Somein situ STM contributions to the characterization of electrochemical systems

We present a critical review on the use of STM as anin situ technique to characterize electrochemical systems based on the work performed in our laboratory. Contributions ofin situ STM studies include: (i) atomic resolution of electrodeposited lead on graphite; (ii) imaging of modifications on metallic electrode surfaces induced by electrochemical oxidation-reduction processes; (iii) imaging of corrosion process on aluminium and Al-Ta alloy electrodes in NaCl solution; (iv) characterization of semiconductor-solution interfaces. These studies allowed: (a) establishment of STM as a technique which, for some systems, yields atomic resolution of metallic surfaces in air and in solution; (b) establishment of a mechanism for the electrochemical growth of oxide films on metal electrodes; (c) establishment of a corresponding mechanism for the reduction of those electrochemically grown oxide films; (d) direct monitoring of corrosion processes on a scale of nm to m; and (e) determination of the presence of surface states and their energy position at the semiconductor-solution interfaces.This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday and in recognition of his outstanding contribution to electrochemistry.     

Compatibility of polysaccharide/maleic copolymer blends. IV. Thermal behavior of hydroxypropyl cellulose‐containing blends

The compatibility of the hydroxypropyl cellulose (HPC) with maleic acid–vinyl acetate copolymer in the solid state was studied by thermogravimetry, thermo‐optical analysis, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and optical microscopy. It was established that physical interactions are prevalent in blends with a high content of HPC, whereas chemical interactions predominate in blends with a medium and low content of HPC. By increasing the temperature, the thermochemical reactions are favored. Thermal properties are dependent on the mixing ratio of the components. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2585–2597, 2003     

Preconditioning the solution of the time-dependent neutron diffusion equation by recycling Krylov subspaces

Spectral preconditioners are based on the fact that the convergence rate of the Krylov subspace methods is improved if the eigenvalues of the smallest magnitude of the system matrix are ‘removed’. In this paper, two preconditioning strategies are studied to solve a set of linear systems associated with the numerical integration of the time-dependent neutron diffusion equation. Both strategies can be implemented using the matrix–vector product as the main operation and succeed at reducing the total number of iterations needed to solve the set of systems.     

Processing of a Silicon-Carbide-Whisker-Reinforced Glass-Ceramic Composite by Microwave Heating

A calcium magnesium aluminosilicate-based glass that contained 10 wt% of silicon carbide whiskers (SiC _w ) as reinforcement was prepared by tape casting, followed by sintering either in a conventional furnace or in a microwave oven. The results were consistent with retardation of glass sintering through whisker bridging. The glass, by itself, was sintered to almost-full density at 750°C for 4 h by conventional furnace sintering; the best sintered composite, with an estimated density of ∼90%, was obtained at 800°C with a dwell time of 4 h. Sintering at a temperature of >800°C did not improve the densification but rather resulted in severe whisker oxidation. A reduced densification rate was observed for the samples that were sintered in nitrogen. By contrast, in the microwave oven, almost-full density for the glass and ∼95% of the theoretical density for the composite were obtainable at 850°C for 15 min, which represented a reduction of ∼10 h of the total processing time and a reduced SiC _w oxidation.     

Enzymatic degradation of thermoresponsive poly(N‐isopropylacrylamide) grafted to carboxymethylcellulose copolymers

The enzymatic degradation of poly(N‐isopropyl acrylamide) (PNIPAM) grafted to carboxymethylcellulose (CMC) copolymers with a cellulasic preparation (Trichoderma viride) was studied. The enzymatic activity of the cellulasic preparation against CMC and the grafted copolymers was determined by the Petterson–Porath method, while their reduced viscosity variation in the presence of the same preparation was also followed. It has been shown that the enzymatic degradation behavior depends on the copolymer composition and the reaction temperature. Reducing sugars analysis showed that the experimental values for the grafted copolymers were higher than the calculated ones. At 50°C, the enzymatic reaction is completed in about 20 min for the copolymers, whereas for CMC it takes more than 40 min. It can be concluded that their enzymatic degradation is facilitated by the presence of the PNIPAM grafts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1383–1386, 2003     

Role of cognitive and functional performance in the interactions between elderly people with cognitive decline and an avatar on TV

The complexity of new information technologies (IT) may limit the access of elderly people to the information society, exacerbating what is known as “the digital divide,” as they appear to be too challenging for elderly citizens regardless of the integrity of their cognitive status. This study is an attempt to clarify how some cognitive functions (such as attention or verbal memory) may determine the interaction of cognitively impaired elderly people with technology. Twenty participants ranging from mild cognitive impairment to moderate Alzheimer’s disease were assessed by means of a neuropsychological and functional battery and were asked to follow simple commands from an avatar appearing on a TV by means of a remote control, such as asking the participant to confirm their presence or to respond Yes/No to a proposal to see a TV program. The number of correct answers and command repetitions required for the user to respond were registered. The results show that participants with a better cognitive and functional state in specific tests show a significantly better performance in the TV task. The derived conclusion is that neuropsychological assessment may be used as a useful complementary tool for assistive technology developers in the adaptation of IT to the elderly with different cognitive and functional profiles. Further studies with larger samples are required to determine to what extent cognitive functions can actually predict older users’ interaction with technology.     

Design recommendations for camera-based head-controlled interfaces that replace the mouse for motion-impaired users

This work focuses on camera-based systems that are designed for mouse replacement. Usually, these interfaces are based on computer vision techniques that capture the user’s face or head movements and are specifically designed for users with disabilities. The work identifies and reviews the key factors of these interfaces based on the lessons learnt by the authors’ experience and by a comprehensive analysis of the literature to describe the specific points to consider in their design. These factors are as follows: user features to track, initial user detection (calibration), position mapping, feedback, error recovery, event execution, profiles and ergonomics of the system. The work compiles the solutions offered by different systems to help new designers avoid problems already discussed by the others.     

New thermosets obtained by cationic copolymerization of DGEBA with γ‐caprolactone with improvement in the shrinkage. II. Time–temperature–transformation (TTT) cure diagram

Mixtures of diglycidylether of bisphenol A (DGEBA) with different proportions of γ‐caprolactone (γ‐CL) were cured with ytterbium triflate as initiator. The curing was studied with differential scanning calorimetry (DSC) and thermo mechanical analysis (TMA). The results are presented in the form of a time–temperature–transformation diagram. The kinetic analysis was performed by means of the isoconversional integral procedure and the kinetic model was also determined using the Coats–Redfern method. Gelation was determined by means of combined experiences of DSC and TMA. The relationship between the glass transition temperature (T_g) and the degree of conversion α was determined by DSC. Using the isoconversional lines and the T_g‐α relationship, the vitrificacion curve was obtained. The methodology developed makes it possible to obtain the TTT diagram using only no‐isothermal experiments with equivalent results to those using classical isothermal procedures. The addition of γ‐CL accelerates the curing and reduces the shrinkage after gelation and consequently the internal stresses in the material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Biochemical,functional, and histochemical effects of essential fatty acid deficiency in rat kidney

The present study was designed to examine the effects of EFA deficiency (EFAD) on biochemical, functional, and structural aspects of the kidney in growing and adult rats fed a normal or EFAD diet for 9 wk after weaning. Food and fluid intake (FI), urine volume, and Na⁺ and K⁺ excretions were measured weekly from weeks 4 to 8 by placing the rats in individual metabolic cages for 24 h. At week 9, Li⁺ and a 5% water load, respectively, were administered at 14 and 1.5 h prior to glomerular and proximal tubular function studies, as assessed by 3-h creatinine (C_Cr) and Li⁺ (C_Li+) clearances. Hematocrit and urine volume; serum and urine [Cr], [Li⁺], [Na⁺], and [K⁺]; and renal FA distribution were also measured. Data [corrected to 100 g/body weight (bw) and presented as means ±SEM] were significant, at P<-0.05. Despite a similar ingestion of solids from weeks 4 to 7 (weeks 7 to 10 of life), the rats on the EFAD diet showed a decreased body weight from week 5. From weeks 4 to 8, Fl and urine volume were similar for both groups, but the Fl increased at week 6 in the EFAD group; 24-h Na⁺ and K⁺ excretions were similar at all weeks, except for an increase in the EFAD group for both ions at week 7. In the EFAD group, C_Cr and C_Li+ decreased by 27 and 56.3%, respectively (385.7±33.4 vs. 280±21.1, and 21.0±2.1 vs. 9.2±1.1 μL/min/100 g; n=9 vs. 10), the latter result suggesting increased proximal reabsorption. The 3-h Na⁺ and K⁺ excretions were similar, but the Li⁺ decreased (0.78±0.06×10⁻² vs. 0.32±0.03×10⁻² μeq/min/100 g) in the EFAD group, giving additional support to the suggestion. Renal structure was normal and similar for both groups, but the EFAD group showed a more prominent proximal tubule brush border, together with heavier periodic acid-Schiff staining in all specimens from weeks 5 to 9. In the EFAD group, FA of the n−9 and n−7 series were higher, but most of the n−6 series were lower as a percentage of total lipids in the medulla and cortex. Medullary levels of 20∶4n−6 were maintained, 22∶4n−6 declined twice, arachidonic acid was maintained, and 20∶5n−3 was lower. The EFAD diet affected glomerular function, proximal tubular structure and function, and FA distribution in the rat kidney.     

Behaviour of a copper-AISI 304 stainless steel mixed anode in electrolytic copper refining with periodic current reversal

In the search for suitable materials to be used as anode supports in the periodic current reversal refining process this work covers the study of austenitic AISI 304 stainless steel. Experimental results show that the resistance of this steel to the aggressive action of the refining electrolyte is good at the working temperature of 60°C since no corrosion was detected after 24 h of electrolysis. The periodic polarization of this material results in a progressive passivation which was observed by operating under different initial surface conditions and by detecting remnant anodic currents which gradually decreased with time. For time ratios lower than twenty, a build up of metallic copper deposit on the steel part of the mixed anode occurred whatever the current density used.