Studying the formation process of chromate conversion coatings on aluminium using continuous electrochemical noise resistance measurements

A unique electrochemical technique, namely continuous noise resistance calculation (CNRC), was used to obtain electrochemical kinetic information from the formation process of chromate conversion coatings (CCC) on aluminium electrodes. It was found that the noise resistance (R_n) of aluminium electrodes remained almost unchanged during electrodes' immersion in a chromate containing acidic solution where the CCC films were supposed to form rapidly. This result indicates that the formation of CCC was associated with continuous corrosion of the aluminium electrodes and that the CCC films formed on aluminium surface were not intact barrier films, but most likely porous layers. The CCCs became protective only after they were aged in the environment. Based on these findings, the formation and inhibition mechanisms of CCC have been discussed.     

Collaborative test of determination of iodine value in fish oils. 1. Reaction time and carbon tetrachloride or cyclohexane as solvents

Twenty-two laboratories participated in a collaborative test to determine the iodine value (IV) of eight samples of fish oil (four with IV<150, four with IV>150) with either carbon tetrachloride (AOCS Official Method Cd 1–25) or cyclohexane (AOCS Recommended Practice Cd 1b-87) as solvent and either 1 or 2 h of reaction time. Laboratories received coded duplicate samples (hidden duplicates) and carried out duplicate determinations on each oil by each solvent-time combination (open duplicates). Replacing carbon tetrachloride with cyclohexane resulted in a lower IV (P<0.001). The decrease averaged 1.6 IV units for low-IV oils and 3.8 IV units for high-IV oils; this difference in response of 2.2 IV units between low- and high-IV oils was significant (P<0.001). Increasing the reaction time had a relatively small effect (0.34±0.18). There was no interaction of reaction time with solvent or oil type. Cyclohexane caused emulsions, which made it difficult to titrate residual iodine and thus increased the variability of the determination. The repeatability standard deviations (s _r ), based on hidden duplicates, for 1-h reaction time with carbon tetrachloride and cyclohexane were 2.17 and 3.35, respectively. The corresponding reproducibility standard deviations were 2.73 and 4.53.     

Au/ZnO and Au/Fe2O3 catalysts for CO oxidation at ambient temperature: comments on the effect of synthesis conditions on the preparation of high activity catalysts prepared by coprecipitation

The preparation of Au/ZnO and Au/Fe₂O₃ catalysts using two coprecipitation methods is investigated to determine the important factors that control the synthesis of high activity catalysts for the oxidation of carbon monoxide at ambient temperature. In particular, the factors involved in the preparation of catalysts that are active without the need for a calcination step are evaluated. The two preparation methods differ in the manner in which the pH is controlled during the precipitation, either constant pH throughout or variable pH in which the pH is raised from an initial low value to a defined end point. Non-calcined Au/ZnO catalysts prepared using both methods are very sensitive to pH and ageing time, and catalysts prepared at a maximum pH = 5 with a short ageing time (ca. 0–3 h) exhibit high activity. Catalysts prepared at higher pH give lower activity. However, all catalysts require a short operation period during which the oxidation activity increases. In contrast, the calcined catalysts are not particularly sensitive to the preparation conditions. Non-calcined Au/Fe₂O₃ catalysts exhibit high activity when prepared at pH ≥ 5. Calcined Au/Fe₂O₃ prepared using the controlled pH method retain high activity, whereas calcined catalysts prepared using the variable pH method are inactive. The study shows the immense sensitivity of the catalyst performance to the preparation methods. It is therefore not surprising that marked differences in the performance of supported Au catalysts for CO oxidation that are apparent in the extensive literature on this subject, particularly the effect of calcination, can be expected if the preparation parameters are not carefully controlled and reported.     

Formation and Properties of Ln-Si-O-N Glasses (Ln = Lanthanides or Y)

Homogeneous Y-Si-O-N glasses containing 15 or 20 eq% nitrogen (N) were prepared from compositions with Y/Si ratios in the vicinity of that of the lowest eutectic point on the Y₂O₃–SiO₂ phase diagram. The liquidus on the phase diagram shifted toward lower temperatures by incorporation of N. The density, the elastic moduli, and the glass transition temperature of the Y-Si-O-N glasses increased with incorporation of N. This is due to the closer packing of atoms in the glasses by the substitution of N, which is in three-fold coordination with Si, for O which is in two-fold coordination, and the stronger covalent nature of the Si–N bond compared with the Si–O bond. The coefficient of thermal expansion of the Y-Si-O-N glasses increased with increasing Y content, because the discontinuity of the glass network developed with increasing nonbridging anions by the introduction of Y. In contrast, the glass transition temperature and the elastic moduli increased with Y content due to the high coordination of Y for O, and the relatively high cationic field strength of Y. Furthermore, the effect of cationic field strength on properties of Ln-Si-O-N glasses (Ln = lanthanides or Y) is discussed.     

Oxidation of Butane to Maleic Anhydride using Vanadium Phosphate Catalysts: Comparison of Operation in Aerobic and Anaerobic Conditions using a Gas-gas Periodic Flow Reactor

The use of a periodic flow reactor is described for the oxidation of butane to maleic anhydride to compare the catalytic performance of vanadium phosphate catalysts operating under aerobic and anaerobic conditions. It is found that for the catalyst prepared via a standard VPO method, operation in the absence of oxygen leads to a very small enhancement in selectivity when butane concentrations in the range 0.9–2.9% are used. Operation in the absence of oxygen leads to very small differences in conversion such that the overall yield is enhanced and this effect is maximised for reactor feeds containing 1.5% butane. However, the enhancement is negligible when the catalyst is operated at high conversion required for commercial operation, indicating that reactors operating with continuous flow with aerobic conditions are preferred. Similar experiments are conducted for a catalyst prepared by the VPD method and, in contrast, this catalyst gives lower butane conversion and maleic anhydride selectivity when operated in the absence of oxygen.     

Laser Specular Reflectance and the Optical rms Roughness of Alumina

Using laser specular reflectance, the optical rms roughnesses (σ₀'S) of 42 polycrystalline aluminas (PCA's) were determined. From these conventional experimental results, a nomogram was constructed so that single grazing angle (α) measurements could be used to predict σ₀. Subsequently, the nomogram was reassessed using five commercially important PCA's and one single-crystal sapphire (SC). The outcomes were twofold: that this nomogram was valid for PCA's over the range of 0.28 σ₀ 0.10 μm, but that the nomogram was invalid for SC sapphire. When the conventional experimental method was compared with the nomogram method at three different single-angle values, a 1:1 correspondence was observed for α= 78°, 80°, and 82°. The present noncontact method is advocated for speed and cleanliness, particularly when a quality assurance method is desired.     

Morphology and properties of poly(vinyl chloride)–polyurethane blends

The objective of this research was to study the morphology and properties of PVC–polyurethane blends. Studies on blends of a segmented polyether polyurethane with PVC were carried out utilizing differential scanning calorimetry, Rheovibron, stress–strain, infrared peak position studies, and infrared dichroism experiments. This thermodynamically incompatible system was made kinetically compatible by precipitation from tetrahydrofuran (THF) solutions. THF–dioxane solution casting and melt processing produced an incompatible system. The compatible polyurethane–PVC system contains a well-mixed PVC–polyether matrix phase as evidenced by T_g shifts, orientation characteristics, and infrared peak position changes. The aromatic urethane segments which exhibit microphase separation in the pure polyurethane are not solubilized by blending with PVC by any of sample preparation methods used in this study.     

Metallo-Supramolecular Polymerization: A Route to Easy-To-Process Organic/Inorganic Hybrid Materials

The self-assembly polymerization of ditopic macromolecules via metal–ligand binding is a facile route for the preparation of metallo-supramolecular polymers (MSPs). We herein review our recent work focused on the synthesis and investigation of metallo-supramolecular polymers based on 2,6-bis(1′-methylbenzimidazolyl)pyridine endcapped poly(p-phenylene ethynylene) and poly(p-xylene) macromonomers. These materials are readily solution-processable and display appreciable mechanical properties as well as other attractive properties such as specific opto/electrical functions or high thermal stability. Our work illustrates that metallosupramolecular polymerization offers an attractive approach to assemble high-molecular-weight macromolecules from well-defined, easy to process precursors. Variation of the ditopic ligands and metal ions allows one to easily tailor the desired properties. This paper is dedicated to Professor Ian Manners and his scientific accomplishments.