Spectrophotometric simultaneous determination of nitrite, nitrate and ammonium in soils by flow injection analysis

A new rapid flow injection procedure for the simultaneous determination of nitrate, nitrite and ammonium in single flow injection analysis system is proposed. The procedure combines on-line reduction of nitrate to nitrite and oxidation of ammonium to nitrite with spectrophotometric detection of nitrite by using the Griess-llosvay reaction. The formed azo dye was measured at 543 nm. The influence of reagent concentration and manifold parameters were studied. Nitrite, nitrate and ammonium can be determined within the range of 0.02–1.60 μg mL⁻¹, 0.02–1.60 μg mL⁻¹ and 0.05–1.40 μg mL⁻¹, respectively. R.S.D. values (n = 10) were 2.66; 1.41 and 3.58 for nitrate, nitrite and ammonium, respectively. This procedure allows the determination and speciation of inorganic nitrogen species in soils with a single injection in a simple way, and high sampling rate (18 h⁻¹). Detection limits of 0.013, 0.046 and 0.047 μg mL⁻¹were achieved for nitrate, nitrite and ammonium, respectively. In comparison with others methods, the proposed one is more simple, it uses as single chromogenic reagent less injection volume (250 mL in stead of 350 mL) and it has a higher sampling rate.     

Qualitative Properties of the Solution Set for Time-Delayed Discontinuous Dynamics

This article presents a survey of several properties of the set of solutions for a differential inclusion involving a time-delayed component and with right-hand side parametrized by either an upper semicontinuous or lower semicontinuous multifunction. Our results include: existence of solutions, compactness and contractibility of the solution and reachable sets in the upper semicontinuous case, precompactness and connectedness of the solution and reachable sets in the lower semicontinuous case, regularity of the solution and reachable mappings with respect to parameters, and existence of solutions for a dynamic optimization problem.

     

Stabilization and functionalization of single-walled carbon nanotubes with polyvinylpyrrolidone copolymers for applications in aqueous media

In spite of their useful electronic and mechanical properties, the utility of single-walled carbon nanotubes (SWNT) is limited by their inherent insolubility in aqueous environments and the difficulty in functionalizing the material while retaining opto-electric properties. In this article, the synthesis of polyvinylpyrrolidone (PVP) copolymers for wrapping SWNTs is described. Studies include the effect of polymer composition and charge on SWNT stability in aqueous solution and the variation of the stability of wrapped SWNTs during high-dilution conditions using dialysis studies. Finally, the PVP-copolymer strategy is used to create polymer wrappers with functional handles for the incorporation of useful chemical functionality. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 337–343     

A characterization of those categories whose internal logic is Hilbert's ε-calculus

We characterize categories whose internal logic is Hilbert's ε-calculus as those categories which have a proper factorization system satisfying the axiom of choice and in which every non-initial object is injective. We provide an example of such a category where the law of excluded middle is not valid.     

Thermal and morphological characterization of micronized acetylsalicylic acid powders prepared by rapid expansion of a supercritical solution

Aim of this work was to investigate the solid-state characteristics of micronized acetylsalicylic acid (ASA), produced by rapid expansion of a supercritical carbon dioxide solution (RESS) and to assess whether a correlation could be found between process parameters and solid-state characteristics. Drug solubility in supercritical CO₂ was first assessed under various pressure and temperature conditions. DSC, FT-IR, PXRD, SEM, laser light scattering and HPLC were used to characterise the solid phases produced by the RESS. The obtained particles were crystalline, with spectroscopical and diffractometrical pattern overlapping those of the starting available product. However, a strong reduction of particle size was obtained, linearly correlated to pressure imposed during the RESS process, while temperature did not seem to have a major effect. Similar influence of pressure was observed on the final melting temperature of the micronized ASA. The application of a mathematical model allowed to conclude that the melting temperature depression of RESS-prepared ASA powders can be attributed to the decrease of particle dimension rather than to the formation of different solid phases or impurities. This revised version was published online in July 2006 with corrections to the Cover Date.     

Theoretical modeling of microstructured liquids: a simple thermodynamic approach

A new method is presented for accounting for microstructural features of flowing complex fluids at the level of mesoscopic, or coarse-grained, models by ensuring compatibility with macroscopic and continuum thermodynamics and classical transport phenomena. In this method, the microscopic state of the liquid is described by variables that are local expectation values of microscopic features. The hypothesis of local thermodynamic equilibrium is extended to include information on the microscopic state, i.e., the energy of the liquid is assumed to depend on the entropy, specific volume, and microscopic variables. For compatibility with classical transport phenomena, the microscopic variables are taken to be extensive variables (per unit mass or volume), which obey convection-diffusion-generation equations. Restrictions on the constitutive laws of the diffusive fluxes and generation terms are derived by separating dissipation by transport (caused by gradients in the derivatives of the energy with respect to the state variables) and by relaxation (caused by non-equilibrated microscopic processes like polymer chain stretching and orientation), and by applying isotropy. When applied to unentangled, isothermal, non-diffusing polymer solutions, the equations developed according to the new method recover those developed by the Generalized Bracket [J. Non-Newtonian Fluid Mech. 23 (1987) 271; A.N. Beris, B.J. Edwards, Thermodynamics of Flowing Systems with Internal Microstructure, first ed., Oxford University Press, Oxford, 1994] and by the Matrix Model [J. Rheol. 38 (1994) 769]. Minor differences with published results obtained by the Generalized Bracket are found in the equations describing flow coupled to heat and mass transfer in polymer solutions. The new method is applied to entangled polymer solutions and melts in the general case where the rate of generation of entanglements depends nonlinearly on the rate of strain. A link is drawn between the mesoscopic transport equations of entanglements and conformation and the microscopic equation describing the configurational distribution of polymer segment stretch and orientation. Constraints are derived on the generation terms in the transport equations of entanglements and conformation, and the formula for the elastic stress is generalized to account for reversible formation and destruction of entanglements. A simplified version of the transport equation of conformation is presented which includes many previously published constitutive models, separates flow-induced polymer stretching and orientation, yet is simple enough to be useful for developing large-scale computer codes for modeling coupled fluid flow and transport phenomena in two- and three-dimensional domains with complex shapes and free surfaces.     

Forward roll coating flows of viscoelastic liquids

Roll coating is distinguished by the use of one or more gaps between rotating cylinders to meter and apply a liquid layer to a substrate. Except at low speed, the two-dimensional film splitting flow that occurs in forward roll coating is unstable; a three-dimensional steady flow sets in, resulting in more or less regular stripes in the machine direction. For Newtonian liquids, the stability of the two-dimensional flow is determined by the competition of capillary and viscous forces: the onset of meniscus nonuniformity is marked by a critical value of the capillary number. Although most of the liquids coated industrially are non-Newtonian polymeric solutions and dispersions, most of the theoretical analyses of film splitting flows relied on the Newtonian model. Non-Newtonian behavior can drastically change the nature of the flow near the free surface; when minute amounts of flexible polymer are present, the onset of the three-dimensional instability occurs at much lower speeds than in the Newtonian case.Forward roll coating flow is analyzed here with two differential constitutive models, the Oldroyd-B and the FENE-P equations. The results show that the elastic stresses change the flow near the film splitting meniscus by reducing and eventually eliminating the recirculation present at low capillary number. When the recirculation disappears, the difference of the tangential and normal stresses (i.e., the hoop stress) at the free surface becomes positive and grows dramatically with fluid elasticity, which explains how viscoelasticity destabilizes the flow in terms of the analysis of Graham [M.D. Graham, Interfacial hoop stress and instability of viscoelastic free surface flows, Phys. Fluids 15 (2003) 1702–1710].     

Effect of Non-Calcined Sugarcane Bagasse Ash as an Alternative Precursor on the Properties of Alkali-Activated Pastes

BFS-MK-based alkali-activated materials are well established as an alternative for sustainable and green construction. This work aims to collaborate and encourage the use of biomass ashes, such as sugarcane bagasse ash (SCBA), as a precursor in alkali-activated materials (AAM). This ash is a rich source of aluminosilicate, which is a primary requirement for this application. In addition, this waste is still an environmental liability, especially in developing countries, and with a large volume of annual production. Thus, in this research, alkali-activated pastes (AA) were produced using sugarcane bagasse ash (SCBA), granulated blast furnace slag (BFS) and metakaolin (MK) as precursors. In addition, environmental gains were encouraged with energy savings, with no extra reburn or calcination steps in the SCBA. Thus, the precursors were characterized by laser granulometry, X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The pastes were produced by mixing the precursors with the activator, composed of a mixture of sodium hydroxide 8 mol/L and sodium silicate. Aiming to study the incorporation of SCBA, all samples have a precursor/activator ratio and a BFS/(BFS + MK) ratio constant of 0.6. The compressive strength analysis, FTIR, XRD, TGA, SEM and isothermal calorimetry analyses pointed out the occurrence of alkaline activation in all proposed samples for curing times of 7, 28 and 91 days. The sample GM0.6-BA0 (15% SCBA) achieved the highest compressive strength among the samples proposed (117.7 MPa, at 91 days), along with a good development of strength throughout the curing days. Thus, this work presents the properties of alkaline-activated pastes using SCBA as a sustainable and alternative precursor, seeking to encourage the use of raw materials and alternative waste in civil construction.     

A stability problem for holonomic systems

Sunto Si studia il problema della stabilità di una posizione di equilibrio di un sistema meccanico olonomo soggetto ad una sollecitazione derivante da un potenziale del tipo U(q, t)=f(t) U*(q), conf funzione periodica, e ad una sollecitazione dissipativa. I risultati ottenuti estendono a sistemi con un numero finito qualsiasi di gradi di libertà risultati noti per sistemi ad un solo grado di libertà.

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Work performed under the auspices of the Italian Council of Research (C.N.R.): National Group of Mathematical Physics (G.N.F.M.), and Italian Ministry of Public Education (M.P.I.).

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The author wishes to thank professors S.Busenberg and L.Salvadori for many useful discussions.     

Su una classe di equazioni integrali lineari in teoria del trasporto

Sunto. In questa nota si discutono le proprietà funzionali di una classe di equazioni integrali lineari che si incontrano in teoria del trasporto sia di particelle sia di calore, e si imposta il problema della loro risoluzione per via costruttiva.

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Summary The functional properties of a class of linear integral equations governing various transport phenomena are discussed in this note. A constructive method relevant to their solution is also presented.

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A Dario Graffi nel suo 70° compleanno

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Entrata in Redazione il 6 settembre 1975.