Synthesis of heterocyclic metal complexes and their evaluation as marine antifoulants

4-Amino-3-thio-1,24-triazolidine (L₁) and 4-amino-5-thio-1,3,4-thiadiazole (L_II) as well as their metal complexes of the general formulae ML_I·2H₂O and ML_IICl (M; Pb(II), Cd(II) and Zn(II)) were prepared. With Sn(II), we obtained Sn(L_I)₂·2H₂O and SnL_IICl, respectively. The structures of the compounds were identified through elemental analysis, and IR and UV spectra measurements, in addition to thermal analysis in case of the metal complexes. The antifouling properties of the compounds were tested by their incorporation into paint formulations which were applied to PVC substrates and tested in water from Alexandria western harbour. When the compounds were added at 17·5% by volume, the coated panels were fouled after 3 months of immersion. The addition of 6·7% by volume of tributyltin oxide to 15·8% of the prepared compounds in one formulation elevated the paint efficiency and prevented fouling for 11 months. Paint containing solely tributyltin oxide at the same concentration was inactive against algae.     

Polymer networks based on α,ω-methacrylate-terminated poly(1,3-dioxolane)

α,ω-Methacrylate-terminated poly(1,3-dioxolane)s (polyDXL) were synthesized by cationic ring-opening polymerization of DXL in the presence of methylene-bis(oxyethylmethacrylate) as transfer agent. If the initiator concentration is small compared with the transfer agent concentration, the molecular weights of the polymers are governed by the ratio of the reacted monomer to the reacted transfer agent. The α,ω-methacrylate-terminated polyDXLs obtained undergo free radical polymerization with formation of polyacetal networks. The properties of the networks as function of the molecular weight of the corresponding prepolymers are reported.     

Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.     

Kinetic model for water/oil absorption of mesquite gum (Prosopis juliflora) and gum arabic (Acacia senegal)

The water and oil uptake of mesquite and arabic gums in powdered form was studied at temperatures of 23, 35 and 45°C. A previously proposed equation to predict osmotic equilibrium was tested using the experimental data with both gums and a good statistical fit was obtained. Mesquite gum showed the highest water and oil absorption at all temperatures studied. Temperature dependence of the reciprocal of the S₁ and WL_∞ were determined using an Arrhenius equation. The activation energy for water and oil absorption for gum arabic was 21.98 and 39.57 kJ mol⁻¹, compared to that of mesquite gum having values of 15.79 and 46.16 kJ mol⁻¹, respectively. A second order kinetic model was obtained for water and oil absorption for both gums.     

Water-soluble copolymers: 22. Copolymers of acrylamide with 2-acrylamido-2-methylpropanedimethylammonium chloride: Aqueous solution properties of a polycation

The viscometric, turbidimetric and potentiometric properties of copolymers of acrylamide (AM) with 2-acrylamido-2-methylpropanedimethylammonium chloride (AMPDAC) were studied in aqueous solutions. The AMPDAC polymers exhibit poor salt tolerance and large, negative viscosity/temperature coefficients. Furthermore, the polymers were found to be sensitive to changes in pH. The AMPDAC polymers undergo phase separation in the presence of dianions as a function of temperature and AMPDAC composition.     

Nucleation of copper on an assembly of carbon microelectrodes

The initial stage of copper electrodeposition on the electrochemically activated assembly of carbon microelectrodes from an acid solution of copper sulfate was investigated using cyclic voltammetry, potentiostatic pulse technique and electrochemical impedance spectroscopy. Analysis of the experimental current transients has been carried out using a non-linear fitting procedure according to the model that takes into account spherical diffusion towards a disc-shaped microelectrode. The higher values of diffusion coefficient in comparison with those observed on planar electrodes were explained with an increased diffusion caused by the electrode geometry. Impedance spectra showed two time constants, the high-frequency related to the charge transfer process and the low-frequency corresponded to the deposit morphology.