TiAlN coatings deposited by triode magnetron sputtering varying the bias voltage

TiAlN films were deposited on AISI O1 tool steel using a triode magnetron sputtering system. The bias voltage effect on the composition, thickness, crystallography, microstructure, hardness and adhesion strength was investigated. The coatings thickness and elemental composition analyses were carried out using scanning electron microscopy (SEM) together with energy dispersive X-ray (EDS). The re-sputtering effect due to the high-energy ions bombardment on the film surface influenced the coatings thickness. The films crystallography was investigated using X-ray diffraction characterization. The X-ray diffraction (XRD) data show that TiAlN coatings were crystallized in the cubic NaCl B1 structure, with orientations in the {111}, {200} {220} and {311} crystallographic planes. The surface morphology (roughness and grain size) of TiAlN coatings was investigated by atomic force microscopy (AFM). By increasing the substrate bias voltage from -40 to -150 V, hardness decreased from 32 GPa to 19 GPa. Scratch tester was used for measuring the critical loads and for measuring the adhesion. (C) 2011 Elsevier B. V. All rights reserved.

Assessment of the cavitation erosion resistance in high nitrogen austenitic stainless steels: study of the wear mechanisms

Specimens of a UNS S31803 steel were submitted to high temperature gas nitriding and then to vibratory pitting wear tests. Nitrided samples displayed fully austenitic microstructures and 0.9 wt. % nitrogen contents. Prior to pitting tests, sample texture was characterized by electron backscattering diffraction, EBSD. Later on, the samples were tested in a vibratory pit testing equipment using distilled water Pitting tests were periodically interrupted to evaluate mass loss and to characterize the surface wear by SEM observations. At earlier pit erosion, stages intense and highly heterogeneous plastic deformation inside individual grains was observed. Later on, after the incubation period, mass loss by debris detachment was observed. Initial debris micro fracturing was addressed to low cycle fatigue. Damage started at both sites, inside the grains and grain boundaries. The twin boundaries were the most prone to mass-loss incubation. Grains with (101) planes oriented near parallel to the sample surface displayed higher wear resistance than grains with other textures. This was attributed to lower resolved stresses for plastic deformation inside the grains with (101)

Fretting fatigue in overhead conductors: Rig design and failure analysis of a Grosbeak aluminium cable steel reinforced conductor

The performance optimisation of overhead conductors depends on the systematic investigation of the fretting fatigue mechanisms in the conductor/clamping system. As a consequence, a fretting fatigue rig was designed and a limited range of fatigue tests was carried out at the middle high cycle fatigue regime in order to access an exploratory S-N curve for a Grosbeak conductor, which was mounted on a mono-articulated aluminium clamping system. Subsequent to these preliminary fatigue tests, the components of the conductor/clamping system, such as ACSR conductor, upper and lower clamps, bolt and nuts, were subjected to a failure analysis procedure in order to investigate the metallurgical free variables interfering on the fatigue test results, aiming at the optimisation of the testing reproducibility. The results indicated that the rupture of the planar fracture surfaces observed in the external At strands of the conductor tested under lower bending amplitude (0.9 mm) occurred by fatigue cracking (I mm deep), followed by shear overload. The V-type fracture surfaces observed in some At strands of the conductor tested under higher bending amplitude (1.3 mm) were also produced by fatigue cracking (approximately 400 mu m deep), followed by shear overload. Shear overload fracture (45 degrees fracture surface) was also observed on the remaining At wires of the conductor tested under higher bending amplitude (1.3 mm). Additionally, the upper and lower Al-cast clamps presented microstructure-sensitive cracking, which was folowed by particle detachment and formation of abrasive debris on the clamp/conductor tribo-interface, promoting even further the fretting mechanism. The detrimental formation of abrasive debris might be inhibited by the selection of a more suitable class of as-cast At alloy for the production of clamps. Finally, the bolt/nut system showed intense degradation of the carbon steel nut (fabricated in ferritic-pearlitic carbon steel, featuring machined threads with 190 HV), with intense plastic deformation and loss of material. Proper selection of both the bolt and nut materials and the finishing processing might prevent the loss in the clamping pressure during the fretting testing. It is important to control the specification of these components (clamps, bolt and nuts) prior to the start of large scale fretting fatigue testing of the overhead conductors in order to increase the reproducibility of this assessment. (c) 2008 Elsevier Ltd. All rights reserved.

Mechanical Blocking Mechanism for the Columnar to Equiaxed Transition

Mechanical blocking of the columnar front during the columnar to equiaxed transition (CET) is studied by quantitatively comparing the CET positions obtained with one stochastic model and two deterministic models for the unidirectional solidification of an Al-7 (wt pct) Si alloy. One of the deterministic models is based on the solutal blocking of the columnar front, whereas the other model is based on the mechanical blocking. The solutal-blocking model and the mechanical-blocking model with the traditional blocking fraction of 0.49 give columnar zones larger than those predicted with the stochastic model. When a blocking fraction of 0.2 is adopted, however, the agreement is very good for a range of nucleation undercoolings and number density of equiaxed grains. Therefore, changing the mechanical-blocking fraction in deterministic models from 0.49 to 0.2 seems to model more accurately the mechanical-blocking process that can lead to the CET.

Failure assessments of corroded pipelines with axial defects using stress-based criteria: Numerical studies and verification analyses

Conventional procedures used to assess the integrity of corroded piping systems with axial defects generally employ simplified failure criteria based upon a plastic collapse failure mechanism incorporating the tensile properties of the pipe material. These methods establish acceptance criteria for defects based on limited experimental data for low strength structural steels which do not necessarily address specific requirements for the high grade steels currently used. For these cases, failure assessments may be overly conservative or provide significant scatter in their predictions, which lead to unnecessary repair or replacement of in-service pipelines. Motivated by these observations, this study examines the applicability of a stress-based criterion based upon plastic instability analysis to predict the failure pressure of corroded pipelines with axial defects. A central focus is to gain additional insight into effects of defect geometry and material properties on the attainment of a local limit load to support the development of stress-based burst strength criteria. The work provides an extensive body of results which lend further support to adopt failure criteria for corroded pipelines based upon ligament instability analyses. A verification study conducted on burst testing of large-diameter pipe specimens with different defect length shows the effectiveness of a stress-based criterion using local ligament instability in burst pressure predictions, even though the adopted burst criterion exhibits a potential dependence on defect geometry and possibly on material`s strain hardening capacity. Overall, the results presented here suggests that use of stress-based criteria based upon plastic instability analysis of the defect ligament is a valid engineering tool for integrity assessments of pipelines with axial corroded defects. (C) 2008 Elsevier Ltd. All rights reserved.

Influence of cerium (IV) ions on the mechanism of organosilane polymerization and on the improvement of its barrier properties

In this work, the effect of cerium (IV) ammonium nitrate (CAN) addition on the polymerization of bis-[triethoxysilyl]ethane (BTSE) film applied on carbon steel was studied. The electrochemical characterization of the films was carried out in 0.1 mol L(-1) NaCl solution by open-circuit potential measurements, anodic and cathodic polarization curves and electrochemical impedance spectroscopy (EIS). Morphological and chemical characterization were performed by atomic force microscopy (AFM), contact angle measurements, infrared-spectroscopy, nuclear magnetic resonance and thermogravimetric analysis. The results have clearly shown the improvement on the protective properties of the Ce(4+) modified film as a consequence of the formation of a more uniform and densely reticulated silane film. A mechanism is proposed to explain the accelerating role of Ce(4+) ions on the cross-linking of the silane layer. (C) 2008 Elsevier Ltd. All rights reserved.

Who should wear mask against airborne infections? Altering the contact network for controlling the spread of contagious diseases

There are several ways of controlling the propagation of a contagious disease. For instance, to reduce the spreading of an airborne infection, individuals can be encouraged to remain in their homes and/or to wear face masks outside their domiciles. However, when a limited amount of masks is available, who should use them: the susceptible subjects, the infective persons or both populations? Here we employ susceptible-infective-recovered (SIR) models described in terms of ordinary differential equations and probabilistic cellular automata in order to investigate how the deletion of links in the random complex network representing the social contacts among individuals affects the dynamics of a contagious disease. The inspiration for this study comes from recent discussions about the impact of measures usually recommended by health public organizations for preventing the propagation of the swine influenza A (H1N1) virus. Our answer to this question can be valid for other eco-epidemiological systems. (C) 2010 Elsevier BM. All rights reserved.

Study of copper electrodeposition mechanism from a strike alkaline bath prepared with 1-hydroxyethane-1,1-diphosphonic acid through cyclic voltammetry technique

Copper strike baths are extensively used in metal plating industry as they present the ability to plate adherent copper layers on less-noble metal substrates such as steel and zinc die castings. However, in the last few years, due to environmental controls and safety policies for operators, the plating industry has been interested in replacing the toxic cyanide copper strike baths with environmentally friendly baths. A broad bibliographic review showed that the published papers, referring to the new nontoxic copper strike baths, are patents, having little or no emphasis focused on electrodeposition mechanisms. Therefore, it was decided to study the copper electrodeposition mechanism from a strike alkaline bath prepared with one of the most nontoxic chelating agents cited in many patents which is the 1-hydroxyethane-1,1-diphosphonic acid, known as HEDP. This acid forms very stable water soluble complexes with Cu(2+) ions, thus cupric sulfate was used for preparing the plating bath. The results obtained through a cyclic voltammetry technique showed that Cu(2+) ion reduction to Cu from an HEDP electrodeposition bath occurs via a direct reduction reaction without a formation of Cu(+) intermediates. (C) 2010 Elsevier Ltd. All rights reserved.

Squeeze flow as a tool for developing optimized gypsum plasters

This paper presents a rheological investigation of pure gypsum (PG) and a commercial gypsum-lime-filler plaster (CP) using the modified Vicat apparatus and squeeze flow method. The samples were tested at several different intervals after manual or mechanical mixing. The results confirmed squeeze flow to be more sensitive in determining fresh paste behavior than the modified Vicat apparatus. PG set faster when prepared in mechanical mixer than when manually mixed. Conversely, the CP composition presented longer setting when mixed mechanically. The study also included the analysis of two ready-to-use polymer-based products for leveling and rendering (drywall joint compound - DJC; acrylic putty - AP) measured by squeeze flow and compared to the commercial composition. (C) 2008 Elsevier Ltd. All rights reserved.

Storage as a tool to improve wood fuel quality

This work analysed the influence of storage in the quality of forest biomass for energy generation in the region of Lages, Brazil. Logs of Pinus taeda L. and Eucalyptus dunnii Maiden were harvested and piled during the four different seasons: spring, summer, fall and winter. The analyses were performed immediately after harvesting (without being stored), after two, four and six months of storage. The evaluated properties were: moisture content, gross and net calorific value, ash content and solubility in cold water, hot water and sodium hydroxide. The species composition, storage span, harvesting season and storage season influenced the forest biomass characteristics. In general, eucalyptus presented better results than pine, losing moisture faster, having less alteration in the chemical composition and producing greater energetic gain over storage time. For both species, the ideal storage time was four months. Furthermore, spring and summer were the best harvesting seasons. Thus, if the forest biomass is harvested at the end of winter or beginning of spring with subsequent storage during the summer, this biomass will have the best performance for energy production. (C) 2011 Elsevier Ltd. All rights reserved.

Enzymatic-spectrophotometric determination of paraquat in urine samples: A method based on its toxic mechanism

Paraquat is a broad-spectrum contact herbicide that has been encountered worldwide in several cases of accidental, homicidal, and suicidal poisonings. The pulmonary toxicity of this compound is related to the depletion of NADPH in the pneumocytes, which is continuously consumed by the reduction/oxidation of paraquat and reductase enzyme systems in the presence of O(2) (redox cycling). Based on this mechanism, an enzymatic-spectrophotometric method was developed for the determination of paraquat in urine samples. The velocity of NADPH consumption was monitored at 340 nm, every 10 s during 15 min. The velocity of NADPH oxidation correlated with the paraquat levels found in samples. The enzymatic-spectrophotometric method showed to be sensitive, making possible the detection of paraquat in urine samples at concentrations as low as 0.05 mg/L.

Intrinsic Dissolution as a Tool for Evaluating Drug Solubility in Accordance with the Biopharmaceutics Classification System

The Biopharmaceutics Classification System (BCS) is a tool that was created to categorize drugs into different groups according to their solubility and permeability characteristics. Through a combination of these factors and physiological parameters, it is possible to understand the absorption behavior of a drug in the gastrointestinal tract, thus contributing to cost and time reductions in drug development, as well as reducing exposure of human subjects during in vivo trials. Solubility is attained by determining the equilibrium under conditions of physiological pH, while different methods may be employed for evaluating permeability. On the other hand, the intrinsic dissolution rate (IDR), which is defined as the rate of dissolution of a pure substance under constant temperature, pH, and surface area conditions, among others, may present greater correlation to the in vivo dissolution dynamic than the solubility test. The purpose of this work is to discuss the intrinsic dissolution test as a tool for determining the solubility of drugs within the scope of the Biopharmaceutics Classification System (BCS).

Molecular modeling as a promising tool to study dendrimer prodrugs delivery

Molecular modeling methodologies were applied to perform preliminary studies concerning the release of active agents from potentially antichagasic and antileishmanial dendrimer prodrugs. The dendrimer was designed having myo-inositol as a core, L-malic acid as a spacer group, and hydroxymethylnitrofurazone (NFOH), 3-hydroxyflavone or quercetin, as active compounds. Each dendrimer presented a particular behavior concerning to the following investigated properties: spatial hindrance, map of electrostatic potential (MEP), and the lowest unoccupied molecular orbital energy (E(LUMO)). Additionally, the findings suggested that the carbonyl group next to the active agent seems to be the most promising ester breaking point. (C) 2009 Elsevier B.V. All rights reserved.

Self-Organizing Maps as a New Tool for Classification of Plants at Lower Hierarchical Levels

A chemotaxonomic analysis is described of a database containing various types of compounds from the Heliantheae tribe (Asteraceae) using Self-Organizing Maps (SOM). The numbers of occurrences of 9 chemical classes in different taxa of the tribe were used as variables. The study shows that SOM applied to chemical data can contribute to differentiate genera, subtribes, and groups of subtribes (subtribe branches), as well as to tribal and subtribal classifications of Heliantheae, exhibiting a high hit percentage comparable to that of an expert performance, and in agreement with the previous tribe classification proposed by Stuessy.

Structural complexes of human adenine phosphoribosyltransferase reveal novel features of the APRT catalytic mechanism

Adenine phosphoribosyltransferase (APRT) is an important enzyme component of the purine recycling pathway. Parasitic protozoa of the order Kinetoplastida are unable to synthesize purines de novo and use the salvage pathway for the synthesis of purine bases rendering this biosynthetic pathway an attractive target for antiparasitic drug design. The recombinant human adenine phosphoribosyltransferase (hAPRT) structure was resolved in the presence of AMP in the active site to 1.76 angstrom resolution and with the substrates PRPP and adenine simultaneously bound to the catalytic site to 1.83 angstrom resolution. An additional structure was solved containing one subunit of the dimer in the apo-form to 2.10 angstrom resolution. Comparisons of these three hAPRT structures with other `type I` PRTases revealed several important features of this class of enzymes. Our data indicate that the flexible loop structure adopts an open conformation before and after binding of both substrates adenine and PRPR Comparative analyses presented here provide structural evidence to propose the role of Glu 104 as the residue that abstracts the proton of adenine N9 atom before its nucleophilic attack on the PRPP anomeric carbon. This work leads to new insights to the understanding of the APRT catalytic mechanism.