Laboratório de Ensaios Desgaste e Materiais

Abstract Additive manufacturing (AM) of metallic powder particles has been establishing itself as sustainable, whatever the technology selected. Material extrusion (MEX) integrates the ongoing effort to improve AM sustainability, in which low-cost equipment is associated with a decrease of powder waste during manufacturing. MEX has been gaining increasing interest for building 3D functional/structural metallic parts because it incorporates the consolidated knowledge from powder injection moulding/extrusion feedstocks into the AM scope—filament extrusion layer-by-layer. Moreover, MEX as an indirect process can overcome some of the technical limitations of direct AM processes (laser/electron-beam-based) regarding energy-matter interactions. The present study reveals an optimal methodology to produce MEX filament feedstocks (metallic powder, binder, and additives), having in mind to attain the highest metallic powder content. Nevertheless, the main challenges are also to achieve high extrudability and a suitable ratio between stiffness and flexibility. The metallic powder volume content (vol.%) in the feedstocks was evaluated by the critical powder volume concentration (CPVC). Subsequently, the rheology of the feedstocks was established by means of the mixing torque value, which is related to the filament extrudability performance.

Piston rings (PR) are known for almost a quarter of the friction losses in internal combustion engines. This research work aims to improve the tribological performance of PR by a recently developed variant of Diamond-like Carbon (DLC) coatings deposited in a mixture of Ar and Ne plasma atmosphere (Ne-DLC) by high-power impulse magnetron sputtering (HiPIMS). For the benchmark, the widely used Chromium Nitride (CrN) and DLCs deposited in pure Ar plasma atmosphere (Ar-DLC) were used. The tribological tests were performed on a block-on-ring configuration under different lubrication regimes by varying temperatures and sliding speeds. The analysis of the results was performed by Stribeck curves corresponding to each sample. An improvement of the tribological performance was observed for Ne-DLC films by up to 22.8% reduction in COF compared to CrN in the boundary lubrication regime, whereas, for the Ar-DLC film, this reduction was only 9.5%. Moreover, the Ne-DLC films achieved ultralow friction of less than 0.001 during the transition to a hydrodynamic lubrication regime due to better wettability (lower contact angle) and higher surface free energy. Increasing the Ne up to 50% in the discharge gas also leads to an increase of hardness of DLC films from 19 to 24 GPa.

Micro-structured coatings with functional properties have been investigated due to a wide range of applications. It is known that micro-structures can play an important role in surface interactions determining the materials’ performance. Amongst the other materials, there has been an increasing interest in tantalum oxide (Ta2O5). This attention is mainly due to its variety of properties: biocompatibility and bioactivity; high dielectric constant; good thermal and chemical stability; excellent corrosion and mechanical resistance. Moreover, there is a wide range of applications in which the properties can be fitted. Furthermore, according to the final application, these properties can be enhanced or tailored through surface micro-structures manipulation. Due to this purpose, over the past decade, Ta surface modification by micro-arc oxidation (MAO) has been investigated mostly for biomedical applications. Therefore, this review focuses on Ta surface functionalization using the MAO technique. A clear understanding of the micro-discharge phenomena and the formation mechanism of a Ta2O5 anodic coating by MAO is supplied. The Ta2O5 coating morphology, topography, chemistry, and structure are explored, establishing their correlation with the MAO parameters. Additionally, an understanding of Ta2O5’s biological, mechanical, and electrochemical properties is provided and reviewed.

In this work, the effect of Ag content on the morphology, structure, mechanical properties, thermal stability, and oxidation resistance of multilayered TiSiN/TiN(Ag) films, with Si concentration in the range of 6.3–7.0 at.%, is investigated. The coatings are deposited by DC reactive magnetron sputtering, with increasing Ag content from 0 to 13.9 at.%. All coatings exhibit a face-centered cubic structure (f.c.c NaCl type) and the Ag diffraction peaks progressively increase with increasing Ag content. The hardness and the reduced elastic modulus of the as-deposited films decrease with increasing Ag; these mechanical properties are higher after annealing at 800 °C in protective atmosphere due to the improvement of the crystallinity of the films. The multilayered architecture of the coatings promotes a good barrier against Ag diffusion towards the surface in protective atmosphere. Ag addition does not influence the onset point of oxidation of the films, but it degrades the oxidation resistance due to the Ag diffusion during the oxidation process, which promotes extra paths for ions diffusion.

One of the main problems in ships is corrosion, which reduces the lifetime usage of ship parts and increases maintenance costs. Ceramic coatings can contribute to solving this situation. Zirconium nitrides obtained by reactive unbalanced magnetron sputtering technology are largely reported as coatings with high corrosion resistance. The present study used high-power impulse magnetron sputtering in a reactive atmosphere (R-HiPIMS), varying the nitrogen amount. SEM, EDS, XRD, AFM, and contact angle measurements were used to assess the obtained coatings’ performance. Corrosion resistance was evaluated using electrochemical impedance spectroscopy (EIS) (up to 168 h exposure) and potentiodynamic polarization (PP) in NaCl (3.5% wt.—“artificial seawater”) solution. According to the results, cross section micrographs showed strong densification of ZrN films regardless of the nitrogen amount. Besides, nitrogen increases during deposition influenced the drop of applied peak power (Pp) to the target and, consequently, influenced other film properties, such as roughness, wettability, and corrosion resistance. PP and EIS tests demonstrate the protective behavior of films under artificial seawater exposure. The results prove that the implementation of HiPIMS technology to obtain ZrN films could contribute to increasing the corrosion resistance of coated ship metallic parts and, hence, help maritime transportation to reduce maintenance time and cost.

In recent years, physical vapor deposition (PVD) has emerged as a powerful technique for surface modification, offering a wide range of possibilities to improve the properties of medical devices. This review explores the fundamentals and versatility of PVD coatings in biomedical applications, highlighting their potential to revolutionise the field. Biocompatibility is crucial in successfully integrating medical devices with the human body. The precise modification of thin films to improve biocompatibility, reduce adverse reactions, and promote better tissue integration is discussed. Osseointegration, another critical factor for the success of orthopaedic and dental implants, is also explored in the context of magnetron sputtering coatings. The ability of these coatings to provide a bioactive surface that promotes bone cell adhesion and growth is analyzed, shedding light on the potential of tailor-made coatings in improving implant success rates. Infections associated with medical devices pose a significant challenge in healthcare settings. Strategies, such as the incorporation of antimicrobial agents and surface modifications, are discussed, highlighting the potential of this waste-zero technique in effectively addressing this critical issue. Overall, the versatility, coupled with the ability to enhance corrosion resistance, mechanical properties, tribological performance, biocompatibility, osseointegration, and antimicrobial activity, makes PVD coatings highly promising for improving the performance and functionality of medical devices. Continued research and development in this field will undoubtedly lead to further advancements in PVD coatings, revolutionising the biomedical industry. • Reviews recent advances in magnetron sputtering for biomedical devices • Evaluates PVD coatings for corrosion resistance, durability, biocompatibility, and infection control • Links structure–property relationships to coating design strategies

The influence of V content on the morphology, structure, hardness (H) and reduced Young's modulus (E), adhesion, and oxidation resistance of TiAlSiN coatings is investigated. The coatings were produced by DC reactive magnetron sputtering, with increasing V contents from 0, 4.8 and 11.0 at.%. All coatings exhibit a fcc type structure. The coating with 4.8 at.% of V shows the highest values of H and E, whereas the values are similar for the reference coating and the coating with 11.0 at.% of V. The coatings adhere well to the substrates and show a dense and compact columnar growth extending from the adhesive interlayer to the top surface of the coatings. The dynamic thermal gravimetric oxidation curves reveal that V additions decreases the onset point of oxidation significantly and degrades the oxidation resistance of the coatings. A dual oxide layer is formed on the top surface of the reference coating: an outer porous Ti–Al–O rich layer with plate-like features on the top, which classified to TiO2 (rutile and anatase) and Al2O3 phases, and an inner Ti–Si–O rich layer with Al depletion that identified as mixture of amorphous Si–O and Ti–Si–O protective oxides. The diffusion of V to the top surface governs the oxidation process of the V-containing coatings, i.e. increasing V concentration leads to disrupt the formation of the protective continuous oxide layers easily.

Recently, the use of Ne as a processing gas has been shown to increase the ionization degree of carbon in High Power Impulse Magnetron Sputtering (HiPIMS) plasmas. In this work, time-resolved measurements of the substrate’s current density were carried out in order to study the time evolution of the ionic species arriving at the growing film. The addition of Ne to the plasma resulted in a steep increase of the sp3/sp2 ratio in the films once the Ne contents in the processing atmosphere exceeded 26%. Increasing the Ne content is shown to increase both the total number of C ions generated in the plasmas and the ratio of C/gaseous ions. The time-resolved substrate ion current density was used to evaluate the possibility of substrate biasing synchronizing with the discharge pulses in the HiPIMS process. It is shown that in pure Ar plasmas, substrate biasing should be confined to the time interval between 25 and 40 µs after the pulse starts, in order to maximize the C+/Ar+ ratio bombarding the substrate and minimize the formation of film stresses. However, Ne addition to the processing gas shortens the traveling time of the carbon species towards the substrate, reducing the separation between the gaseous and carbon ion arrival times.

Hard coatings are applied in various applications to protect substrates from wear and corrosion. In the present study, multi-element ceramic films are deposited by reactive sputtering. The level of substrate bias voltage (−50, −125 and −200 V) is changed to investigate the structural and mechanical properties of Cr-Nb-Ti-Zr-N thin films. Chemical analysis (using EDS, XRD and Raman spectroscopy) reveals that these thin films (with a high amount of oxygen) are composed of a nanocomposite phase structure (amorphous and nano-crystalline phases). CrO2 and NbxN crystalline phases exist in an amorphous matrix in the coatings. By increasing the substrate voltage (from −50 to −200 V), the nitrogen content (from 30 to 40 at. %) increases, and CrxN crystalline phases are generated in S125 and S200. Morphological, topological and image analysis (employing FESEM and AFM) data show that the intermediate level of substrate bias voltage (sample S125) can produce a uniform surface with minimum defect density (15%). In addition, S125 has the minimum level of roughness (16.6 nm), skewness (0.2) and kurtosis (2.8). Therefore, the hardness, toughness and wear resistance (extracted from indentation and scratch tests) of this sample is maximum (H is 24.5 GPa and H/E is 0.107), while sample S50 shows complete fracture and delamination.

The influence of energetic ion bombardment on the properties of tantalum coatings was studied. To achieve such energetic ion bombardment during the deposition process of tantalum coatings, a combination of deep oscillation magnetron sputtering (DOMS), an ionized physical vapour deposition technique, with substrate biasing was used. The substrate biasing was varied between 0 and −120 V. In this work, the structure (XRD), microstructure (SEM), surface morphology (AFM) and hardness, and Young’s modulus (nanoindentation) of the coatings were characterized. The results show with the use of such conditions it was possible to deposit a pure α-Ta (the most desired at industrial level) with improved mechanical properties (hardness equal to 22.4 GPa and Young’s modulus equal to 235 GPa). The roughness of the Ta coatings decreases up to values of about 1 nm with an increase of substrate biasing. It was possible to deposit very dense Ta coatings with 2 µm of thickness. Therefore, these results are significantly different than in previous works, offering Ta coatings with a combination of very interesting properties.

Diamond-like-carbon “DLC” coatings can be deposited in many different ways, giving a large range of material properties suitable for many different types of applications. Hydrogen content significantly influences the mechanical properties and the tribological behavior of DLC coatings, but its determination requires techniques that are not available in many research centers. Thus, it is important to find alternative indirect techniques, such as Raman spectroscopy or nanoindentation (hardness measurements), which can give comparative and indicative values of the H contents in the coatings, particularly when depositions with a reactive gas flow are being studied. In this work, “DLC” composite coatings with varying H content were deposited via Physical Vapor Deposition (PVD) magnetron sputtering in a reactive atmosphere (Ar + CH4). An Ion Beam Analysis was used to determine the elemental depth profile across the coating thickness (giving both average C:W:H ratios and film density when combined with profilometer measurements of film thickness). The hardness was evaluated with nanoindentation, and a decrease from 16 to 6 GPa (and a decrease in the film density by a factor of two) with an increasing CH4 flow was observed. Then, the hardness and Raman results were correlated with the H content in the coatings, showing that these indirect methods can be used to find if there are variations in the H content with the increase in the CH4 flow. Finally, the adhesion and tribological performance of the coatings were evaluated. No significant differences were found in the adhesion as a function of the H content. The tribological properties presented a slight improving trend with the increase in the H content with a decrease in the wear rate and friction.

Abstract Lubricants are of paramount importance in protecting metallic contact surfaces and reducing friction. The viscosity of lubricating oil can be engineered by introducing long linear polymers, such as poly(lauryl methacrylate) (PLMA). In particular, the formation of adsorption films by using polymers with hydroxy or amino side groups has attracted much attention in recent years. In this study, copolymers with controlled structure were synthesised by SARA ATRP, which can be used in large scale production. A comparison of friction and wear under boundary lubrication was conducted using both statistical and block copolymers with low Ð . Friction test results using a reciprocating sliding machine (SRV) showed that the block copolymers were less likely to desorb from the metal surface than the statistical copolymers. In addition, the wear evaluation after the SRV test showed that the block copolymer had less wear and less wear debris.

Diamond-like carbon (DLC) films are a class of amorphous carbon materials with unique properties, including high hardness and wear resistance, making them attractive for aerospace and automotive applications. Recently, High Power Impulse Magnetron Sputtering (HiPIMS) has emerged as a new route for magnetron-sputtered hard DLC films. The authors have previously demonstrated that adding Ne to the plasma significantly improves the properties of DLC films deposited by Deep Oscillation Magnetron Sputtering (DOMS), a HiPIMS variant. In this study, the sp3 content evolution with DLC film thickness was measured by Electron Energy Loss Spectroscopy (EELS) and Near Edge X-ray Absorption Spectroscopy (NEXAFS). The sp3 content in the top section of the film deposited in Ar + Ne plasma is close to 40 % and remains constant across the film thickness. Conversely, in films deposited in pure Ar plasma, the sp3 content decreases from approximately 30 % to 18 % towards the surface. Ne addition increases the sp3 content by enhancing the carbon ion flux and counteracting the atomic shadowing effect. These findings provide novel insights into the role of Ne in reducing the atomic shadowing effect and improving the overall quality of DLC films, paving the way for their optimized industrial use.

Hydrogen-free diamond-like carbon (DLC) thin films can be employed for numerous applications, including engine components, once they exhibit good properties for that. They have been used as coatings due to their attractive properties, including high hardness, high wear resistance, and low CoF even under high load/pressure. One of the major limitations of hard hydrogen-free ta-C coatings applications is related to the low reactivity with oil additives used nowadays. The Ionic liquids (ILs) emerged as a novel class of lubricants that can be used in future lubricated systems due to possessing unique physical properties, like high thermal stability and conductivity. To improve the lubrication performance of DLC with ILs, the films were doped with rare earth metals such as Gd and Eu. These non-carbide-forming elements can be introduced in the DLC matrix, incorporated as single atoms, and improve the surface adsorption and reactivity of phosphorus-based IL, and consequently, the lubricating properties of DLC/ILs sliding contacts. However, many demanding applications require good performance across the different regimes (from boundary to hydrodynamic regime). Across all regimes, the boundary is the most challenging, where metal-to-metal contact occurs. Therefore, it is essential to study the influence of the doping elements on the doped-DLCs performance under the boundary regime. For comparison, a pure-DLC was used. In this study, Eu and Gd-DLC tribological systems are characterized by pin-on-disk test in dry conditions and by scratch test. Also, mechanical properties are studied through nano-indentation. Results show that samples doped with a low atomic concentration of Eu or Gd (1%–3%), despite having a CoF higher than un-doped DLC films, show typical values for pure-DLC coatings, like low specific wear rate (<10 −16 m 3 /Nm) and high hardness (23 GPa), permitting, in the future, the combination of novel nanostructured alloyed-DLCs and ILs needed to achieve the optimal lubrication performance.

Inert ceramic implants suffer from significant complications such as lack of osseointegration, biofilm formation, and infections, necessitating the development of novel materials with both osteogenic and antibacterial properties to prevent implant failure. In this study, we aimed to multifunctionalize a tridimensional macroporous alumina scaffold with a biomimetic calcium phosphate (CaP) coating combined with a silver-based extra-thin film to enhance bioactivity and provide an additional antibacterial effect. The porous alumina scaffolds were fabricated through a powder metallurgy technique, followed by biomimetic deposition and DC magnetron sputtering. The coatings were characterized using SEM/EDS and AFM measurements to examine their morphology and topography. To evaluate the osteoconductive response of the materials, in vitro tests were conducted by immersing the samples in Simulated Body Fluid (SBF). The bioactivity tests revealed that the CaP-AgO coating, in line with the roughness surface and free surface energy values, exhibited a higher Ca/P ratio formation. This indicated an increased affinity for apatite adhesion, ultimately leading to a higher osseointegration ability compared to the CaP-Ag coating. Furthermore, the CaP-AgO coating demonstrated superior activity against S. aureus . These findings demonstrate the potential of the multifunctional coatings to address the challenges associated with inert ceramic implants by promoting bioactivity and combating bacterial infections.

The electrical characteristics and conduction mechanisms of ZrAlN thin films for their potential use as thermistors sensors were assessed. Various compositions of Zr1-xAlxN were synthesized by sputtering and studied up to 200 °C to understand their sensitivity and applicability. Among the compositions studied, the ones with x = 0.34 and x = 0.46 showed the highest sensitivities, reaching values close to 3000 K. However, the thermo-resistive properties exhibited by these compositions limited their utilization above 100 °C. Zr1-xAlxN film compositions with x higher than 0.46 showed amorphous structures and were found to be insulative. Composition with x = 0.26, within the cubic phase, showed the most promising electrical properties regarding temperature sensing in the studied range. XPS analysis of this composition confirmed the presence of Zr-N and Al-N bonds, with a Zr3+ oxidation state, which suggests the availability of a free electron contributing to the electrical conduction. Impedance measurements performed at different temperatures for this composition revealed the dominant role of the grain boundaries in the conduction mechanism, based upon electron hopping between grains, overcoming the energy barrier imposed by the grain boundaries. ZrAlN thin films demonstrate negative temperature coefficient (NTC) thermistor behavior, expanding their applications beyond protective coatings to temperature monitoring.

This study investigates an approach to temperature sensing by integrating Titanium Aluminum Nitride (TiAlN), originally engineered for wear and corrosion applications, as a temperature sensor within a multilayered thin film system. A nitride multilayer system was developed by physical vapor deposition (PVD) using a single four-target magnetron sputtering chamber; intermediate vacuum interruption steps were employed for masking procedures. The multilayer architecture design aimed to provide the sensor layer with mechanical protection and electrical shielding. Structural and electrical characterization of the TiAlN single layer revealed semiconductor behavior and stable electrical resistance up to 750 °C, with minimal signal stabilization requirements. Despite the higher Al content, the TiAlN temperature sensor exhibited a cubic crystal structure characterized by diffuse nanolayers resulting from a two-fold rotational deposition and target configuration. Detailed examination of the multilayer system cross-section, containing the TiAlN sensor, was conducted by scanning transmission electron microscopy (STEM). The analysis revealed its columnar morphology with the presence of typical PVD growth defects, including voids and droplets. While the presence of these defects may impact the electrical characteristics of the sensor, the selected experimental conditions effectively maintained the structural integrity of the multilayer system, despite the vacuum interruptions caused by masking procedures. Validation experiments confirmed the functionality of the multilayer system for temperature measurements up to 400 °C. The signal acquisition system addressed room temperature resistance variations and low sensitivity (thermistor coefficient ∼100 K), resulting in a measured error of approximately 6%. This study demonstrates promising results of TiAlN as a temperature sensor within a multilayered system, expanding its range of potential applications.

Titanium alloys such as Ti-6Al-4V are widely used in biomedical implants due to their excellent mechanical properties and biocompatibility, but their bioinert nature limits osseointegration and antibacterial performance. This study proposes a multifunctional surface coating system integrating a thermally oxidized TiO2 interlayer with a hydroxyapatite (HAp) top layer synthesized via a green route using Hylocereus undatus extract. The HAp was deposited by electrophoretic deposition (EPD), enabling continuous coverage and strong adhesion to the pre-treated Ti-6Al-4V substrate. Structural, morphological, chemical, and electrical characterizations were performed using XRD, SEM, EDS, Raman spectroscopy, and impedance spectroscopy. Bioactivity was assessed through apatite formation in simulated body fluid (SBF), while antibacterial properties were evaluated against Staphylococcus aureus. The results demonstrated successful formation of crystalline TiO2 (rutile phase) and calcium-rich HAp with good surface coverage. The HAp-coated surfaces exhibited significantly enhanced bioactivity and strong antibacterial performance, likely due to the combined effects of surface roughness and the bioactive compounds present in the plant extract. This study highlights the potential of eco-friendly, bio-inspired surface engineering to improve the biological performance of titanium-based implants.

Hydroxyapatite (HAp), a bioceramic and calcium phosphate-based material, has attracted significant attention, mainly because it serves as a biocompatible material with promising dielectric properties, suitable for enhancing osseointegration. In this work, HAp was synthesized via sol-gel method using a novel green template approach, incorporating the extract of Hylocereus undatus cladodes, thereby achieving an environmentally friendly synthesis. Thermogravimetric and Differential Scanning Calorimetry (TGA/DSC) analysis revealed a clear pattern involving adsorbed water evaporation, lattice water loss, formation and dehydroxylation of HAp. XRD and Raman spectroscopy verified phase composition and the presence of secondary NaNO 3 , which was substantially reduced by a post-synthesis washing step. Scanning Electron Microscopy (SEM) analysis revealed that particle morphology and size were influenced by extract concentration and heat treatment temperature, with higher extract concentrations promoting equiaxed particles, while lower extract concentrations favoured the formation of rod-like shapes, both relevant for biomedical applications. Impedance Spectroscopy demonstrated that, regardless of the extract concentration and heat treatment temperature, the dielectric properties were strongly influenced by the excitation frequency, with all samples exhibiting a behavior typical of dielectric materials. Sample 12wHT400 meets the desired criteria across four frequencies (100, 1,000, 10,000, and 100,000 Hz), exhibiting a dielectric constant between 18.5 and 22.0, higher than the dielectric losses, and the lowest conductivity values (3×10 -9 to 1×10 -5 Ω -1 ·m -1 ), indicating suitability for prolonged polarization retention.

This study investigates the mechanical properties, microstructure, and tribological performance of CrN and CrAlN coatings. The coatings were deposited by low power DC reactive magnetron sputtering (PVD) on semicrystalline polyether-ketone-ketone (PEKK) substrates. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) confirmed PEKK's thermal stability, with a glass transition temperature of 158.0 °C and a melting point of 309.1 °C, ensuring compatibility with low-temperature coating processes. Microstructural analysis revealed dense, columnar coatings, with CrAlN exhibiting finer grains but minor interfacial voids/cracks that unaffected its adhesion. Tribological tests against stainless steel balls (SS) showed that CrN outperformed CrAlN, reducing the coefficient of friction (COF) by 39 % and specific wear volume by 78 % compared to uncoated PEKK, owing to its higher hardness and the formation of a protective Cr-oxides tribolayer. These results establish CrN as the superior coating for enhancing PEKK's durability and tribological performance, highlighting its potential for applications demanding high durability and wear resistance. • CrN and CrAlN coatings deposited on PEKK using low-power DC magnetron sputtering. • PEKK showed high thermal stability, enabling low-temperature PVD coating. • CrN coating achieved superior tribological performance than CrAlN coating. • CrN reduced friction by 39 % and wear by 78 % compared to uncoated PEKK.