Thermal analysis of corrosion products formed on carbon steel in ammonium chloride solution

The influence of different ions NO₃ ^? and SO₄ ^2? on the carbon steel corrosion in ammonium chloride was investigated using mass loss measurements and potentiodynamic polarization. Corrosion products were analyzed using X-ray photoelectron spectroscopy (XPS) and simultaneous thermal and differential scanning calorimetry (TG/DSC). XPS analysis shows that the main product of corrosion is a non-stoichiometric Fe³⁺ oxyhydroxide, consisting of a mixture of FeO(OH) and FeO(OH) containing inclusions of these anions, species such as Fe³⁺O(OH,Cl^?); Fe³⁺O(OH,SO₄ ^2?); and Fe³⁺O(OH,NO₃ ^?). TG/DSC confirms the decomposition of the rusty products formed by chemical corrosion, compounds like Fe³⁺ oxyhydroxides, with β-FeOOH as the major phase, crystal structure of which may contain Cl^?, NO₃ ^?, and SO₄ ^2?—e.g., akaganeite [Fe³⁺O(OH,A)].     

Linker depletion for missing cluster defects in non-UiO metal–organic frameworks

Defect engineering is a valuable tool to tune the properties of metal–organic frameworks. However, defect chemistry remains still predominantly limited to UiO-type MOFs. We describe the preferential formation of missing cluster defects in heterometallic titanium–organic frameworks of the MUV-10 family when synthesised in sub-stoichiometric linker conditions. Our results show the value of integrating experimental work, computational modelling and thorough characterization in rationalizing the impact of defects over the porosity and structure of this family of materials. Correlation of experiment with computational models reveals the dominance of missing cluster vacancies in the pore size distribution of defective MUV-10. These same models were used to investigate the correlation of defects by synchrotron X-ray diffraction. The diffraction at low reflection angles is dominated by diffuse scattering that is indicative of short-range order and cannot be indexed to the defective structural models generated. In addition to the low atomic scattering factor of titanium, these results confirm the need for high-resolution electron microscopy methods for modelling nanoscale disorder in titanium MOFs.

Synthesis of MUV-10 in sub-stoichiometric linker conditions favours the formation of missing cluster vacancies for direct impact in their porosity.     

Experimental and numerical study of mixed convection with flow reversal in coaxial double-duct heat exchangers

Velocity vectors in a vertical coaxial double-duct heat exchanger for parallel ascending flow of water under conditions of laminar mixed convection have been determined experimentally using the particle image velocimetry technique. The measured velocity distributions for large annular flow rates, resulting in an essentially isothermal environment for the stream in the inner tube, are in very good agreement with corresponding numerical predictions. For flow rates of the same order of magnitude in the inner tube and the annulus, and corresponding temperature differences of about 20 °C, experimental observations show that flow reversal occurs simultaneously in both streams over large axial distances for both heating and cooling of the flow in the inner tube.     

Faber-hypercyclic operators

Let Ω be a bounded domain of the complex plane whose boundary is a closed Jordan curve and (F _n ) _n≥0 the sequence of Faber polynomials of Ω. We say that a bounded linear operator T on a separable Banach space X is Ω-hypercyclic if there exists a vector x of X such that {F _n (T)x: n ≥ 0} is dense in X. We show that many of the results in the spectral theory of hypercyclic operators involving the unit disk or its boundary have Ω-hypercyclic counterparts which involve the domain Ω or its boundary. The influence of the geometry of Ω or the smoothness of its boundary on Faber-hypercyclicity is also discussed.     

Compatibility study between indomethacin and excipients in their physical mixtures

Thermal analysis is a routine method for analysis of drugs and substances of pharmaceutical interest. Thermogravimetry/derivative thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC) are thermoanalytical methods which offer important information about the physical and chemical properties of drugs (purity, stability, phase transition, polymorphism, compatibility, kinetic analysis, etc.). This work exemplifies a general method of studying the drug-excipient interactions with the aim of predicting rapidly and inexpensively the long thermal stability of their mixtures. The TG/DTG and DSC were used as screening techniques for assessing the compatibility between indomethacin (IND) and its physical associations as binary mixtures with some common excipients. Based on their frequent use in preformulations eleven different excipients: corn starch, microcrystalline cellulose (PH 101; PH 102), colloidal silicon dioxide, lactose (monohydrate and anhydre), polyvinilpyrrolidone K30, magnesium stearate, talc, stearic acid, and manitol were blended with IND. The samples were prepared by mixing the analyte and excipients in a proportion of 1:1 (w:w). In order to investigate the possible interactions between the components, the thermal curves of IND and each selected excipient were compared with those of their 1:1 (w/w) physical mixtures. FT-IR spectroscopy and X-ray powder diffraction were used as complementary techniques to adequately implement and assist in interpretation of thermal results. On the basis of thermal results, confirmed by FT-IR and X-ray analyses, a possible interaction was found between IND with polyvinylpyrrolidone K30, magnesium stearate, and stearic acid.     

Analysis and discretization of an optimal control problem for the time-periodic MHD equations

We consider the mathematical formulation and analysis of an optimal control problem associated with the tracking of the velocity and the magnetic field of a viscous, incompressible, electrically conducting fluid in a bounded two-dimensional domain through the adjustment of distributed controls. Existence of optimal solutions is proved and first-order necessary conditions for optimality are used to derive an optimality system of partial differential equations whose solutions provide optimal states and controls. Semidiscrete-in-time approximations are defined and their convergence to the exact optimal solutions is shown.     

Amine oxidase amperometric biosensor coupled to liquid chromatography for biogenic amines determination

A selective and sensitive method is presented for biogenic amines (BA) determination. The novelty consists in coupling a highly selective electrochemical biosensor to a weak acid cation-exchange column for online detection of amines. A bienzyme design, based on a recently isolated amine oxidase from grass pea and commercial horseradish peroxidase, was used for the biosensor construction. The enzymes were co-immobilized on the surface of a graphite electrode together with the electrochemical mediator (Os-redox polymer). The electrochemical detection was performed at a low applied potential (?50 mV vs. Ag/AgCl, KCl_0.1 M), where biases from interferences are minimal. The separation and determination of six BA, with relevance in food analysis (tyramine, putrescine, cadaverine, histamine, agmatine and spermidine), were investigated. Irrespective of the BA nature, the amine oxidase-based biosensor showed a linear response up to 5 mM, and its sensitivity decreases in the following order: cadaverine, putrescine, spermidine, agmatine, histamine and tyramine. The approach was used to estimate the BA content in fish samples, after their extraction with methanesulfonic acid.     

Analysis of an optimal control problem for the three-dimensional coupled modified Navier-Stokes and Maxwell equations

The mathematical formulation and analysis of an optimal control problem associated with a viscous, incompressible, electrically conducting fluid in a bounded three-dimensional domain with fixed perfectly conducting boundaries is considered. The objective of control is the matching of the velocity and magnetic fields to given target fields; control is effected through distributed mechanical force and current controls. The existence of optimal solutions is shown, the Gâteaux differentiability for the magnetohydrodynamic system with respect to controls is proved, and the optimality system is obtained.     

Generalized inverses and the maximal radius of regularity of a Fredholm operator

Operators possessing analytic generalized inverses satisfying the resolvent identity are studied. Several characterizations and necessary conditions are obtained. The maximal radius of regularity for a Fredholm operatorT is computed in terms of the spectral radius of a generalized inverse ofT. This provides a partial answer to a conjecture of J. Zemánek.