Wear Mechanisms, Composition and Thickness of Antiwear Tribofilms Formed from Multi-Component Lubricants.

The antiwear properties of tribofilms formed on steel surfaces lubricated with various multi-component lubricants were investigated at an elevated temperature and under load-speed conditions conducive to sliding in the boundary lubrication regime. The lubricants contained base oil, reduced-level (secondary) zinc dialkyl dithiophosphate (ZDDP), and nitrogenous dispersant. The wear resistance of the tribofilms produced from different oil blends was evaluated in the context of the rate of change in the sliding track volume (wear rate for material loss) and the load-bearing capacity, chemical composition, and thickness of the tribofilms. Surface profilometry and scanning electron microscopy were used to quantify the wear performance and detect the prevailing wear mechanisms, whereas X-ray photoelectron spectroscopy elucidated the chemical composition and thickness of the tribofilms. The oil blends without ZDDP did not produce tribofilms with adequate antiwear properties, whereas the oil blends containing ZDDP and dispersant generated tribofilms with antiwear characteristics comparable to those of tribofilms produced from blends with a higher ZDDP content. Although dispersants can suspend oil contaminants and preserve the cleanness of the sliding surfaces, it was found that they can also reduce the antiwear efficacy of ZDDP. This was attributed to an additive-dispersant antagonistic behavior for surface adsorption sites affecting tribofilm chemistry and mechanical properties. Among the blends containing a mixture of ZDDP and dispersant, the best antiwear properties were demonstrated by the tribofilm produced from the blend consisting of base oil, 0.05 wt% ZDDP, and a bis-succinimide dispersant treated with ethylene carbonate. The findings of this investigation demonstrate the potential of multi-component lubricants with reduced-content ZDDP and nitrogen-based dispersant to form effective antiwear tribofilms.

Microstructure Evolution and Fretting Wear Mechanisms of Steels Undergoing Oscillatory Sliding Contact in Dry Atmosphere.

Variations in the microstructure and the dominant fretting wear mechanisms of carbon steel alloy in oscillatory sliding contact against stainless steel in a dry atmosphere were evaluated by various mechanical testing and microanalytical methods. These included scanning electron microscopy and energy dispersive spectrometry with corresponding elemental maps of the wear tracks, in conjunction with cross-sectional transmission electron microscopy of samples prepared by focused ion beam machining to assess subsurface and through-thickness changes in microstructure, all as a function of applied load and sliding time. Heavily dislocated layered microstructures were observed below the wear tracks to vary with both the load and sliding time. During the accumulation of fretting cycles, the subsurface microstructure evolved into stable dislocation cells with cell walls aligned parallel to the surface and the sliding direction. The thickness of the damaged subsurface region increased with the load, consistent with the depth distribution of the maximum shear stress. The primary surface oxide evolved as Fe2O3 and Fe3O4 with increasing sliding time, leading to the formation of a uniform oxide scale at the sliding surface. It is possible that the development of the dislocation cell structure in the subsurface also enhanced oxidation by pipe diffusion along dislocation cores. The results of this study reveal complex phase changes affecting the wear resistance of steels undergoing fretting wear, which involve a synergy between oxidative wear, crack initiation, and crack growth along dislocation cell walls due to the high strains accumulating under high loads and/or prolonged surface sliding.

Dynamics of Tribofilm Formation in Boundary Lubrication Investigated Using In Situ Measurements of the Friction Force and Contact Voltage.

The complex dynamics of tribofilm formation on boundary-lubricated steel surfaces were investigated in real time by combining in situ measurements of the temporal variation of the coefficient of friction and contact voltage. Sliding experiments were performed with various blends consisting of base oil, zinc dialkyl dithiophosphate (ZDDP) additive, and two different dispersants at an elevated oil temperature for a wide range of normal load and fixed sliding speed. The evolution of the transient and steady-state coefficient of friction, contact voltage, and critical sliding distance (time) for stable tribofilm formation were used to evaluate the tribological performance of the tribofilms. The blend composition affected the load dependence of the critical sliding distance for stable tribofilm formation. Tribofilm friction was influenced by competing effects between the additive and the dispersants. Among various formulations examined, the tribofilm with the best friction characteristics was found to be the blend consisting of base oil, a small amount of ZDDP, and a bis-succinimide dispersant treated with ethylene carbonate. The results of this study demonstrate the effectiveness of the present experimental approach to track the formation and removal of protective tribofilms under boundary lubrication conditions in real time.

In vitro degradation of fibrous bilayer poly-L-lactic acid scaffolds.

Polymer degradation and mechanical properties are of paramount importance in tissue engineering. The degradation rate of polymeric scaffolds is influenced by several important material and environmental factors. In particular, the mechanical support provided by the scaffold to the surrounding tissue during tissue regeneration is critical for that it directly impacts the cell behavior through mechanical signals sensed by mechanoreceptors on the cell surface. Consequently, the principal objective of the present study was to investigate the degradation behavior of electrospun poly-L-lactic acid (PLLA) bilayer microfibrous scaffolds in pH-neutral medium. Changes in the morphology, molecular weight, crystallinity, mass loss, and thermomechanical properties of the scaffolds over an extended period were studied by scanning electron microscopy, differential scanning calorimetry, gel permeation chromatography, and tensile testing. An interplay between chain scission and orderly chain rearrangement in the polymer scaffold commenced during degradation, leading to the decrease of the molecular weight and stiffness, a constant mass loss, and an increase in crystallinity, tensile strength, and glass transition temperature, with virtually constant yield strength and melting temperature. The unchanged structure morphology and adequate matrix stiffness after prolonged degradation illuminated the potential of the bilayer PLLA scaffolds for tissue engineering and drug delivery applications. Nonetheless, modifications to the scaffold structure or surface may be required to accordingly tune the degradation rate in these applications. The experimental methodology introduced in this study can be extended to potentially investigate material degradation in other fields, such as agriculture, packaging, and disposable products.

Mechanical Behavior of Bamboo-Like Structures under Transversal Compressive Loading.

Inspired by many biological structures in nature, biomimetic structures demonstrate significantly better mechanical performance than traditional engineering structures. The exceptional mechanical properties of natural materials are attributed to the hierarchical architecture of their structure. Consequently, the implementation of biomimetic structures in the design of lightweight structures with tailored mechanical properties has been constantly increasing in many fields of science and engineering. The bamboo structure is of particular interest because it combines a light weight and excellent mechanical properties, often surpassing those of several engineering materials. The objective of this study was to evaluate the mechanical behavior of bamboo-inspired structures subjected to transversal compressive loading. Structures consisting of bamboo-like thin-walled hexagonal building blocks (unit cells) with different dimensions were fabricated by stereolithography 3D printing and their mechanical performance was evaluated by mechanical testing, high-speed camera video recordings, and finite element simulations. The results of the elastic modulus, yield strength, and strain energy density at fracture were interpreted in terms of characteristic dimensions of the unit cell structure. The failure process was elucidated in the light of images of the fractured structures and simulation strain maps. The results of this study demonstrate that ultralight bamboo-like structures with specific mechanical characteristics can be produced by optimizing the dimensions and number density of the hexagonal unit cell.

Novel Electrospun Polycaprolactone/Calcium Alginate Scaffolds for Skin Tissue Engineering.

After decades of research, fully functional skin regeneration is still a challenge. Skin is a multilayered complex organ exhibiting a cascading healing process affected by various mechanisms. Specifically, nutrients, oxygen, and biochemical signals can lead to specific cell behavior, ultimately conducive to the formation of high-quality tissue. This biomolecular exchange can be tuned through scaffold engineering, one of the leading fields in skin substitutes and equivalents. The principal objective of this investigation was the design, fabrication, and evaluation of a new class of three-dimensional fibrous scaffolds consisting of poly(ε-caprolactone) (PCL)/calcium alginate (CA), with the goal to induce keratinocyte differentiation through the action of calcium leaching. Scaffolds fabricated by electrospinning using a PCL/sodium alginate solution were treated by immersion in a calcium chloride solution to replace alginate-linked sodium ions by calcium ions. This treatment not only provided ion replacement, but also induced fiber crosslinking. The scaffold morphology was examined by scanning electron microscopy and systematically assessed by measurements of the pore size and the diameter, alignment, and crosslinking of the fibers. The hydrophilicity of the scaffolds was quantified by contact angle measurements and was correlated to the augmentation of cell attachment in the presence of CA. The in vitro performance of the scaffolds was investigated by seeding and staining fibroblasts and keratinocytes and using differentiation markers to detect the evolution of basal, spinous, and granular keratinocytes. The results of this study illuminate the potential of the PCL/CA scaffolds for tissue engineering and suggest that calcium leaching out from the scaffolds might have contributed to the development of a desirable biological environment for the attachment, proliferation, and differentiation of the main skin cells (i.e., fibroblasts and keratinocytes).

Design Challenges in Polymeric Scaffolds for Tissue Engineering.

Numerous surgical procedures are daily performed worldwide to replace and repair damaged tissue. Tissue engineering is the field devoted to the regeneration of damaged tissue through the incorporation of cells in biocompatible and biodegradable porous constructs, known as scaffolds. The scaffolds act as host biomaterials of the incubating cells, guiding their attachment, growth, differentiation, proliferation, phenotype, and migration for the development of new tissue. Furthermore, cellular behavior and fate are bound to the biodegradation of the scaffold during tissue generation. This article provides a critical appraisal of how key biomaterial scaffold parameters, such as structure architecture, biochemistry, mechanical behavior, and biodegradability, impart the needed morphological, structural, and biochemical cues for eliciting cell behavior in various tissue engineering applications. Particular emphasis is given on specific scaffold attributes pertaining to skin and brain tissue generation, where further progress is needed (skin) or the research is at a relatively primitive stage (brain), and the enumeration of some of the most important challenges regarding scaffold constructs for tissue engineering.

Thermal stability and diffusion characteristics of ultrathin amorphous carbon films grown on crystalline and nitrogenated silicon substrates by filtered cathodic vacuum arc deposition.

Amorphous carbon (a-C) films are widely used as protective overcoats in many technology sectors, principally due to their excellent thermophysical properties and chemical inertness. The growth and thermal stability of sub-5-nm-thick a-C films synthesized by filtered cathodic vacuum arc on pure (crystalline) and nitrogenated (amorphous) silicon substrate surfaces were investigated in this study. Samples of a-C/Si and a-C/SiNx/Si stacks were thermally annealed for various durations and subsequently characterized by high-resolution transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). The TEM images confirmed the continuity and uniformity of the a-C films and the 5-nm-thick SiNx underlayer formed by silicon nitrogenation using radio-frequency sputtering. The EELS analysis of cross-sectional samples revealed the thermal stability of the a-C films and the efficacy of the SiNx underlayer to prevent carbon migration into the silicon substrate, even after prolonged heating. The obtained results provide insight into the important attributes of an underlayer in heated multilayered media for preventing elemental intermixing with the substrate, while preserving the structural stability of the a-C film at the stack surface. An important contribution of this investigation is the establishment of an experimental framework for accurately assessing the thermal stability and elemental diffusion in layered microstructures exposed to elevated temperatures.

A molecular dynamics study of the oxidation mechanism, nanostructure evolution, and friction characteristics of ultrathin amorphous carbon films in vacuum and oxygen atmosphere.

Amorphous carbon (a-C) films are characterized by extraordinary chemical inertness and unique thermophysical properties that are critical to applications requiring oxidation-resistant, low-friction, and durable overcoats. However, the increasing demands for ultrathin (a few nanometers thick) a-C films in various emerging technologies, such as computer storage devices, microelectronics, microdynamic systems, and photonics, make experimental evaluation of the structural stability and tribomechanical properties at the atomic level cumbersome and expensive. Consequently, the central objective of this study was to develop comprehensive MD models that can provide insight into the oxidation behavior and friction characteristics of ultrathin a-C films exhibiting layered through-thickness structure. MD simulations were performed for a-C films characterized by relatively low and high sp3 contents subjected to energetic oxygen atom bombardment or undergoing normal and sliding contact against each other in vacuum and oxygen atmosphere. The effect of energetic oxygen atoms on the oxidation behavior of a-C films, the dependence of contact deformation and surface attractive forces (adhesion) on surface interference, and the evolution of friction and structural changes (rehybridization) in the former a-C films during sliding are interpreted in the context of simulations performed in vacuum and oxidizing environments. The present study provides insight into the oxidation mechanism and friction behavior of ultrathin a-C films and introduces a computational framework for performing oxidation/tribo-oxidation MD simulations that can guide experimental investigations.

Structure evolution during deposition and thermal annealing of amorphous carbon ultrathin films investigated by molecular dynamics simulations.

The evolution of the structure of amorphous carbon (a-C) films during deposition and thermal annealing is of significant interest from both the materials science and application perspectives. However, despite the voluminous literature of studies dealing with the deposition and physical properties of a-C films, basic understanding of the structure evolution due to phase change during film growth and heating is fairly sparse and empirical, presumably due to the lack of high-resolution instruments that can probe structural changes at the atomic and molecular levels in real time. Molecular dynamics (MD) is a powerful computational method for studying atomic/molecular-scale movement and interactions. Thus, the objective of this study was to perform MD simulations that provide insight into changes in the structure of ultrathin a-C films during deposition and annealing. Simulation results reveal a multi-layer film structure, even for a-C films as thin as ~20 Å, the existence of a deposition energy that yields a-C films with the highest sp3 content, the transient and steady-state stages of the structure evolution during annealing at different temperatures, and the changes in the hybridization state (mainly in the bulk layer) encountered during annealing at elevated temperatures. The MD results of this study are of particular importance to applications where the deposition conditions and operation temperature affect the structure and, in turn, the physical properties of ultrathin a-C films used as protective overcoats.

Highly flexible, foldable, and rollable microsupercapacitors on an ultrathin polyimide substrate with high power density.

The design and functionality of extremely flexible, foldable, and rollable microsupercapacitors (MSCs) with in-plane interdigital electrodes that consist of single-walled carbon nanotube (SWCNT) networks on an ultrathin polyimide substrate are demonstrated through experiments and finite element simulations. The all-solid-state MSCs can be reversibly bent, folded, and rolled purely elastically without degradation of their electrical performance. The simulation results confirm that the deformation in bent, folded, and rolled MSCs is purely elastic. The high power density (1125 W cm-3) and small time constant (1 ms) of the present MSCs are comparable to those of aluminum electrolytic capacitors. The MSCs operate at scan rates of up to 1000 V s-1, are characterized by a volumetric capacitance of 18 F cm-3 and an energy density of 1.6 mWh cm-3, and exhibit superior electrochemical stability with 96% capacity retention even after 100,000 charge/discharge cycles. The developed MSCs demonstrate high potential for integration in flexible and wearable electronic systems.

Highly Stretchable Microsupercapacitor Arrays with Honeycomb Structures for Integrated Wearable Electronic Systems.

The rapid development of portable and wearable electronics has greatly increased the demand for energy storage devices with similar physical properties and integration capability. This paper introduces a honeycomb polydimethylsiloxane substrate for stretchable microsupercapacitor (MSC) arrays, which enables facile integration with other electronics. The honeycomb structure can accommodate a large deformation without producing excessive strain in the MSCs and interconnects. The results of this study show that such stretchable MSC arrays with single-walled carbon nanotube electrodes demonstrate excellent rate capability and power performance as well as electrochemical stability up to 150% (zero prestrain) or 275% (-50% prestrain) stretching and under excessive bending or twisting. The present stretchable MSC arrays with honeycomb structures show high potential for integration with other electronics, such as energy harvesters, power management circuits, wireless charging circuits, and various sensors, encompassing a wide range of wearable, bioimplantable electronic systems.

Failure mechanisms of single-crystal silicon electrodes in lithium-ion batteries.

Long-term durability is a major obstacle limiting the widespread use of lithium-ion batteries in heavy-duty applications and others demanding extended lifetime. As one of the root causes of the degradation of battery performance, the electrode failure mechanisms are still unknown. In this paper, we reveal the fundamental fracture mechanisms of single-crystal silicon electrodes over extended lithiation/delithiation cycles, using electrochemical testing, microstructure characterization, fracture mechanics and finite element analysis. Anisotropic lithium invasion causes crack initiation perpendicular to the electrode surface, followed by growth through the electrode thickness. The low fracture energy of the lithiated/unlithiated silicon interface provides a weak microstructural path for crack deflection, accounting for the crack patterns and delamination observed after repeated cycling. On the basis of this physical understanding, we demonstrate how electrolyte additives can heal electrode cracks and provide strategies to enhance the fracture resistance in future lithium-ion batteries from surface chemical, electrochemical and material science perspectives.

High-energy-density, all-solid-state microsupercapacitors with three-dimensional interdigital electrodes of carbon/polymer electrolyte composite.

Novel all-solid-state microsupercapacitors (MSCs) with three-dimensional (3D) electrodes consisting of active materials (i.e., graphene or activated carbon (AC) particles) and polymer electrolyte (PE) designed for high-energy-density storage applications were fabricated and tested in this work. The incorporation of PE in the electrode material enhances the accessibility of electrolyte ions to the surface of active materials and decreases the ion diffusion path during electrochemical charge/discharge. For a scan rate of 5 mV s(-1), the MSCs with graphene/PE and AC/PE composite electrodes demonstrate a very high areal capacitance of 95 and 134 mF cm(-2), respectively, comparable to that of 3D MSCs with liquid electrolyte. In addition, the graphene/PE MSCs show a ∼70% increase in specific capacitance after 10 000 charge/discharge cycles, attributed to an electro-activation process resulting from ion intercalation between the graphene nanosheets. The AC/PE MSCs also demonstrate excellent stability. The results of this study illustrate the potential of the present 3D MSCs for various high-density solid-state energy storage applications.

A catalytic path for electrolyte reduction in lithium-ion cells revealed by in situ attenuated total reflection-Fourier transform infrared spectroscopy.

Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

Electrospun bilayer fibrous scaffolds for enhanced cell infiltration and vascularization in vivo.

Bilayer poly(L-lactic acid) fibrous scaffolds consisting of a thin aligned-fiber layer (AFL) and a relatively thick random-fiber layer (RFL) were fabricated by an electrospinning technique, which uses two slowly rotating parallel disks as the collector. The morphology and structure of the bilayer scaffolds were examined by high-magnification scanning electron microscopy and confocal microscopy. The bilayer scaffolds demonstrated a gradual variation in through-thickness porosity and fiber alignment and an average porosity much higher than that of conventionally electrospun scaffolds (controls) with randomly distributed fibers. The biocompatibility and biological performance of the bilayer fibrous scaffolds were evaluated by in vivo experiments involving subcutaneous scaffold implantation in Sprague-Dawley rats, followed by histology and immunohistochemistry studies. The results illustrate the potential of the bilayer scaffolds to overcome major limitations of conventionally electrospun scaffolds associated with intrinsically small pores, low porosity and, consequently, poor cell infiltration. The significantly higher porosity and larger pore size of RFL enhances cell motility through the scaffold thickness, whereas the relatively dense structure of AFL provides the scaffold with the necessary mechanical strength. The bilayer scaffolds show more than two times higher cell infiltration than controls during implantation in vivo. The unique structure of the bilayer scaffolds promotes collagen fiber deposition, cell proliferation, and ingrowth of smooth muscle cells and endothelial cells in vivo. The results of this study illustrate the high prospect of the fabricated bilayer fibrous scaffolds in tissue engineering and regeneration.

Sum frequency generation vibrational spectroscopy of 1,3-butadiene hydrogenation on 4 nm Pt@SiO2, Pd@SiO2, and Rh@SiO2 core-shell catalysts.

1,3-Butadiene (1,3-BD) hydrogenation was performed on 4 nm Pt, Pd, and Rh nanoparticles (NPs) encapsulated in SiO2 shells at 20, 60, and 100 °C. The core-shells were grown around polyvinylpyrrolidone (PVP) coated NPs (Stöber encapsulation) prepared by colloidal synthesis. Sum frequency generation (SFG) vibrational spectroscopy was performed to correlate surface intermediates observed in situ with reaction selectivity. It is shown that calcination is effective in removing PVP, and the SFG signal can be generated from the metal surface. Using SFG, it is possible to compare the surface vibrational spectrum of Pt@SiO2 (1,3-BD is hydrogenated through multiple paths and produces butane, 1-butene, and cis/trans-2-butene) to Pd@SiO2 (1,3-BD favors one path and produces 1-butene and cis/trans-2-butene). In contrast to Pt@SiO2 and Pd@SiO2, SFG and kinetic experiments of Rh@SiO2 show a permanent accumulation of organic material.

Mechanical properties of electrospun bilayer fibrous membranes as potential scaffolds for tissue engineering.

Bilayer fibrous membranes of poly(l-lactic acid) (PLLA) were fabricated by electrospinning, using a parallel-disk mandrel configuration that resulted in the sequential deposition of a layer with fibers aligned across the two parallel disks and a layer with randomly oriented fibers, both layers deposited in a single process step. Membrane structure and fiber alignment were characterized by scanning electron microscopy and two-dimensional fast Fourier transform. Because of the intricacies of the generated electric field, bilayer membranes exhibited higher porosity than single-layer membranes consisting of randomly oriented fibers fabricated with a solid-drum collector. However, despite their higher porosity, bilayer membranes demonstrated generally higher elastic modulus, yield strength and toughness than single-layer membranes with random fibers. Bilayer membrane deformation at relatively high strain rates comprised multiple abrupt microfracture events characterized by discontinuous fiber breakage. Bilayer membrane elongation yielded excessive necking of the layer with random fibers and remarkable fiber stretching (on the order of 400%) in the layer with fibers aligned in the stress direction. In addition, fibers in both layers exhibited multiple localized necking, attributed to the nonuniform distribution of crystalline phases in the fibrillar structure. The high membrane porosity, good mechanical properties, and good biocompatibility and biodegradability of PLLA (demonstrated in previous studies) make the present bilayer membranes good scaffold candidates for a wide range of tissue engineering applications.

In vitro investigation of skin damage due to microscale shearing.

Despite several studies dealing with the mechanical and tribological properties of skin, the majority of these investigations have been performed at macroscopic levels. However, because of the multilayer structure of skin, it is necessary to perform studies at microscopic scales to reveal the effect of individual layer constituents on the overall skin response to mechanical stimuli. To bridge the gap in knowledge of the micromechanical behavior of skin, a custom-made mechanical tester, optical microscopy, and cross-sectional histology were used to examine the deformation and tribological behavior of porcine skin subjected to various normal and shear loadings. Representative friction and wear results of skin tested under unidirectional and reciprocating (cyclic) shearing (scratching) conditions are interpreted in terms of the scratching speed, normal load, and number of scratch cycles to illustrate the effects of stratum corneum, cellular epidermis, and dermis on the friction and wear characteristics of skin. Depending on the normal load and scratch time (cycles), different friction mechanisms (i.e., adhesion, plowing, and squeeze-film lubrication) and wear mechanisms (i.e., surface plasticity/plowing, bulk shearing, cohesive failure, tearing, and delamination) were found to control shear-induced skin damage. The results of this study provide insight into microscale friction and wear processes influencing the mechanical response of skin subjected to normal and shear surface tractions.

Tuning the electronic structure of titanium oxide support to enhance the electrochemical activity of platinum nanoparticles.

Two times higher activity and three times higher stability in methanol oxidation reaction, a 0.12 V negative shift of the CO oxidation peak potential, and a 0.07 V positive shift of the oxygen reaction potential compared to Pt nanoparticles on pristine TiO2 support were achieved by tuning the electronic structure of the titanium oxide support of Pt nanoparticle catalysts. This was accomplished by adding oxygen vacancies or doping with fluorine. Experimental trends are interpreted in the context of an electronic structure model, showing an improvement in electrochemical activity when the Fermi level of the support material in Pt/TiOx systems is close to the Pt Fermi level and the redox potential of the reaction. The present approach provides guidance for the selection of the support material of Pt/TiOx systems and may be applied to other metal-oxide support materials, thus having direct implications in the design and optimization of fuel cell catalyst supports.