Biofouling and microbially influenced corrosion of stainless steels

Stainless steels are among the most investigated materials on biofouling and microbially-influenced corrosion (MIC). Although, generally corrosion-resistant owing to tenacious and passive surface film due to chromium, stainless steels are susceptible to extensive biofouling in subsoil, fresh water and sea water and chemical process environments. Biofilms influence their corrosion behavior due to corrosion potential ennoblement and sub-surface pitting. Both aerobic and anaerobic microorganisms catalyse microbial corrosion of stainless steels through biotic and abiotic mechanisms. MIC of stainless steels is common adjacent to welds at the heat-affected zone. Both austenite and delta ferrite phases may be susceptible. Even super stainless steels are found to be amenable to biofouling and MIC. Microbiological, electrochemical as well as physicochemical aspects of MIC pertaining to stainless steels in different environments are analyzed.

Film thickness mediated transition in the kinetics of electric current induced flow of thin liquid metal films

Application of high electric-field between two points in a thin metallic film results in liquefaction and subsequent flow of the liquid-film from one electrode to another in a radially symmetric fashion. Here, we report the transition of the flow kinetics driven by the liquid film thickness varying from 3 to 100 nm. The mechanism of the flow behavior is observed to be independent of the film thickness; however, the kinetics of the flow depends on the film thickness and the applied voltage. An analytical model, incorporating viscosity and varying electrical resistivity with film thickness, is developed to explain the experimental observations. (C) 2014 AIP Publishing LLC.

Effect of boron addition and processing of Ti-6Al-4V on corrosion behaviour and biocompatibility

Ti-6Al-4V is widely used to prepare biomedical implant for orthopaedic and dental applications, but it is an expensive choice relative to other implant materials such as stainless steels and Co-Cr alloys, in large part due to the high manufacturing cost. Adding boron to refine the as cast microstructure of Ti-6Al-4V can eliminate the need for extensive hot working and thereby reduce processing costs. The effect of 0.1 wt-% boron addition and the choice of processing route (forging or extrusion) was studied in the context of potential biomedical applications. Corrosion tests in simulated body fluid indicated that the presence of boron increased the corrosion rate of Ti-6Al-4V and that the increase was higher for forged alloys than for extruded alloys. Boron addition and processing route were found to have a minimal effect on the viability of osteoblasts on the alloy surfaces. It is concluded that the addition of boron could offer advantages during the processing of Ti-6Al-4V for biomedical applications.

Specroelectrochemical, Switching Kinetics, and Chronoamperometric Studies of Dibenzyl Derivative of Poly(3,4-propylenedioxythiophene) Thin-Film-Based Electrochromic Device

The dibenzyl derivative of poly(3,4-propylenedioxythiophene) (PProDOT-Bz(2)) thin film is deposited onto ITO-coated glass substrate by electropolymerization technique. The electropolymerization of ProDOT-Bz(2) is carried out by a three-electrode electrochemical cell. The cyclic voltammogram shows the redox properties of electrochemically prepared films deposited at different scan rates. The thin films prepared were characterized for its morphological properties to study the homogeniety. Classic six-layer structure of PProDOT-Bz(2) electrochromic device using this material was fabricated and reported for the first and its characterizations such as spectroelectrochemical, switching kinetics, and chronoamperometric studies are performed. The color contrast of the thin film and the device achieved are 64 and 40%, respectively, at lambda(max) (628 nm). The switching time is recorded and the observed values are 5 s from the coloring state to the bleaching state and vice versa. The chronoamperometry shows that the device performed up to 400 cycles, and it is capable of working up to 35 cycles without any degradation. (C) 2014 Wiley Periodicals, Inc.

An extended finite element model coupled with level set method for stable pitting corrosion

Mass balance between metal and electrolytic solution, separated by a moving interface, in stable pit growth results in a set of governing equations which are solved for concentration field and interface position (pit boundary evolution), which requires only three inputs, namely the solid metal concentration, saturation concentration of the dissolved metal ions and diffusion coefficient. A combined eXtended Finite Element Model (XFEM) and level set method is developed in this paper. The extended finite element model handles the jump discontinuity in the metal concentrations at the interface, by using discontinuous-derivative enrichment formulation for concentration discontinuity at the interface. This eliminates the requirement of using front conforming mesh and re-meshing after each time step as in conventional finite element method. A numerical technique known as level set method tracks the position of the moving interface and updates it over time. Numerical analysis for pitting corrosion of stainless steel 304 is presented. The above proposed method is validated by comparing the numerical results with experimental results, exact solutions and some other approximate solutions.

Role of surface chemistry in modulating drug release kinetics in titania nanotubes

Surface chemistry and the intrinsic porous architectures of porous substrates play a major role in the design of drug delivery systems. An interesting example is the drug elution characteristic from hydrothermally synthesised titania nanotubes with tunable surface chemistry. The variation in release rates of Ibuprofen (IBU) is largely influenced by the nature of the functional groups on titania nanotubes and pH of suspending medium. To elucidate the extent of interaction between the encapsulated IBU and the functional groups on titania nanotubes, the release profiles have been modelled with an empirical Hill equation. The analysis aided in establishing a probable mechanism for the release of IBU from the titania nanotubes. The study of controlled drug release from TiO2 has wider implication in the context of biomedical engineering. (C) 2014 Elsevier B.V. All rights reserved.

An extended finite-element model coupled with level set method for analysis of growth of corrosion pits in metallic structures

Mass balance between metal and electrolytic solution, separated by a moving interface, in stable pit growth results in a set of governing equations which are solved for concentration field and interface position (pit boundary evolution). The interface experiences a jump discontinuity in metal concentration. The extended finite-element model (XFEM) handles this jump discontinuity by using discontinuous-derivative enrichment formulation, eliminating the requirement of using front conforming mesh and re-meshing after each time step as in the conventional finite-element method. However, prior interface location is required so as to solve the governing equations for concentration field for which a numerical technique, the level set method, is used for tracking the interface explicitly and updating it over time. The level set method is chosen as it is independent of shape and location of the interface. Thus, a combined XFEM and level set method is developed in this paper. Numerical analysis for pitting corrosion of stainless steel 304 is presented. The above proposed model is validated by comparing the numerical results with experimental results, exact solutions and some other approximate solutions. An empirical model for pitting potential is also derived based on the finite-element results. Studies show that pitting profile depends on factors such as ion concentration, solution pH and temperature to a large extent. Studying the individual and combined effects of these factors on pitting potential is worth knowing, as pitting potential directly influences corrosion rate.

Kinetics of phase separation in polymer mixtures: A molecular dynamics study

We present detailed results from a molecular dynamics (MD) simulation of phase-separation kinetics in polymer mixtures. Our MD simulations naturally incorporate hydrodynamic effects. We find that polymeric phase separation (with dynamically symmetric components) is in the same universality class as segregation of simple fluids: the degree of polymerization only slows down the segregation kinetics. For d = 2 polymeric fluids, the domain growth law is L(t) similar to t(phi) with phi showing a crossover from 1/3 -> 1/2 -> 2/3. For d = 3 polymeric fluids, we see the crossover phi = 1/3 -> 1. Our MD simulations do not yet access the inertial hydrodynamic regime (with L similar to t(2/3)) of phase separation in 3-d fluids. (C) 2014 AIP Publishing LLC.

Enhancement of Corrosion Resistance of Zinc Coatings Using Green Additives

In the present work, morphology, microstructure, and electrochemical behavior of Zn coatings containing non-toxic additives have been investigated. Zn coatings were electrodeposited over mild steel substrates using Zn sulphate baths containing four different organic additives: sodium gluconate, dextrose, dextrin, and saccharin. All these additives are ``green'' and can be derived from food contents. Morphological and structural characterization using electron microscopy, x-ray diffraction, and texture co-efficient analysis revealed an appreciable alteration in the morphology and texture of the deposit depending on the type of additive used in the Zn plating bath. All the Zn coatings, however, were nano-crystalline irrespective of the type of additive used. Polarization and electrochemical impedance spectroscopic analysis, used to investigate the effect of the change in microstructure and morphology on corrosion resistance behavior, illustrated an improved corrosion resistance for Zn deposits obtained from plating bath containing additives as compared to the pure Zn coatings.

Pressure induced manifold enhancement of Li-kinetics in FCC fullerene

The reduction of the diffusion energy barrier for Li in electrodes is one of the required criteria to achieve better performances in Li ion batteries. Using density functional theory based calculations, we report a pressure induced manifold enhancement of Li-kinetics in bulk FCC fullerene. Scanning of the potential energy surface reveals a diffusion path with a low energy barrier of 0.62 eV, which reduces further under the application of hydrostatic pressure. The pressure induced reduction in the diffusion barrier continues till a uniform volume strain of 17.7% is reached. Further enhancement of strain increases the barrier due to the repulsion caused by C-C bond formation between two neighbouring fullerenes. The decrease in the barrier is attributed to the combined effect of charge transfer triggered by the enhanced interaction of Li with the fullerene as well as the change in profile of the local potential, which becomes more attractive for Li. The lowering of the barrier leads to an enhancement of two orders of magnitude in Li diffusivity at room temperature making pressurized bulk fullerene a promising artificial solid electrolyte interface (SEI) for a faster rechargeable battery.

A detailed numerical study of NOx kinetics in low calorific value H-2/CO syngas flames

The present study provides an extensive and detailed numerical analysis of NO chemical kinetics in low calorific value H-2/CO syngas flames utilizing predictions by five chemical kinetic mechanisms available out of which four deal with H-2/CO while the fifth mechanism (GRI 3.0) additionally accounts for hydrocarbon chemistry. Comparison of predicted axial NO profiles in premixed flat flames with measurements at 1 bar, 3.05 bar and 9.15 bar shows considerably large quantitative differences among the various mechanisms. However, at each pressure, the quantitative reaction path diagrams show similar NO formation pathways for most of the mechanisms. Interestingly, in counterflow diffusion flames, the quantitative reaction path diagrams and sensitivity analyses using the various mechanisms reveal major differences in the NO formation pathways and reaction rates of important reactions. The NNH and N2O intermediate pathways are found to be the major contributors for NO formation in all the reaction mechanisms except GRI 3.0 in syngas diffusion flames. The GRI 3.0 mechanism is observed to predict prompt NO pathway as the major contributing pathway to NO formation. This is attributed to prediction of a large concentration of CH radical by the GRI 3.0 as opposed to a relatively negligible value predicted by all other mechanisms. Also, the back-conversion of NNH into N2O at lower pressures (2-4 bar) was uniquely observed for one of the five mechanisms. The net reaction rates and peak flame temperatures are used to correlate and explain the differences observed in the peak NO] at different pressures. This study identifies key reactions needing assessment and also highlights the need for experimental data in syngas diffusion flames in order to assess and optimize H-2/CO and nitrogen chemistry. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Phase evolutions, growth kinetics and diffusion parameters in the Co-Ni-Ta system

Diffusion couple experiments are conducted to study phase evolutions in the Co-rich part of the Co-Ni-Ta phase diagram. This helps to examine the available phase diagram and propose a correction on the stability of the Co2Ta phase based on the compositional measurements and X-ray analysis. The growth rate of this phase decreases with an increase in Ni content. The same is reflected on the estimated integrated interdiffusion coefficients of the components in this phase. The possible reasons for this change are discussed based on the discussions of defects, crystal structure and the driving forces for diffusion. Diffusion rate of Co in the Co2Ta phase at the Co-rich composition is higher because of more number of Co-Co bonds present compared to that of Ta-Ta bonds and the presence of Co antisites for the deviation from the stoichiometry. The decrease in the diffusion coefficients because of Ni addition indicates that Ni preferably replaces Co antisites to decrease the diffusion rate. (C) 2014 Elsevier B.V. All rights reserved.

Kinetics of dispersion of nanoparticles in thin polymer films at high temperature

We report the first detailed study of the kinetics of dispersion of nanoparticles in thin polymer films using temperature dependent in situ X-ray scattering measurements. We show a comparably enhanced dispersion at higher temperatures for systems which are otherwise phase segregated at room temperature. Detailed analysis of the time dependent X-ray reflectivity and diffuse scattering data allows us to explore the out-of-plane and in-plane mobility of the nanoparticles in the polymer films. While the out-of-plane motion is diffusive with a diffusion coefficient almost two orders of magnitude lower than that expected in bulk polymer, the in-plane one is found to be super-diffusive resulting in significantly larger in-plane displacement at similar time scales. We discuss the origin of the observed highly anisotropic motion of nanoparticles due to their slaved motion with respect to the anisotropic chain orientation and consequent diffusivity anisotropy of matrix chains. We also suggest strategies to utilize these observations to kinetically improve dispersion in otherwise thermodynamically segregated polymer nanocomposite films.

Observation of photobleaching and intensity dependent kinetics in Ge22As22Se56 thin films under sub-bandgap light illumination

We experimentally demonstrate photobleaching (PB) in Ge22As22Se56 thin films, when illuminated with a diode pumped solid state laser (DPSSL) of wavelength 671 nm, which is far below the optical bandgap of the sample. Interestingly, we found that PB is a slow process and occurs even at moderate pump beam intensity of 0.2 W/cm(2), however the kinetics remain rather different.

Effect of electrical parameters on morphology and in-vitro corrosion resistance of plasma electrolytic oxidized films formed on zirconium

The objective of the present work is to study the effect of electrical process Parameters (duty cycle and frequency) on morphological, structural, and in-vitro corrosion characteristics of oxide films formed on zirconium by plasma electrolytic oxidation in an electrolyte system consisting of 5 g/L of trisodium orthophosphate. The oxide films fabricated on zirconium by systematically varying the duty cycle and frequency are characterized for its phase composition, surface morphology, chemical composition, roughness, wettability, surface energy, scratch resistance, corrosion resistance, apatite forming ability and osteoblast cell adhesion. X-ray diffraction pattern of all the oxide films showed the predominance of m-ZrO2 phase. Dense and uniform films with thickness varying from 9 to 15 mu m and roughness in the range of 0.62 to 1.03 mu m are formed. Porosity of oxide films is found to be increased with an increase infrequency. The water contact angle results demonstrated that the oxide films exhibited similar hydrophilicity to zirconium substrate. All oxide films showed improved corrosion resistance, as indicated by far lower corrosion current density and passive corrosion potential compared to the zirconium substrate in simulated body fluid environment, and among the four different combinations of duty cycle and frequency employed in the present study, the oxide film formed at 95% duty cycle and 50 Hz frequency (HDLF film) showed superior pitting corrosion resistance, which can be attributed to its pore free morpholOgy. Scratch test results showed that the HDLF oxide film adhered firmly to the substrate by developing a notable scratch resistance at 19.5 +/- 1.2.N. Besides the best corrosion resistance and scratch retistance, the HDLF film also showed good apatite forming ability and osteo sarcoma cell adhesion on its surface. The HDLF oxide film on zirconium with superior surface characteristics is believed to be useful for various types of implants in the dental and orthopedic fields. (C) 2015 Elsevier B.V. All rights reserved.