P.A.P. Nascente

Surface characterisation of plasma-nitrided iron by X-ray photoelectron spectroscopy

Abstract The nitriding by plasma has the potential to improve the tribological and mechanical properties on a number of substrates, and offers various advantages as compared with other methods used in the modification of surfaces. We prepared four samples by nitriding the iron substrates in a gas mixture (80% H 2 and 20% N 2 ) under a pressure of 9.0 mbar, discharge frequency of 10 kHz and temperature of 773 K, for periods of 1, 2, 4 and 6 h. We characterised the samples by scanning electron microscopy (SEM), X-ray diffraction (XRD) and microhardness techniques, and detected the presence of Fe 4 N and Fe 2–3 N phases. We employed X-ray photoelectron spectroscopy (XPS) to obtain chemical-state and quantitative information of the plasma-nitrided iron surfaces. In situ cleaning was carried out by argon ion bombardment. The Fe 2p 3/2 photoelectron peaks for all samples presented three components, associated with Fe 0 , Fe 2+ and Fe 3+ , while the N 1s lines showed two components, the main one due to iron nitride and the other is connected with oxidised nitrogen.

Growth of aluminum-free porous oxide layers on titanium and its alloys Ti-6Al-4V and Ti-6Al-7Nb by micro-arc oxidation

The growth of oxides on the surfaces of pure Ti and two of its ternary alloys, Ti-6Al-4V and Ti-6Al-7Nb, by micro-arc oxidation (MAO) in a pH 5 phosphate buffer was investigated. The primary aim was to form thick, porous, and aluminum-free oxide layers, because these characteristics favor bonding between bone and metal when the latter is implanted in the human body. On Ti, Ti-6Al-4 V, and Ti-6Al-7Nb, the oxides exhibited breakdown potentials of about 200 V, 130 V, and 140 V, respectively, indicating that the oxide formed on the pure metal is the most stable. The use of the MAO procedure led to the formation of highly porous oxides, with a uniform distribution of pores; the pores varied in size, depending on the anodizing applied voltage and time. Irrespective of the material being anodized, Raman analyses allowed us to determine that the oxide films consisted mainly of the anatase phase of TiO2, and XPS results indicated that this oxide is free of Al and any other alloying element.

Elaboration and Characterization of Nano-Biocomposites Based on Plasticized Poly(Hydroxybutyrate-Co-Hydroxyvalerate) with Organo-Modified Montmorillonite

Nano-biocomposites based on a biodegradable bacterial copolyester, poly(hydroxybutyrate-co-hydroxyvalerate), have been elaborated with an organo-modified montmorillonite (OMMT) clay as nanofiller, and acetyl tributyl citrate as plasticizer. The corresponding (nano)structures, thermal and mechanical properties, permeability, and biodegradability have been determined. Polyhydroxyalkanoates are very thermal sensitive then to follow the degradation the corresponding matrices have been analyzed by size exclusion chromatography. The results indicate that the addition of the plasticizer decreases the thermo-mechanical degradation, during the extrusion. These nano-biocomposites show an intercalated/exfoliated structure with good mechanical and barrier properties, and an appropriated biodegradation kinetic. Intending to understand the changes in the thermal properties, the nano-biocomposites were characterized by thermal gravimetric analysis and differential scanning calorimetry. The presence of the OMMT clay did not influence significantly the transition temperatures. However, the filler not only acted as a nucleating agent which enhanced the crystallization, but also as a thermal barrier, improving the thermal stability of the biopolymer. The results indicated that the addition of the plasticizer reduces the glass transition temperature and the crystalline melting temperature. The plasticizer acts as a processing aid and increases the processing temperature range (lower melting temperature).

Contactless conductivity biosensor in microchip containing folic acid as bioreceptor

We report a glass/PDMS-based microfluidic biosensor that integrates contactless conductivity transduction and folic acid, a target for tumor biomarker, as a bioreceptor. The device presents relevant advantages such as direct determination--dismiss the use of redox mediators as in faradaic electrochemical techniques--and the absence of the known drawbacks related to the electrode-solution interface. Characterizations of the functionalization processes and chemical sensor are described in this communication.

Effect of thermal aging conditions on the corrosion properties and hardness of a duplex stainless steel

The corrosion properties of a 22.5 wt. (%) Cr duplex stainless steel were investigated after long-term aging of 3000, 5000 and 7000 hours at 300 and 400 oC. The corrosion resistance was measured based on mass loss in a FeCl3 10 wt. (%) solution and electrochemical measurements in a 0.1 M H2SO4 solution. The results indicate that the corrosion resistance decreased steadily up to 5000 hours of aging. However, the samples subjected to 7000 hours of aging showed better corrosion resistance than those aged for 3000 and 5000 hours. This effect is attributed to the phase transformation that occurs during aging, a finding which was confirmed by hardness, transmission electron microscopy and X-ray photoelectron spectroscopy measurements.

X-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and x-ray diffraction characterization of CuO–TiO2–CeO2 catalyst system

X-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and x-ray absorption spectroscopy (XAS) techniques have been applied to characterize the surface composition and structure of a series of CuO–TiO2–CeO2 catalysts. For a small loading of cerium, ceria was mainly dispersed on the titania surface and a minor amount of CeO2 crystallite appeared. At higher loading of cerium, the CeO2 phase increased and the atomic Ce/Ti ratio values were smaller than the nominal composition, as a consequence of cerium agglomeration. This result suggests that only a fraction of cerium can be spread on the titania surface. For titanium-based mixed oxide, we observed that cerium is found as Ce3+ uniquely on the surface. The atomic Cu/(Ce+Ti) ratio values showed no influence from cerium concentration on the dispersion of copper, although the copper on the surface was shown to be dependent on the cerium species. For samples with a high amount of cerium, XPS analysis indicated the raise of second titanium species due c...

Growth and surface characterization of TiNbZr thin films deposited by magnetron sputtering for biomedical applications.

Low modulus of elasticity and the presence of non-toxic elements are important criteria for the development of materials for implant applications. Low modulus Ti alloys can be developed by designing β-Ti alloys containing non-toxic alloying elements such as Nb and Zr. Actually, most of the metallic implants are produced with stainless steel (SS) because it has adequate bulk properties to be used as biomaterials for orthopedic or dental implants and is less expensive than Ti and its alloys, but it is less biocompatible than them. The coating of this SS implants with Ti alloy thin films may be one alternative to improve the biomaterial properties at a relatively low cost. Sputtering is a physical deposition technique that allows the formation of nanostructured thin films. Nanostructured surfaces are interesting when it comes to the bone/implant interface due to the fact that both the surface and the bone have nanoscale particle sizes and similar mechanical properties. TiNbZr thin films were deposited on both Si(111) and stainless steel (SS) substrates. The TiNbZr/Si(111) film was used as a model system, while the TiNbZr/SS film might improve the biocompatibility and extend the life time of stainless steel implants. The morphology, chemical composition, Youngs modulus, and hardness of the films were analyzed by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and nanoindentation.

Oxide surface modification: Synthesis and characterization of zirconia-coated alumina

Four aluminas were used as supports for impregnation with a zirconium oxide with the aim to achieve a coating, without phase separation, between support and modifier. The supports were impregnated with different concentrations of zirconium aqueous resin, obtained through the polymeric precursor method. After impregnation the samples were calcined and then characterized by XRD, which led to identification of crystalline zirconia in different concentrations from each support used. Using a simple geometric model the maximum amount of surface modifier oxide required for the complete coating of a support with a layer of unit cells was estimated. According to this estimate, only the support should be identified below the limit proposed and crystalline zirconium oxide should be identified above this limit when a complete coating is reached. The results obtained from XRD agree with the estimated values and to confirm the coating, the samples were also characterized by EDS/STEM, HRTEM, XPS, and XAS. The results showed that the zirconium oxide on the surface of alumina support reached the coating in the limit of 15 Zr nm(-2), without the formation of the ZrO(2) phase.

XPS characterisation of ceria-stabilised zirconia doped with iron oxide

Abstract The addition of iron oxide on ceria-stabilised zirconia was studied by X-ray photoelectron spectroscopy (XPS). Zirconia presents a monoclinic to tetragonal phase transition at 1443 K, which is accompanied by a volume variation of approximately 3–5%, preventing the formation of a dense polycrystalline monoclinic ceramic. Ceria-stabilised tetragonal zirconia presents high toughness and can be applied as a structural material. However, CeO 2 –ZrO 2 has low sinterability, so it is important to investigate the effect of sintering dopants, such as iron, copper and manganese ions, which could improve the sinterability and the mechanical properties of the ceramic. In previous studies, it was shown that the addition of 0.3 mol% of Fe 2 O 3 helped in sintering the ceramic, and enhanced the electrical conductivity, although it was not determined if this enhancement was due to ionic or electronic contribution. In this work, we employed XPS to characterise ZrO 2 + x mol% CeO 2 +0.3 mol% Fe 2 O 3 , x =12 and 20, ceramics sintered at 1450 and 1600°C in order to better understand the influence of iron in the stabilisation of the tetragonal phase and electrical conductivity.

Treatment of polycarbonate by dielectric barrier discharge (DBD) at atmospheric pressure

Generally most plastic materials are intrinsically hydrophobic, low surface energy materials, and thus do not adhere well to other substances. Surface treatment of polymers by discharge plasmas is of great and increasing industrial application because it can uniformly modify the surface of sample without changing the material bulk properties and is environmentally friendly. The plasma processes that can be conducted under ambient pressure and temperature conditions have attracted special attention because of their easy implementation in industrial processing. Present work deals with surface modification of polycarbonate (PC) by a dielectric barrier discharge (DBD) at atmospheric pressure. The treatment was performed in a parallel plate reactor driven by a 60Hz power supply. The DBD plasmas at atmospheric pressure were generated in air and nitrogen. Material characterization was carried out by contact angle measurements, and X-ray photoelectron spectroscopy (XPS). The surface energy of the polymer surface was calculated from contact angle data by Owens- Wendt method using distilled water and diiodomethane as test liquids. The plasma-induced chemical modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. Due to these surface modifications the DBD-treated polymers become more hydrophilic. Aging behavior of the treated samples revealed that the polymer surfaces were prone to hydrophobic recovery although they did not completely recover their original wetting properties.