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.     

Synthesis and characterization of poly(ethylene aspartate)-metal complexes

Poly(ethylene aspartate) [PEA] was synthesized by the melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing pendent amino and carbonyl groups in its repeating chain was used as the polymeric ligand for complexation with transition metal ions, viz. Co(II), Ni(II), Cu(II), Mn(II), Zn(II), Cd(II), Ca(II), Mg(II), Pb(II) and Hg(II). Complexation was found to be most effective in DMSO. The resulting polyester-metal complexes were solid coloured materials which have been characterized by IR spectroscopy, elemental analysis and magnetic susceptibility measurements. The thermal stability of the polyester-metal complexes was investigated by thermogravimetric analysis (TGA). On the basis of the physico-chemical studies, an oxygen and nitrogen coordinated structure for the polyester-metal complexes is proposed.     

Electrical conductivity in iodine-doped ethyl cellulose

The electrical conductivity of solution-grown ethyl cellulose (EC) films, 5–30 μm thick, has been studied in the sandwich configuration (metal–EC–metal) as a function of iodine concentration from 0.5 to 5.0 wt% ratio. The studies were conducted in the temperature range 333–383 K, while the field was varied over the range (3.0–5.5) × 10⁴V/cm. Aluminium was used as the lower electrode, while the upper electrode was of Al, Ag, Cu, Au or Sn. Certain transient effects such as a large burst of current immediately after the application of field were observed. An attempt was made to identify the nature of the current by comparing the observed dependence on electric field, electrode material and temperature with the respective characteristic features of the existing theories of electrical conduction. The results show that the electrical conduction follows Ohm's law at lower fields, while at higher fields, space-charge limited current (SCLC) was observed. It was also found that Richardson–Schottky emission was responsible, to some extent, for the transport of charge carriers in the polymer. The conductivity of the films increased on doping with iodine. The dopant molecules are considered to act as additional trapping centes and provide links between the polymer molecules in the amorphous region, thus resulting in the formation of charge transfer complexes.     

Mixtures of tertiary amine functionalized azo-containing mesogens with acid-functionalized polymers

A tertiary amine functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S_A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase.     

Simulation of Fe-Al compounds developed during single superphosphate manufacture

In order to analyse iron phosphate complexes and gel-like phases encountered in the single superphosphate process, experiments were performed with a free-Al, Fe apatite crystal of Durango from Mexico phosphate rock and sulfuric acid. Reaction products were studied by X-ray diffraction and surface analysis methods namely X-ray photoelectron spectroscopy and scanning electron microscopy. Results show that in a free Al, Fe-system, part of the Ca(H₂PO₄ )₂.H₂O (MCPM) forms before precipitation of any CaSO₄(CS) and gel-like phase such H₂SO₄.yH₃PO₄.xH₂O is formed. When iron is added, the precipitation rate of (CS) and (MCPM) increases and Fe₃(H₃O)H₈(PO₄)₆.6H₂O is formed. When Fe and Al are added, a gel-like phase is quickly formed with a molar ratio that changes with time and develops into crystalline compounds. The composition of this gel may be represented as a mixture of two phases: H₂SO₄.yH₃PO₄.xH₂O and a gel containing Al-Fe-Si.     

Platinum particle size effect on the oxidative dehydrogenation of aqueous ethanol

The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m^–3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m^–3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.     

Formation of Polymeric Lewis Acid–Lewis Base Complexes with Well-defined Organoboron Polymers

The binding of Lewis bases to organoboron polymeric Lewis acids has been studied and the parameters that determine the complexation equilibrium have been investigated, which include (i) the strength of the individual Lewis acids and Lewis bases, (ii) concentration, and (iii) temperature. While the strongly Lewis acidic borane polymers poly(4-bis(pentafluorophenyl)borylstyrene) (PS-BPf) and poly(4-(di-2-thienylboryl)styrene) (PS-BTh) form isolable complexes with strong Lewis bases such as 4-t-butylpyridine (^tPy), a temperature dependent equilibrium is established with weaker bases such as THF. Similarly, the weakly Lewis acidic boronate polymer poly(4-diethoxyborylstyrene) (PS-BOEt) undergoes a temperature dependent equilibrium with the strong Lewis base 4-dimethylaminopyridine (DMAP), while poly(4-pinacolatoborylstyrene) (PS-BPin) does not significantly bind to pyridine bases. Decomplexation of PS-BTh· ^t Py is achieved by treatment with the stronger Lewis acid, B(C₆F₅)₃, thereby confirming the reversible nature of the polymeric Lewis acid–base adducts. This paper is dedicated to Professor Ian Manners in gratitude of his guidance throughout the years and recognition of his scientific accomplishments     

A new class of corrosion inhibitors for waterborne coatings: 4-methyl-γ-oxo-benzene-butanoic acid complexes

Amine and transition metal based complexes with 4-methyl-γ-oxo-benzene-butanoic acid represent a new class of corrosion inhibitors specifically designed for long-term corrosion protection in waterborne coatings. Today, corrosion protection in waterborne technology is typically achieved using traditional anticorrosive pigments initially developed for use in solventborne coatings. Regulations concerning heavy metals and limitations regarding the compatibility and performance of such materials in waterborne coatings have created a need for novel approaches. Mechanistic aspects are discussed for the 4-methyl-γ-oxo-benzene-butanoic complexes based on electrochemical solution experiments (electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV)) and investigations performed on coated substrates. Exposure results underline the high efficiency of such complexes for both long-term corrosion protection and weld seam rust control in waterborne coatings.     

Role of platinum in the Na2SO4-Induced hot corrosion resistance of aluminum duffusion coatings

Electrochemical corrosion measurements have been carried out with Pt-containing and Pt-free Al-diffusion coatings on IN 738 LC in a 90Na₂SO₄+ 10K₂SO₄ (mol%) melt at 1173 K. Pt improves the resistance to basic fluxing while there are no significant differences between both coating types in their resistance to acidic fluxing. The corrosion resistance of the Pt-containing coating is also higher in the passive potential region where protective scales rich in Al₂O₃ are formed. The reason for the different behavior of both coating types appears to be related to the high corrosion resistance of the Pt-rich surface layer of the coating and an increased Al₂O₃ content in the scale of the Pt-containing type.