scratch and wear resistance of the overlying organic topcoats. In Fig. 2, the residual deformation response after scratch (i.e., depth of the residual scratch pattern) is comparatively evaluated for peened and unpeened substrates. Unpeened substrates show a rapid increase in the depth of the residual scratch pattern with the increase in the applied load (i.e., evaluation length). The

Fig. 2. Residual depth vs. normal force with the peening process parameters.

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Fig. 3. Residual stress distribution during the loaded scan of a progressive mode scratch test of a ductile coating material.

stick (tens of seconds, normal load and driving speed dependent) was much longer then the characteristic time of the slip (less then a second), while in carbon laminates the presumable stick and slip phases last more or less the same time as shown in Fig. 2. An alternative hypothesis to explain the recurrent jumbling of the scratching geometry along the scratch pattern was therefore formulated. The jumbling could be explained in the light of the peculiar stress distribution involved during the progressive mode scratch test of a ductile coating material (Fig. 3) [13]. In an early study, Jardret et al. found that when an indenter advances along the scratch pattern, a compression zone is created inside the outermost layers of the coating as a result of some ductile material accumulating ahead. A tensile zone is, of course, developed behind the indenter. Therefore, the decreasing branch of the jumbling, which takes place at about 7.5 N normal load during the scratch test of the polyester coating onto the unpeened carbon laminate, is due to the indenter overtaking the material accumulated in front of it. The saddle corresponds to the point in which the indenter reaches the peak of the ductile coating material accumulated in front of the advancing scratch geometry. The increasing branch which follows the saddle is ascribable to the indenter descending along the material formerly accumulated in front of it. The jumbling event occurring at higher load (1011 N) is even more pronounced, as the phenomena involved are emphasized by the larger stresses involved inside the coating material. Therefore, the saddle is deeper and, accordingly, the increasing and decreasing branch around it are steeper. The onset of delamination for the ductile coating material onto the unpeened carbon laminates took place at about 13 N normal load, which means earlier than the half of the residual scratch pattern. The measured residual depth averages 100115 m, that is, more or less the prescribed thickness of the polyester coating (120 m 10%). The delamination is, however, well perceivable in Fig. 4, where a SEM image is reported. The rst part (1 mm long) of the scratch pattern is still visible. Then, the coating appears to be completely failed and, moreover, the adhesion seems to be very poor at the interface with the underlying carbon laminates. Beyond the rupture of the coating, a severe delamination occurring around the scratch pattern and propagating in the surrounding zone can be observed. The coating is mostly delaminated ahead of the scheduled scratch pattern. This means that the coating fails according to the mechanism of spallation in agreement with what reported by Bull for ductile materials [14]. Such a large area of delamination is common when the coating is poorly adhered onto the substrate and/or when it is extremely stressed. Under such circumstance, when the indenter penetrates the coating with a sufciently high load, a through-thickness crack could nucleate and propagate at the interface between the coating and the substrate. The crack would propagate a considerable distance over the tracking before coming to a halt, thus causing a larger zone of coating being involved in the delamination.

The interpretation of the coating failure in the light of the aforementioned mechanism could be reliable. However, the jumbling in the residual depth trend in Fig. 2, typically associated to the presence of massive compressive stresses ahead of the advancing stylus during the scratch test procedure, leaves a certain uncertainty. In fact, the delamination of the coating by spallation mechanism could be alternatively ascribed to the development of such a peculiar residual stress distribution (Fig. 3). In this case, the delamination would take place in the attempt to minimize the extent of the elastic energy stored inside the coating material by the large compressive stresses formed in front of the moving indenter. Yet, discerning which one of the proposed mechanisms is the more reliable is, however, still a too much complicated task. At the end of the prescribed scratch pattern of the polyester coating deposited onto the unpeened carbon laminates, it is also possible to note a severe damage onto the substrate itself (Fig. 4). This is due to the fact that the coating delaminates rather soon (that means, at low loads) under the action of the penetrating indenter, hence leaving the unprotected substrate directly exposed to the scratching geometry. This results in a scratch scar which is formed on the surface of the carbon laminate. It is extremely difcult from the SEM image in Fig. 4 to extract the actual nucleation point of the crack along the scratch pattern. In fact, the nucleation is seldom associated to the rst point along the scratch pattern whereas the coating delaminates. As said before, cracks can propagate either side the scheduled scratch scan and, therefore, delamination can involve also zones well behind the actual nucleation point of the crack. The actual location where the onset of the delamination phenomena takes place is more reliably evaluable by the examination of the friction coefcient. Fig. 5 reports the trend of the friction coefcient during the progressive mode scratch test. As concerns the unpeened samples, a massive fracture event takes place at as early as 1011 N normal load, that means, after 1 mm of the prescribed scratch pattern and that event can be strictly correlated to the delamination of the whole coating system. In fact, the sudden decrease in the friction coefcient is due to the coating collapse, which, once failed, is not able to withstand the action of the advancing indenter. Accordingly, the tangential force goes down as the friction coefcient does. These results agree with what found by Barletta et al. in earlier studies on polyester and epoxypolyester powder coatings cured under different time and temperature programs [15,16]. They found full failure for some undercured coatings, whereas they measured a steep decrease in the tangential force (i.e., that means, also in the friction coefcient).

Fig. 4. SEM image of the residual scratch pattern of the polyester coating onto an unpeened carbon laminate.

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Fig. 5. Friction coefcient vs. normal force with the peening process parameters.

3.3. Scratch response of polyester coatings onto peened carbon laminates The polyester coatings deposited onto the peened substrates show a denitely better scratch response whatever the settings of the peening parameters. Peened substrates do exhibit smaller residual scratch patterns if compared with the unpeened one (Fig. 2), whatever the choice of the peening parameters (time and pressure). The maximum residual depths of 4550 m conrm the coatings remain well adhered to the underlying substrates after the scratch tests. The residual depth trends run very regular, that is, according to a very smooth pattern, at low scratch load. First jumbling events take place at 15 N (sample peened at 6 bar for 1 min) and the phenomena intensify at higher load (1820 N), where even the samples exhibiting the smaller residual depths must face some irregularities along their pattern. The better scratch behaviour of the polyester coating onto the peened carbon laminates can be ascribable to the corrugated surface morphology produced on them by the peening process. The micro-grooving of the softer epoxy matrix generates a longer interface between the substrate and the overlying coating which promotes their adhesion [9,17]. Moreover, the peak-to-valley topography physically opposes to the lateral propagation of the surface cracks generated by the action of the scratching indenter inside the outermost layer of the coating material [18]. The peening process also allows the selective removal of the organic contaminants from the surface of the carbon laminates, thus improving their surface wettability and, consequently, the adhesion on them of the overlying organic coatings [10,17]. Finally, the peening process causes a stress-release action benecial to relax the carbon laminates residual stresses [9]. This way, when the coatings are submitted to the scratching procedure, the stresses eld generated by the indenter inside the outermost layer of the material is not superimposed to those already insisting on a highly stressed substrates and this could be benecial to the overall scratching behaviour. However, it is not possible to establish a ranking among the samples peened under different peening time and pressure. For example, the carbon laminate peened at 4 bar for 1 min (i.e., the softer peening program) shows the higher residual depth trend, which potentially means the worse scratch behaviour. Nonetheless, its residual scratch pattern is one of the smoothest with few jumbling events occurring up to 25 N scratch load (Fig. 2). The samples peened under more energetic conditions exhibit less deep residual scratch pattern but some jumbling can occur at lower normal loads (Fig. 2).

Fig. 6. SEM image of the residual scratch pattern of the polyester coating onto a peened carbon laminate (8 bar for 1 min): (a) the whole scratch pattern; (b) zoom of the residual scratch pattern at high scratch load.

The trend of friction coefcient in Fig. 5 is helpful in supporting the interpretation of the leading mechanism involved in the scratching of polyester coatings onto peened carbon laminates. The friction force tends to increase rst as a result of the rapid increase in the penetration depth during the rst moment of the scratch test. Then, the friction force tends to stabilize with a slight decreasing branch. The onset of jumbling takes place at 15 N or little more for the most part of the investigated samples and the agreement with the residual depth data is very good. In fact, the coating exhibiting

Fig. 7. 3D deformation response (ditch and pile-up volume) vs. peening parameters.

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Fig. 8. Wear tracks on polyester powder coatings: (a) unpeened carbon laminates; (b) peened (8 bar for 1 min) carbon laminates.

fewer jumbling events is that deposited onto the under-peened 4 bar for 1 min carbon laminate, as before stated by the examination of its smooth residual depth trend. The analysis of the typical scratch track of a polyester coating onto a peened carbon laminate (peening pressure 8 bar, peening time 1 min) is reported in Fig. 6. The SEM image does not reveal massive delamination phenomena, but only minor damages mostly located at the bottom of the scratch pattern and along its sides.

The scratch behaviour of the polyester coatings is nearly the same whatever the settings of the peening parameters. All the coatings deposited onto the peened substrates did not fail. Yet, they showed large groove formations after scratch. This means that, during the scratching procedure, the load is essentially applied to the advancing half front of the indenter, thus determining a signicant increase in the actual stress induced in the coating material located ahead. This phenomenon also takes to a reduced loading condition

Table 1 Wear rate of the peened (8 bar for 1 min) and unpeened samples. Sample Unpeened 1 m Unpeened 2.5 m Unpeened 5 m Unpeened 25 m Unpeened 50 m Unpeened 100 m Peened 1 m Peened 2.5 m Peened 5 m Peened 25 m Peened 50 m Peened 100 m Worn surface (mm2 ) 2.37 3.1 3.21 4.22 4.64 5.13 0.507 2.32 2.97 4.11 4.26 4.83 Worn volume (mm3 ) 0.00812 0.0175 0.0192 0.0361 0.0442 0.0558 5.4E4 0.00706 0.0154 0.0324 0.0344 0.0476 Maximum height of the wear pattern ( m) 14.3 16.8 15.4 20.3 23.2 26.2 8.44 12.8 18.5 19.1 20.3 23.5 Minimum height of the wear pattern ( m) 3.42 5.65 5.97 8.54 9.53 10.9 1.07 3.04 5.23 7.89 8.08 9.86

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at the rear of the indenter (i.e., at the back half of the indenter). Accordingly, the coating material ahead of the advancing indenter tends to signicantly deform and a pile-up of material is generated as conrmed by the SEM image (Fig. 6b) and in agreement with the mechanism early proposed (Fig. 3). The formation of the plastic pile-up further increases the stress induced into the ductile coating material. In addition, the contact condition between the advancing indenter and the coating generates a radial tensile stress which is presumably the highest at the sides of the indenter. Such stress is further corroborated by a tensile stress developed at the rear of the contact, that is, whereas the indenter is nearly separated from the deformed material. Tensile stress will thus occur initially at the sides of the indenter, thus generating cracks located at the track edge and nearly parallel to the scratch direction (Fig. 6a). Partial ring cracks are generated ahead of the indenter, which, passing over them, tend to push the cracks generated deep into the track. Cracking of the coatings can also be supplemented by its bending into the scratch track as a result of the advancing and deep penetrating indenter. The sum of these failures lead to potentially

through-thickness conformal cracking at the front and sides of the indenter (Fig. 6b). Cracking also occurs at the rear of the contact between the indenter and the coating surface due to the tensile stresses (Fig. 6b). Together with the conformal cracking, the tensile cracking is by far the much contributing mechanism to the visible damage produced in the bottom of the scratch track of the polyester coating onto the peened carbon laminates. 3.4. 3D deformation response of polyester coatings onto carbon laminates Fig. 7 reports the 3D deformation response and, in particular, the ditch and pile-up volume trends according to the peening parameters. No data are available for the polyester coating onto the unpeened carbon laminates, as it catastrophically fails (Fig. 4) and does not allow the measurement of the 3D features of the residual scratch pattern. All the coatings deposited onto the peened samples did not fail and thus allowed the measurements of the ditch and pile-up volume. Yet, it is extremely difcult to establish a ranking

Fig. 9. The appearance of rst cracks during the wear test of the polyester coatings onto the carbon laminates: (a, c and e) unpeened 1 m sliding distance; (b, d and f) peened (8 bar for 1 min) 1 m sliding distance.

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Fig. 10. Wear pattern: (a) unpeened 100 m sliding distance; (b) peened (8 bar for 1 min) 100 m sliding distance; (c) unpeened 25 m sliding distance; (d) peened (8 bar for 1 min) 25 m sliding distance; (e) unpeened 5 m sliding distance; (f) peened (8 bar for 1 min) 5 m sliding distance; (g) unpeened 2.5 m sliding distance; (h) peened (8 bar for 1 min) 2.5 m sliding distance; (i) unpeened 1 m sliding distance; (j) peened (8 bar for 1 min) 1 m sliding distance.

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between the samples peened under the different conditions. The sample peened at 8 bar for 1 min exhibits the best behaviour with a moderate pile-up volume and, above all, with the lowest ditch volume. A slight worsening in the 3D response is observed if, keeping the peening pressure at 8 bar, the samples peened for longer are looked into. This result should be related to a sort of over-peening which could be detrimental to the nal behaviour of the polyester powder coatings. Peening at 6 and 4 bar takes to worse 3D deformation response, with mostly larger pile-up and ditch volume. In particular, the worst behaviour is exhibited by the under-peened 4 bar for 1 min carbon laminate. Under that circumstance, the substrate surface is poorly corrugated and the peening is not so helpful in improving the adhesion between the coating and the underlying carbon laminate. However, no massive failure phenomena or delamination occur, thus revealing, once more, the reliability of the peening process as pre-treatment technique for improving the adhesion between the carbon laminate and the overlying powder coatings. Carbon laminates peened at 6 bar and for any peening time shows intermediate behaviour, with pile-up and ditch volume of intermediate extent. The aforementioned results push towards the denition of three different classes of samples: (i) the under-peened (i.e., those peened at 4 bar for 1 min) or fairly peened samples (those peened at 6 bar for any time and at 4 bar for 2 and 3 min), which do exhibit very high or average pile-up and ditch volume, respectively; (ii) the properly peened samples (i.e., those peened at 8 bar for 1 min), which do exhibit the minimum values of pile-up and ditch volume among the investigated ones; (iii) lastly, the over-peened samples (i.e., those peened at 8 bar for 2 and 3 min), which do exhibit slight larger pileup and ditch volume, despite the more energetic peening process. 3.5. Wear response of polyester coatings on carbon laminates Wear response of the polyester coating onto unpeened carbon laminates was compared with the coating deposited onto the carbon laminates peened at 8 bar for 1 min, even if all the coatings deposited onto the peened samples tend to behave the same way whatever the choice of the peening parameters. Wear rate was affected by the pre-treatments of the carbon laminates, with the coatings onto the peened substrates being worn out slowly than the coatings onto the unpeened substrates. Fig. 8a and b shows a stereoscopic image of the wear tracks on the polyester coatings deposited onto the unpeened and peened (8 bar for 1 min) carbon laminates, respectively. Table 1 summarizes the results of the wear test. After 1 m sliding distance, the wear parameters in Table 1 and the SEM images at varying magnication (Fig. 9) show how the peened samples behave denitely better than the unpeened one. In fact, its worn volume is less than one order of magnitude smaller. Even the extent of the worn surface as clearly visible also from the SEM image (particularly, in Fig. 9c and d) and the minimum and maximum height of the wear pattern are denitely smaller for the coatings deposited onto the peened substrate. These results could be quite surprising as wear in thick coating is generally related to the material properties and less to the way in which the overlying coating material and the substrate interact. Yet, the slower wear phenomena which characterize the coating onto the peened substrate can be more likely ascribed to the different way the stresses inside the coating material are distributed during the wear tests. As said before, when the antagonist (i.e., the steel ball in the wear test) acts onto the surface of a ductile coating, the material is submitted to a very peculiar stress distribution (Fig. 3). This is what probably happens during the wear test of the polyester coating onto the carbon laminates. Such a stress distribution could cause the birth of rst cracks in very short time, as SEM images in Fig. 9e and f show. The propagation of the cracks is therefore accelerated or not depending on the substrate characteristic [9].

Fig. 11. SEM images of the wear pattern after (a) 1 m sliding distance and (b) 100 m sliding distance.

Peened samples present a highly corrugated surface. As said before, the resulting peak-to-valley topography and the larger interfacial area between the substrate and the overlying polyester coating are certainly helpful in withstanding the action of the antagonist to spread and propagate the surface cracks, thus slowing the wear phenomena. To the contrary, a smoother interface between the carbon laminates and the coating is detrimental to the wear response. In fact, there is no opposition to the cracks propagation, which can freely spread over the coating and determine faster wear phenomena. However, the difference in wear behaviour between the coatings deposited onto the peened and unpeened samples tends to decrease by increasing the sliding distance (Table 1 and Fig. 10). In fact, once the cracks due to the action of the antagonist are spread over the coating surface and propagated, the counteraction of a rougher interface between the coating and substrate tend to become even more limited. At higher sliding distance, the difference between the wear volume of the coatings onto peened and unpeened substrates is still appreciable but it averages a mere 1022%. Despite the different kinetic by which the wear track is formed and developed on the polyester coatings deposited onto the peened and unpeened substrates, the mechanism of material removal is basically the same, as SEM images in Fig. 11 conrm. Fractures of the outermost layers of material are provoked by the action of the antagonist during the initial stage of the wear test. By other side, this is the moment in which the pressure applied by the antagonist is the highest as it is concentrated around its tip and, therefore, acts on a restricted portion of coating. The high specic load insist-

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Fig. 12. CLA prolometry of the wear pattern after (a) 1 m sliding distance, (b) 2.5 m sliding distance, (c) 5 m sliding, (d) 25 m sliding distance, (e) 50 m sliding distance and (f) 100 m sliding distance.

ing onto the surface of polyester coating generates a severe stress distribution inside the material according to the model reported in Fig. 3 and provokes a quick and widespread fracturing of the outermost layers of the coating (Fig. 11a). The coating material is therefore torn off as result of the interaction with the antagonist. The residual wear track shows minimum material deformation after the release of the load and, accordingly, minimum is the displacement of coating material sideways. Such fractures progressively spread over the surface until some material is detached from the coating, thus forming debris still perceptible around the wear track (Fig. 10). Increasing the sliding distance, the antagonist tends to deeply penetrate inside the coating and, accordingly, the pressure it is able to apply progressively decreases. The resulting wear track changes its physiognomy (Fig. 11b). The wear track becomes more spread over the coating surface and two different zones can be distinguished: (i) the zone in the bottom of the wear track where the fracturing phenomena are still perceptible; (ii) the outer zone, where fracturing phenomena does not occur. In the latter zone, it is possible to note a remarkable residual deformation of the coating after the release of the load with sort of stripes marking the surface and running parallel to the edge of the wear track. Some coating material is displaced sideways along the border of the wear track. Furthermore, fracturing in the bottom of the wear track is less apparent. The change in contact condition from a more concentrated load during the initial stage of the wear test to a more dispersed one during the nal stage seems to cause a corresponding change in the response of the coating material to the antagonist. There is a sort of transition from a brittle-like to a ductile-like response which was often reported in the pertinent literature [11,15]. 3D analysis of the wear tracks supports the previous considerations (Fig. 12). The transition to a ductile-like response of the polyester coating, when higher sliding distances (5 m) are approached, is conrmed by the typical jumbling of the wear pattern (Fig. 12cf). The jumbling events are even more apparent going towards higher sliding distance during the wear test. They start to be perceptible after 5 m sliding distance (Fig. 12c) and, then, they progressively increase (Fig. 12df). The formation of such jum-

bling was previously found during scratch test at moderate or high load and the phenomenon was ascribed to the typical stick-slip behaviour of some ductile bulk polymers (like PMMA [12]) or, alternatively, to the peculiar stress distribution affecting most of ductile coating material under progressive load scratch test [13,15]. As said before, it is difcult to discern between the two mechanisms and establish which one is the most active one. Yet, both mechanisms are those typical of ductile polymeric materials. Therefore, wear response of the polyester coatings after higher sliding distances is typical of a ductile material, while during the rst stage of the wear test, only fracturing phenomena and brittle removal of material without signicant deformation was clearly observed (Fig. 11a). This supports the hypothesis of a brittle to ductile transition of the polyester coating response to the antagonist by simply increasing the sliding distance during the wear test and, thus, changing the corresponding contact conditions between the antagonist itself and the surface being investigated. Lastly, even after 100 m sliding distance, the coating keeps on being adhered onto the underlying substrates, without the occurrence of noticeable delamination phenomena (Figs. 11b and 12f), thus showing the overall good wear response of the polyester powder coatings onto carbon laminates whatever their starting surface conditions. 4. Conclusions The deposition of environmentally friendly transparent polyester powder nishing onto carbon laminates with particular emphasis on the effect of the substrate pre-treatments onto the scratch and wear response of the overlying coating was the matter of the present investigation. The experimental evidences lead to the following conclusions: The micro-grooved morphology after peening is very promising for promoting a good adhesion between the electrostatically sprayed coatings and the carbon laminates.

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The morphology of the carbon laminates is a function of the peening pressure and time. If they increase, a rougher morphology is reached. Scratch response of the topcoats onto peened and unpeened carbon laminates is different, with the former warranting the best performance as results of the better adhesion strength between the lm and the underling rougher substrates. It is extremely difcult to establish a ranking among the polyester coatings deposited onto the peened carbon laminates using different parameters. Yet, the analysis of 3D deformation response of the coatings allows the denition of three different classes: (i) the under-peened exhibiting the worst scratch response; (ii) the properly peened samples, exhibiting the best scratch response; (iii) the over-peened samples, exhibiting a scratch response worse than the properly peened, despite the more energetic peening process. Wear response of the polyester coating on peened carbon laminates are better, with the largest difference arising at low sliding distance whereas the corrugated surface morphology opposes better to the action of the antagonist. At higher sliding distance, wear of polyester coating onto peened and unpeened carbon laminates are very similar, with wear volume differences averaging 1020%. The change in contact condition from a more concentrated load during the initial stage of the wear test to a more dispersed one during the nal stage is supposed to cause a corresponding change in the response of the coating material to the antagonist, with a transition from a brittle-like to a ductile-like response arising. No delamination was found to affect the polyester coating during the wear test, even after longer sliding distance. References
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