3D multiscale modeling to predict the elastic modulus of polymer/nanoclay composites considering realistic interphase property

The elastic modulus of a nanocomposite reinforced with nanoclay was studied using the 3D finite-element method. It is widely accepted that interphase between nanoparticle and matrix plays an important role in the performance of the nanocomposite. Thus, a representative volume element (RVE) consisted of three phases (i.e. matrix, interphase and nanoclay) was simulated. In addition, to have a realistic estimation of elastic modulus of the interphase region, the modulus was computed using the available analytical formula. Since the nanoclays have been known as platelets and to investigate the effect of the third dimension, the nanoclay was simulated as a thin cuboid. The effect of various geometrical parameters, such as the change of the nanoclay contact area at a constant volume fraction of nanoclay, the variation of the nanoclay angle in the planes perpendicular and parallel to the loading direction, and the RVE dimensions, on the elastic modulus of a nanocomposite was considered. The results revealed that the increase in contact area of the nanoclay at a constant volume of nanoclay led to an increase in the elastic modulus of the nanocomposite. Furthermore, the change in the angle of nanoclay with respect to the plane parallel to loading direction has considerable effects on the elastic modulus of the nanocomposite, whereas this effect is negligible for the alignment angle perpendicular to the plane of the loading direction. Finally, unlike the previous studies, the results of the finite-element modeling were compared with three-phase theory of Mori–Tanaka.     

Inelastic Electron Transport Through a Carbon Fullerene Junction

Effects of inelastic electron–phonon interactions and different contact geometries on the electron transport and thermoelectric properties of the C₆₀ molecule are studied by Green’s function theory within the framework of polaron transformation. It is seen that the current (I _e ) and energy flux (I _Q ) values with respect to the contact types are ordered as I _e/q (C ₁)?I _e/q (C ₆)?I _e/q (C ₅). The results reveal that the thermopower–energy curves have strictly monotonic character which show the staircase structures. Their stair numbers depend on contact types and presence of electron–phonon interactions. It is shown that the oscillatory behavior of thermal conductance is dramatically dependent on contact types and e–p interactions. Also, the values of the dimensionless figures of merit (ZT ₀) lie in the interval [0.322 ×?10^??7, 0.194 ×?10^??3], and effect of contact types is small on the values of ZT ₀s.     

A new application of the homotopy analysis method in solving the fractional Volterra’s population system

This paper considers a Volterra’s population system of fractional order and describes a bi-parametric homotopy analysis method for solving this system. The homotopy method offers a possibility to increase the convergence region of the series solution. Two examples are presented to illustrate the convergence and accuracy of the method to the solution. Further, we define the averaged residual error to show that the obtained results have reasonable accuracy.     

Completeness of intermediate logics with doubly negated axioms

Let denote a first‐order logic in a language that contains infinitely many constant symbols and also containing intuitionistic logic . By , we mean the associated logic axiomatized by the double negation of the universal closure of the axioms of plus . We shall show that if is strongly complete for a class of Kripke models , then is strongly complete for the class of Kripke models that are ultimately in .     

Asymmetric logistic peak as a suitable function for the resolution of highly asymmetric voltammograms in non-bilinear systems

The asymmetric logistic peak is tested as a new function for the parametric signal fitting (PSF) of highly asymmetric electrochemical signals in non-bilinear datasets, such as those obtained in linear sweep voltammetry (LSV) or in the presence of irreversible electrochemical processes. This new multivariate curve resolution strategy (PSF-ALPA) is successfully applied to LS voltammograms measured for the Cd(II)-glutathione system with a hanging mercury drop electrode, where Cd(II) is reversibly reduced, and to differential pulse voltammograms (DPV) measured at a glassy carbon electrode, where Cd(II) reduction becomes irreversible. Matrix augmentation by using LS voltammograms measured at different scan rates provides good results and encourages the development of ALPA methodology for third order data.     

Continuous‐Flow Synthesis of CdSe Quantum Dots: A Size‐Tunable and Scalable Approach

In recent years, continuous‐flow/microreactor processing for the preparation of colloidal nanocrystals has received considerable attention. The intrinsic advantages of microfluidic reactors have opened new opportunities for the size‐controlled synthesis of nanocrystals either in the laboratory or on a large scale. Herein, an experimentally simple protocol for the size‐tunable continuous‐flow synthesis of rather monodisperse CdSe quantum dots (QDs) is presented. CdSe QDs are manufactured by using cadmium oleate as cadmium source, selenium dioxide as selenium precursor, and 1‐octadecene as solvent. Exploiting selenium dioxide as selenium source and 1‐octadecene as solvent allows execution of the complete process in open air without any requirement for air‐free manipulations using a glove box or Schlenk line. Continuous‐flow processing is performed with a stainless steel coil of 1.0 mm inner diameter pumping the combined precursor solution through the reactor by applying a standard HPLC pump. The effect of different reaction parameters, such as temperature, residence time, and flow rate, on the properties of the resulting CdSe QDs was investigated. A temperature increase from 240 to 260 °C or an extension of the residence time from 2 to 20 min affords larger nanocrystals (range 3–6 nm) whereas the size distribution does not change significantly. Longer reaction times and higher temperatures result in QDs with lower quantum yields (range 11–28 %). The quality of the synthesized CdSe QDs was confirmed by UV/Vis and photoluminescence spectroscopy, small‐angle X‐ray scattering, and high‐resolution transmission electron microscopy. Finally, the potential of this protocol for large‐scale manufacturing was evaluated and by operating the continuous‐flow process for 87 min it was possible to produce 167 mg of CdSe QDs (with a mean diameter of 4 nm) with a quantum yield of 28 %.     

Study Kinetics of Thermal Decomposition and Electrochemical Oxidation by Using Nanocomposite Paste of Novel Poly(amide-ether)s Derived from Asymmetric Diamine

A new asymmetric diamine containing diarylimodazole pendant was synthesized from the nucleophilic substitution reaction of 1-fluoro-4-nitrobenzene and 2,4-dihydroxy benzaldehyde in the presence of K₂CO₃, followed by reaction with benzil and ammonium acetate for the preparation of imidazole ring. This novel diamine was used to prepare poly(amide-ether) (PAE) in reaction with different commercially available dicarboxylic acids via direct polycondensation using triphenyl phosphite and pyridine (Py) as catalyst. The PAEs were fully characterized and their properties such as inherent viscosity, solubility, optical, thermal and kinetics of thermal decomposition, and electrochemical oxidation were investigated. The polymers had inherent viscosity in the range of 0.47–0.65 dL/g and were noncrystalline with excellent solubility in various polar aprotic organic solvents. Their T_g values ranged from 200 to 355°C and 10% weight loss temperature above 450°C in nitrogen and left more than 70% residue at 650°C. The kinetic parameters of thermal degradation such as activation energy, entropy, enthalpy and Gibbs free energy of thermal decomposition have been evaluated using different equations. We also report electrochemical oxidation of the resulting polymers in aqueous solution by using cyclic voltammetry technique on the multi-walled carbon nanotube-modified glassy carbon electrode.     

Prediction and characterization of halogen–hydride interaction in Cu n H n ···ClC2Z and Cu n H···ClC2Z complexes (n = 2–5; Z = H, F, CH3)

Halogen–hydride interactions between the lowest energy structure of Cu _n H _n and Cu _n H clusters (n = 2–5) as halogen acceptor and ClC₂Z (Z = H, F, CH₃) as halogen donor have been investigated at the MP2/6-311++G(d,p) level of theory. Different approaches based on structural parameters, energetic analysis, shift in vibrational frequencies, and molecular electrostatic potential were used to characterize the resultant halogen–hydride bonds. Upon complexation, the Cl–C bonds tend to elongate, concomitant with red shifts of the Cl–C vibrational frequencies. Interaction energies of this type of halogen bonds vary from ?2.34 to a maximum ?7.38 kJ mol^?1. The calculated interaction energies were found to be increased in magnitude with increasing of the negative electrostatic potential at a point on the outer side of hydrogen atom of halogen acceptor units. Moreover, decomposition of the interaction energies reveals that the electrostatic interaction plays a main role in the formation of the complexes. The quantum theory of atoms in molecules analysis has also been applied to provide more insight into the nature and properties of these interactions. Our results indicate pure closed-shell interactions in these systems with similar characteristics to the conventional halogen bonds.     

Two‐phase electromembrane extraction followed by gas chromatography‐mass spectrometry analysis

A two‐phase electromembrane extraction (EME) was developed and directly coupled with gas chromatography mass spectrometry (GC‐MS) analysis. The proposed method was successfully applied to the simultaneous determination of imipramine, desipramine, citalopram and sertraline. The model compounds were extracted from neutral aqueous sample solutions into the organic phase filled in the lumen of the hollow fiber. This method was accomplished with 1‐heptanol as organic phase, by means of 60 V applied voltage and with the extraction time of 15 min. Experiments reported recoveries in the range of 69–87% from 1.2 mL neutral sample solution. The compounds were quantified by GC‐MS instrument, with acceptable linearity ranging from 1 to 500 ng mL^?1 (R² in the range of 0.989 to 0.998), and repeatability (RSD) ranging between 7.5 and 11.5% (n = 5). The estimated detection limits (S/N ratio of 3:1) were less than 0.25 ng mL^?1. This novel approach based on two‐phase EME brought advantages such as simplicity, low‐costing, low detection limit and fast extraction with a total analysis time less than 25 min. These experimental findings were highly interesting and demonstrated the possibility of solving ionic species in the organic phase at the presence of electrical potential.     

Complexation studies of Mn2+, Zn2+ and Cd2+ ions with a series of tetradentate (N4) Schiff base ligands containing pyridine moiety in acetonitrile and nitromethane solutions by a competitive NMR technique using 7Li nucleus as a probe

Lithium-7 NMR spectroscopy was used to investigate the stoichiometry and stability of a Li⁺ complex with N¹,N²-bis(pyridin-2-ylmethylene)ethane-1,2-diamine (L¹), N¹,N³-bis(pyridin-2-ylmethylene)propane-1,3-diamine (L²) and N¹,N⁴-bis(pyridin-2-ylmethylene) butane-1,4-diamine (L³) in acetonitrile (AN) and nitromethane (NM) solutions. A competitive ⁷Li NMR method was also employed to probe the complexation of Mn²⁺, Cd²⁺ and Zn²⁺ ions with L¹, L² and L³ in the same solvents. The formation constants of the resulting complexes were evaluated from computer fitting of the mole ratio data to an equation that relates the observed chemical shifts to the formation constant. In both solvents, the stability of the resulting 1:1 complexes were found to vary in the order Zn²⁺>Cd²⁺>Mn²⁺>Li⁺. In addition, the stability of M–L complexes of M²⁺ with the Schiff base ligands found to vary in the order M²⁺–L¹ > M²⁺–L² > M²⁺–L³.