SFG and DFG investigation of Au(111), Au(210), polycrystalline Au,Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN⁻ and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN⁻ and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN⁻ electrolyte, denote changes in the CN⁻ adsorption characteristics and effects of the adsorbed CN⁻ layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN⁻. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN⁻ monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004     

On the observation of inductive high-frequency impedance behaviour during the electrodeposition of Au—Sn alloys

Inductive high-frequency impedance behaviour is often observed in metal electrodeposition systems. This behaviour is typically attributed to equipment limitations or non-idealities in the cell set-up and electrical connections. Such instrumental artefacts would nevertheless be relevant to a frequency range which is expected to be well above that in which inductive behaviour is in fact observed (down to a few tens of Hz). In this paper some results on an acidic Au—Sn electrodeposition system are reported. Electrochemical impedance and potentiostatic transients were measured. These results suggest that the high-frequency inductive behaviour may be related to metal nucleation processes. A correlation is proposed between the pseudo-inductive potentiostatic nucleation transients and the pseudo-inductive behaviour of the impedance spectra.     

Restricted chain segment mobility in poly(amide) 6/clay nanocomposites evidenced by quasi-isothermal crystallization

Modulated temperature differential scanning calorimetry is used to explore the interactions between a poly(amide) 6 matrix and various types of clay reinforcement. During quasi-isothermal crystallization of the polymer/clay nanocomposites, an excess contribution is observed in the recorded heat capacity signal, due to reversible melting and crystallization. It is proposed that the magnitude of this excess contribution can be used to qualify the polymer/clay interfacial interaction, as it is directly linked to the segmental mobility of the polymer chains in the interphase region, where both the crystalline and amorphous polymer fractions are affected. It is shown that the interfacial interaction strongly depends on the type of clay filler used. These interactions play a key role in the development of specific material properties for the different types of nanocomposites. A simple interphase model for the poly(amide) 6/clay nanocomposites is proposed.     

Designing biomass supply chains within planetary boundaries

The design of sustainable supply chains, which recently emerged as an active area of research in process systems engineering, is vital to ensure sustainable development. Despite past and ongoing efforts, the available methods often overlook impacts beyond climate change or incorporate them via standard life cycle assessment metrics that are hard to interpret from an absolute sustainability viewpoint. We here address the design of biomass supply chains considering critical ecological limits of the Earth—planetary boundaries—which should never be surpassed by anthropogenic activities. Our method relies on a mixed-integer linear program that incorporates a planetary boundaries-based damage model to quantify absolute sustainability precisely. We apply this approach to the sugarcane-to-ethanol industry in Argentina, identifying the optimal combination of technologies and network layout that minimize the impact on these ecological boundaries. Our framework can find applications in a wide range of supply chain problems related to chemicals and fuels production, energy systems, and agriculture planning.     

Novel ferrofluids coated with a renewable material obtained from cashew nut shell liquid

In this work, we present the synthesis and characterization of a new surfactant molecule obtained from a byproduct of the cashew nut processing (diphosphorylated cardol, DPC). It is herein used to overcoat magnetic nanoparticles showing spinel structures in order to create new ferrofluids. The nanoparticle structure and magnetic properties have been deeply investigated. DPC-functionalized Fe₃O₄ and NiFe₂O₄ samples exhibit higher magnetic saturation than DPC–CoFe₂O₄. These new ferrofluids reveal appealing as possible nanoparticle stabilizing molecules, magnetic resonance imaging agents, storage systems or in any material science field that requires the employment of biocompatible magnetic stable fluids.     

Electrochemical behaviour of titanium in fluoride-containing saliva

The effect of fluoride on the electrochemical behaviour of titanium was studied. Open circuit potentials, breakdown potentials (E _b) and potentiostatic transient currents were measured in synthetic salivas of different compositions. Optical and scanning electron microscopic observations were also made. Results show that the growth rate of Ti oxide layer is affected by fluoride anions and tensile stresses are developed. The OCP/time relationship of Ti immersed in salivas A and B obeys a logarithmic law which depends on the saliva composition. The E _b value is influenced by the thickness of the oxide layer, by the composition of the saliva (including fluoride concentration), and by the technique utilised for its evaluation. Thus, results reported in the literature, which seem to be contradictory, could be explained taking into account the experimental conditions assayed. A careful control of the titanium-containing dental materials should be made after long treatments with fluoride-containing prophylactic products or when fluoride-releasing restorative materials are present in the vicinity.     

Microdroplet-based multiplex PCR on chip to detect foodborne bacteria producing biogenic amines

The development of fast, reliable and culture-independent molecular tools to detect bacteria producing biogenic amines deserves the attention of research and ultimately of the food industry in order to protect consumers' health. Here we present the application of a simple, low-cost, fast and sensitive method to perform microdroplet-based multiplex PCR, directly on a food matrix, for the simultaneous detection of bacterial genes involved in biogenic amine biosynthesis. After inoculating wine with Lactobacillus brevis IOEB 9809, cell lysis and DNA amplification are performed in one single step, without preliminary nucleic acid extraction or purification treatments. The assay is performed in about 30 min, requiring 150 nL of starting sample and it enables the detection of down to 15 bacterial cells. With respect to traditional culture techniques, the speed, the simplicity and the cheapness of this procedure allow an effective monitoring of microbial cells during food-making and processing.     

Design and planning of infrastructures for bioethanol and sugar production under demand uncertainty

In this paper, we address the strategic planning of integrated bioethanol–sugar supply chains (SC) under uncertainty in the demand. The design task is formulated as a multi-scenario mixed-integer linear programming (MILP) problem that decides on the capacity expansions of the production and storage facilities of the network over time along with the associated planning decisions (i.e., production rates, sales, etc.). The MILP model seeks to optimize the expected performance of the SC under several financial risk mitigation options. This consideration gives a rise to a multi-objective formulation, whose solution is given by a set of network designs that respond in different ways to the actual realization of the demand (the uncertain parameter). The capabilities of our approach are demonstrated through a case study based on the Argentinean sugarcane industry. Results include the investment strategy for the optimal SC configuration along with an analysis of the effect of demand uncertainty on the economic performance of several biofuels SC structures.     

Chemical stability of doped ZnO thin films

We present the results of a chemical etching stability study carried out on ZnO thin films doped with several elements deposited by spray pyrolysis. Prior to the etching, a structural study was done by X-ray diffraction and the texture of the samples was obtained by scanning electron microscopy. The samples were etched employing a solution of dilute hydrochloric acid. The etching rates obtained for the different samples depend on the dopant element and our results confirm that films doped with Cr present the highest stability against chemical etching.