Nanoindentation and scratch behaviour of Ni–P electroless coatings

ABSTRACT

In the present paper, the mechanical properties and the scratch failure mechanisms of Ni–P electroless coatings are described. The material microstructure was studied in as-deposited and annealed conditions through SEM and EDS analyses. Nanoindentation measurements on the coatings showed a remarkable hardening due to the crystallization and precipitation behaviour produced by annealing. The scratch tests, conducted by increasing the load during scratch, revealed the coating failure mechanisms in a broad range of applied stresses up to delamination.     

Energetics and Structure of Polymer‐Derived Si–(B–)O–C Glasses: Effect of the Boron Content and Pyrolysis Temperature

The structure and properties of polymer‐derived Si–(B–)O–C glasses have been shown to be significantly influenced by the boron content and pyrolysis temperature. This work determined the impact of these two parameters on the thermodynamic stability of these glasses. High‐temperature oxide melt solution calorimetry was performed on a series of amorphous samples, with varying boron contents (0–7.7 at.%), obtained by pyrolysis of precursors made by a sol–gel technique. Thermodynamic analysis of the calorimetric results demonstrated that at a constant pyrolysis temperature, adding boron makes the materials energetically less stable. While the B‐containing glasses pyrolyzed at 1000°C were energetically less stable than the competitive crystalline components, increasing the pyrolysis temperature to 1200°C led to their enthalpic stability. ²⁹Si and ¹¹B MAS nuclear magnetic resonance (NMR) spectroscopy measurements on selected samples confirmed a decrease in the concentrations of mixed Si‐centered SO_iC_4?i and B‐centered BO_jC_3?j bonds at the expense of formation of SiO₄ and B(OSi)₃ species (indicating a tendency toward phase separation) when the boron content and pyrolysis temperature increased. In light of the findings from calorimetry and NMR spectroscopy, we propose a structure–energetic relationship in Si–(B–)O–C glasses.     

Piperazine and methyldiethanolamine interrelationships in CO2 absorption by aqueous amine mixtures. Part II—Saturation rates of mixed reagent solutions

This work is a companion to a previous article, Part I, published in The Canadian Journal of Chemical Engineering, dealing with CO₂ absorption in aqueous solutions containing a single aminic reagent (specifically methyldiethanolamine (MDEA) or piperazine (PZ)). In this second part, different PZ/MDEA mixtures are experimentally studied and their performances are compared with that of the single reagents. It is indeed well known that small quantities of PZ added to MDEA aqueous solutions are sufficient to obtain a significant improvement in the kinetics of the process. PZ is considered an activator or promoter for MDEA, but the mechanism of this synergy has still not been clearly demonstrated. The aim of this study is an attempt to understand how PZ and MDEA can interact by experimentally analyzing this beneficial mutual effect and by explaining it with the help of a suitable yet not complex model. We believe that the involved chemistry is not more complex than that reported in Part I for the single reagents. According to our findings, it is MDEA that enhances the action of PZ, as opposed to what many authors claim. Moreover, our results seem to rule out the existence of any PZ shuttle effect.     

Evaluation of performance of various color‐difference formulae using an experimental black dataset

The objective of this study was to develop a specific visual dataset comprising black‐appearing samples with low lightness (L* ranging from approximately 10.4 to 19.5), varying in hue and chroma, evaluating their visual differences against a reference sample, and testing the performance of major color difference formulas currently in use as well as OSA‐UCS‐based models and more recent CAM02 color difference formulas including CAM02‐SCD and CAM02‐UCS models. The dataset comprised 50 dyed black fabric samples of similar structure, and a standard (L*= 15.33, a* = 0.14, b* = ?0.82), with a distribution of small color differences, in ΔE^*_ab, from 0 to approximately 5. The visual color difference between each sample and the standard was assessed by 19 observers in three separate sittings with an interval of at least 24 hours between trials using an AATCC standard gray scale for color change, and a total of 2850 assessments were obtained. A third‐degree polynomial equation was used to convert gray scale ratings to visual differences. The Standard Residual Sum of Squares index (STRESS) and Pearson's correlation coefficient (r), were used to evaluate the performance of various color difference formulae based on visual results. According to the analysis of STRESS index and correlation coefficient results CAM02 color difference equations exhibited the best agreement against visual data with statistically significant improvement over other models tested. The CIEDE2000 (1:1:1) equation also showed good performance in this region of the color space. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 589–598, 2014     

Transition Metal‐Free Direct C?H (Hetero)arylation of Heteroarenes: A Sustainable Methodology to Access (Hetero)aryl‐Substituted Heteroarenes

In recent years, environmental and economic reasons have motivated the development of transition metal‐free carbon‐carbon bond forming reactions and some excellent reviews have covered this research area of particular interest for the pharmaceutical industry. However, none of these reviews has been specifically dedicated to summarize and discuss the results achieved in the rapidly growing field of the transition metal‐free direct (hetero)arylation reactions of heteroarenes. This review, which covers the literature from 2008 to 2014, aims to provide a thorough insight into the synthetic and mechanistic aspects of these atom economic and environmentally benign reactions also highlighting their advantages and possible disadvantages compared to conventional methods for the synthesis of arylheteroarenes and biheteroaryls via transition metal‐catalyzed reactions.

     

Detection of frozen salt in pipes using gamma-ray spectrometry of potassium self-activity

Solar plants that use molten salts as heat transfer fluid need careful control to avoid the freezing of the salt in the pipes; if such a problem occurs, a diagnostic instrument to localize where is the frozen salt plug and to determine its length is useful. If the salt contains potassium (as is the case of the most common mixture used in solar plants, NaNO₃/KNO₃ 60/40% by weight), the gamma decay of the natural unstable isotope ⁴⁰K can be exploited to detect the frozen salt in a non-invasive way. Simulations and experimental results regarding the detectability of such plugs with different masses/lengths are presented.     

The effect of low‐power microwaves on the growth of bacterial populations in a plug flow reactor

A plug flow reactor (PFR) which permits the growth of bacteria in a microwave environment is described. The apparatus is used to analyse the effect of microwave radiation at the frequency of 2.45 GHz and at 37°C on the growth rate of three bacterial species: Bacillus clausii, Pseudomonas aeruginosa, and Staphylococcus aureus. The growth constant is determined for reacting mixtures irradiated with microwaves of different powers ranging from 0 to 400 mW. Analyses show that (a) the apparatus is able to perform the experimental runs maintaining an aseptic environment; (b) under the microwave power levels examined in the present study, no effects are detected for the Bacillus clausii and Pseudomonas aeruginosa species, while for the Staphylococcus aureus species, a few small effects are found (a minimum value of the growth constant at 200 mW and an increase of the constant between 200 and 400 mW). © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Study of different nanostructured carbon supports for fuel cell catalysts

Pt clusters were deposited by an impregnation process on three carbon supports: multi-wall carbon nanotubes (MWNT), single-wall carbon nanohorns (SWNH), and Vulcan XC-72 carbon black to investigate the effect of the carbon support structure on the possibility of reducing Pt loading on electrodes for direct methanol (DMFC) fuel cells without impairing performance. MWNT and SWNH were in-house synthesised by a DC and an AC arc discharge process between pure graphite electrodes, respectively. UV-vis spectrophotometry, scanning and transmission electron microscopy, X-ray diffraction, and cyclic voltammetry measurements were used to characterize the Pt particles deposited on the three carbon supports. A differential yield for Pt deposition, not strictly related to the surface area of the carbon support, was observed. SWNH showed the highest surface chemical activity toward Pt deposition. Pt deposited in different forms depending on the carbon support. Electrochemical characterizations showed that the Pt nanostructures deposited on MWNT are particularly efficient in the methanol oxidation reaction.