Energy dissipation in depth-sensing indentation as a characteristic of the nanoscratch behavior of coatings

Wear behavior of coatings has usually been described in terms of mechanical properties such as hardness (H) and effective elastic modulus (E*). Alternatively, an energy approach appears as a promising analysis taking into account the influence of those properties. In a nanoindentation test, the dissipated energy depends not only on the hardness and elastic modulus, but also on the elastic recovery (W(e)). This work aims to establish a relation between plastic deformation energy (E(p)) during depth-sensing indentation method and the grooving resistance of coatings in nanoscratch tests. An energy dissipation coefficient (K(d)) was defined, calculated as the ratio of the plastic to the total deformation energy (E(p)/E(t)), which represents the energy dissipation of materials. Reactive depositions using titanium as the target and nitrogen and methane as reactive gases were obtained by triode magnetron sputtering, in order to assess wear and nanoindentation data. A topographical, chemical and microstructural characterization has been conducted using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), wave dispersion spectroscopy (WDS), scanning electron (SEM) and atomic force microscopy (AFM) techniques. Nanoscratch results showed that the groove depth was well correlated to the energy dissipation coefficient of the coatings. On the other hand, a reduction in the coefficient was found when the elastic recovery was increased. (C) 2009 Elsevier B.V. All rights reserved.

Comparison of adsorbent films obtained by plasma polymerization of oxygenated organic compounds

Thin films obtained by plasma polymerization of ethyl ether, methyl or ethyl acetate, acetaldehyde, acetone and 2-propanol were compared. Infrared spectroscopy (FFIR), resistance to chemicals, contact angle measurements, X-ray photoelectron spectroscopy (XPS), optical and scanning electron microscopy (SEM), and quartz crystal microbalance (QCM) were carried out. For all films FTIR showed high intensity for polar bonds yet the films are not resistant to polar solvents. Contact angle measurements revealed hydrophilic and organophilic surfaces and XPS pointed out a high proportion of oxygenated bonds. All films showed good step coverage and peeling was significant only with acetone and 2-propanol. All films are adsorbent for organic compounds in a large scale of polarity but acetaldehyde and 2-propanol act like a selective membrane. Also, deposition of these films on hydrophobic substrates leads to island formation. A possible model to explain the results must consider the hydrogen bridge formation on 2-propanol and acetaldehyde films. Ethyl ether, ethyl and methyl acetate showed good characteristics for development of sensor and sample pretreatment using miniaturized devices. (C) 2007 Elsevier B.V. All rights reserved.

Interface excess and polymorphic stability of nanosized zirconia-magnesia

Controlling the phase stability of ZrO2 nanoparticles is of major importance in the development of new ZrO2-based nanotechnologies. Because of the fact that in nanoparticles the surface accounts for a larger fraction of the total atoms, the relative phase stability can be controlled throughout the surface composition, which can be toned by surface excess of one of the components of the system., The objective of this work is to delineate a relationship between surface excess (or solid solution) of MgO relative to ZrO2 and the polymorphic stability of (ZrO2)(1-x) - (MgO), nanopowders, where 0.0 <= x <= 0.6. The nanopowders were prepared by a liquid precursor method at 500 degrees C and characterized by N-2 adsorption (BET), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), and Raman spectroscopy. For pure ZrO2 samples, both tetragonal and monoclinic polymorphs were detected, as expected considering the literature. For MgO molar fractions varying from 0.05 to 0.10, extensive solid solution could not be detected, and a ZrO2 surface energy reduction, caused by Mg surface excess detected by XPS, promoted tetragonal polymorph thermodynamic stabilization with relation to monoclinic. For MgO molar fractions higher than 0.10 and up to 0.40, Mg solid solution could be detected and induced cubic phase stabilization. MgO periclase was observed only at x = 0.6. A discussion based on the relationship between the surface excess, surface energy, and polymorph stability is presented.

Electrochemical study of modified cerium-silane bi-layer on Al alloy 2024-T3

In this paper, the performance of bis-1, 2-(triethoxysilyl) ethane (BTSE) as a pre-treatment to protect the AA 2024-T3 against corrosion has been investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, and the scanning vibrating electrode technique (SVET). The microstructural and morphological characterizations were carried out via scanning electron microscopy and atomic force microscopy and the chemical composition evaluated using contact angle measurements and X-ray photoelectron spectroscopy (XPS). The electrochemical results showed that the additives improved the anticorrosion properties of the coating. The chemical characterization indicated that additives contribute to an increased degree of surface coverage, as well as to a more complete reticulation. The SVET results evidenced the self-healing abilities of Ce ions. (C) 2009 Elsevier Ltd. All rights reserved.

Morphological and electrochemical investigation of RuO(2)-Ta(2)O(5) oxide films prepared by the Pechini-Adams method

Preparation methods can profoundly affect the structural and electrochemical properties of electrocatalytic coatings. In this investigation, RuO(2)-Ta(2)O(5) thin films containing between 10 and 90 at.% Ru were prepared by the Pechini-Adams method. These coatings were electrochemically and physically characterized by cyclic voltammetry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The composition and morphology of the oxide were investigated before and after accelerated life tests (ALT) by EDX and SEM. SEM results indicate typical mud-flat-cracking morphology for the majority of the films. High resolution SEMs reveal that pure oxide phases exhibit nanoporosity while binary compositions display a very compact structure. EDX analyses reveal considerable amounts of Ru in the coating even after total deactivation. XRD indicated a rutile-type structure for RuO(2) and orthorhombic structure for Ta(2)O(5). XPS data demonstrate that the binding energy of Ta is affected by Ru addition in the thin films, but the binding energy of Ru is not likewise influenced by Ta. The stability of the electrodes was evaluated by ALT performed at 750 mA cm(-2) in 80 degrees C 0.5 mol dm(-3) H(2)SO(4). The performance of electrodes prepared by the Pechini-Adams method is 100% better than that of electrodes prepared by standard thermal decomposition.

Effects of oxide promoters on metal dispersion and metal-support interactions in Ni catalysts supported on activated carbon

Various oxide-promoted Ni catalysts supported on activated carbon were prepared, and the effect of promoters on the surface structure and properties of Ni catalysts was studied. Physical adsorption (Na adsorption), thermogravimetric analysis (TGA), temperature-programmed desorption (TPD), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It is found that nickel is fairly uniformly distributed in the pores of the carbon support. Addition of promoters produces a more homogeneous distribution of nickel ion in carbon. However, distributions of promoters in the pores are varying. Addition of promoters increases the dispersion of nickel in carbon. Promoters also change the interaction between the carbon and Ni, resulting in significantly different behaviors of catalysts under various environments. CaO and MgO promoters improve the reactivity of nickel catalysts with O-2 but retard the interaction between nickel oxide and carbon. La2O3 shows some inhibiting effect on the interactions between nickel oxide and oxygen as well as carbon.

A study of the oxidation of two aromatic polyimide fluoropolymers containing phenylphosphine oxide by a water plasma and gamma-radiolysis in air

The oxidation of two fluorinated polyimides containing phenylphosphine oxide units, TOR-RC and TOR-RC ODPA, have been studied at 300 K for treatment by a water plasma and gamma -radiolysis in air. The changes in the O 1s/C 1s ratios obtained from x-ray photoelectron spectroscopy (XPS) analysis showed that for exposure to the water plasma the ratio increases at short exposure times and then levels to a constant value. Evidence for the formation of phosphate species was also obtained from the XPS analyses. Similar observations were made for gamma -radiolysis of the polymers in air. The polymers containing phenylphosphine oxide were found to be more resistant to oxidation in the water plasma than Kapton(R). Radiolysis of the polymers in air to high doses were also accompanied by a red shift in the visible absorption spectra.

Thin films of a tetracationic porphyrin

Langmuir-Blodgett films of the tetracationic porphyrin tetrakis( octadecyl-4-pyridinium) porphinatozinc(ii) bromide transferred from subphases containing different salts were studied using X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. In contrast to previous results at the air/water interface, we found that the porphyrin adopted a fixed conformation at the air/solid interface regardless of composition of the subphase or whether the films were transferred above or below the primary phase transition. This conformation was assigned to the formation of an interdigitated bilayer structure.

Ageing effects on the wettability behavior of laser textured silicon

In the present work we investigate the ageing of acid cleaned femtosecond laser textured < 100 > silicon surfaces. Changes in the surface structure and chemistry were analysed by Rutherford backscattering spectrometry (RBS) and X-ray photoelectron spectroscopy (XPS), in order to explain the variation with time of the water contact angles of the laser textured surfaces. It is shown that highly hydrophobic silicon surfaces are obtained immediately after laser texturing and cleaning with acid solutions (water contact angle >120 degrees). However these surfaces are not stable and ageing leads to a decrease of the water contact angle which reaches a value of 80 degrees. XPS analysis of the surfaces shows that the growth of the native oxide layer is most probably responsible for this behavior. (C) 2010 Elsevier B.V. All rights reserved.

Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

Electrochemical response of 70Co-30Ni highly branched 3D-dendritic structures for charge storage electrodes

A 70Co-30Ni dendritic alloy was produced on stainless steel by pulse electrodeposition in the cathodic domain, and oxidized by potential cycling. X-ray diffraction (XRD) identified the presence of two phases and scanning electron microscopy (SEM) evidenced an open 3D highly branched dendritic morphology. After potential cycling in 1 M KOH, SEM and X-ray photoelectron spectroscopy (XPS) revealed, respectively, the presence of thin nanoplates, composed of Co and Ni oxi-hydroxides and hydroxides over the original dendritic film. Cyclic voltammetry tests showd the presence of redox peaks assigned to the oxidation and reduction of Ni and Co centres in the surface film. Charge/discharge measurements revealed capacity values of 121 mAh g(1) at 1 mA cm(2). The capacity retention under 8000 cycles was above 70%, stating the good reversibility of these redox materials and its suitability to be used as charge storage electrodes. Electrochemical impedance spectroscopy (EIS) spectra, taken under different applied bias, showed that the capacitance increased when the electrode was fully oxidized and decreased when the electrode was reduced, reflecting different states-of-charge of the electrode. (C) 2015 Elsevier Ltd. All rights reserved.

Development of new biomaterials based on liquid crystalline phases of cellulose derivatives

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do Grau de Mestre em Engenharia Biomédica

Development of thermoresponsive (polysulfone/polyacrylonitrile) - based membranes for bioseparation processes

Mestrado integrado em Engenharia Química e Bioquímica

Storage of water molecules into biomimetic heterostructures: the role of roughness

The development of devices based on heterostructured thin films of biomolecules conveys a huge contribution on biomedical field. However, to achieve high efficiency of these devices, the storage of water molecules into these heterostructures, in order to maintain the biological molecules hydrated, is mandatory. Such hydrated environment may be achieved with lipids molecules which have the ability to rearrange spontaneously into vesicles creating a stable barrier between two aqueous compartments. Yet it is necessary to find conditions that lead to the immobilization of whole vesicles on the heterostructures. In this work, the conditions that govern the deposition of open and closed liposomes of 1.2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (sodium Salt) (DPPG) onto polyelectrolytes cushions prepared by the layer-by-layer (LbL) method were analyzed. Electronic transitions of DPPG molecules as well as absorption coefficients were obtained by vacuum ultraviolet spectroscopy, while the elemental composition of the heterostructures was characterized by x-ray photoelectron spectroscopy (XPS). The presence of water molecules in the films was inferred by XPS and infrared spectroscopy. Quartz crystal microbalance (QCM) data analysis allowed to conclude that, in certain cases, the DPPG adsorbed amount is dependent of the bilayers number already adsorbed. Moreover, the adsorption kinetics curves of both adsorbed amount and surface roughness allowed to determine the kinetics parameters that are related with adsorption processes namely, electrostatic forces, liposomes diffusion and lipids re-organization on surface. Scaling exponents attained from atomic force microscopy images statistical analysis demonstrate that DPPG vesicles adsorption mechanism is ruled by the diffusion Villain model confirming that adsorption is governed by electrostatic forces. The power spectral density treatment enabled a thorough description of the accessible surface of the samples as well as of its inner structural properties. These outcomes proved that surface roughness influences the adsorption of DPPG liposomes onto surfaces covered by a polyelectrolyte layer. Thus, low roughness was shown to induce liposome rupture creating a lipid bilayer while high roughness allows the adsorption of whole liposomes. In addition, the fraction of open liposomes calculated from the normalized maximum adsorbed amounts decreases with the cushion roughness increase, allowing us to conclude that the surface roughness is a crucial variable that governs the adsorption of open or whole liposomes. This conclusion is fundamental for the development of well-designed sensors based on functional biomolecules incorporated in liposomes. Indeed, LbL films composed of polyelectrolytes and liposomes with and without melanin encapsulated were successfully applied to sensors of olive oil.

Antibacterial properties of fibrous stents coated with silver oxide nanocoatings

Stents are rigid and perforated tubular structures, which are inserted into blood vessels in order to prevent or inhibit the constriction of blood flow, restoring the normal blood flow, when blood vessels are clogged, being used in 70% of angioplasties. These medical devices assume great importance in the treatment of cardiovascular diseases (CVD) which are the leading cause of death worldwide. In the European Union CVD account for 40% of deaths and assume an estimated annual cost of 196 billion euros[1]. Stents must possess certain requirements, in order to, adequately, perform its function, such as biocompatibility (so that its use does not c ause damage on the health of its user), mechanical strength, radiopacity (so that it is easy to view), longitudinal flexibility, ease of handling, corrosion resistance and having high strength and high radial expansion ability to recover. Stents can be made of different materials, but metals, particularly stainless steel, are the most common. However, metallic stents present several dRawbacks such as corrosion and restenosis, leading to health complications for the patient, or even death. In order to minimize these disadvantages, new materials, like fibrous materials, have been used [2]. Monofilaments present high potential for stents development because, in addition to its biocompatibility, these materials allow the application of various surface treatments, such as antibacterial coatings. Furthermore, monofilament exhibit excellent mechanical properties, like greater stiffness and good results when subjected to compression, tensile and bending forces, since these forces will be directly supported by the monofilament [3]. To minimize the reaction of the human body and Limit the adhesion of microorganisms to the stent surface, some coatings have been developed, including the use of novel metals with antimicrobial properties, like silver. The main objective of this study was the development of fibrous stents, incorporation of silver oxide nanocoating. For the development of the stent, polyester monofilaments with 0.27mm of diameter were used in braiding technology, with a mandrel diameter of 6mm and a braiding angle of 35⁰. The mechanical behaviour of the stent were evaluated by mechanical testing under longitudinal and radial compression, bending. The results of compressive strength tests are according with value from literature: 1.13 to 2.9 N for radial compression and 0. 16-5.28N to longitudinal compression. From literature is also possible to verify that stents must present 75% of unchanged diameter during the bending test and must possess a porosity between 70% and 80% [4]. The produced polyester stent presents values of 1.29N for radial compression, 0.23N for longitudinal compression, 80% of porosity and 85.5% of unchanged diameter, during bending tests. For the antibacterial functionalization, silver oxide nanocoatings were prepared, through reactive magnetron g, with an Ag target in an Ar +O2 atmosphere. In order to evaluate the nanostructure and morphology of the coatings, d ifferent technique s like X-ray diffraction (XRD), scanning electron microscopy (SEM) and and X- ray photoelectron spectroscopy (XPS were used. From the analyses of XRD it is possible to verify that the peaks corresponds to planes of Ag2 O and MATERIAIS 2015 Porto, 21-23 June, 2015 characterize a cubic phase. The presence of Ag2 O is corroborated by XPS spectrum, where it is possible to observe silver, not only, in oxide state, but a lso in mettalic state, and it is possible to verify the presence of silver clusters, confirmed by SEM analysis. Films’ roughness and topography, parameters influencing the wettability of the surface and microorganism adhesion, were measured by Atomic Force Microscopy (AFM), and it was observed that the roughness is very low (under 10 nm). Coatings’ hydrophobicity and surface tension parameters were determined by contact angle measurement, and it was verified the hydrophobic behavior of the coatings. For antibacterial tests were used Staphylococcus epidermidis strain (IE186) and Staphylococcus aureus(ATCC 6538), and halo inhibition zone tests were realized. Ag+release rates were studied by means of inductively coupled plasma mass spectrometry (ICP -MS). The obtained results suggest that silver oxide coatings do not modify significantly surface properties of the substrate, like hydrophobicity and roughness, and present antimicrobial properties for both bacteria used.