Volumetric, Compressibility, and Surface Tension Studies on Micellization Behavior of SDS in Aqueous Medium: Effect of Sugars

The densities , velocities of sound , and surface tension , of anionic surfactant sodium dodecyl sulfate in presence of aqueous saccharides (fructose and maltose) with concentrations 0.01 and 0.10 mol kg^?1 have been reported over a wide temperature range (293.15–313.15 K) at an interval of 5 K. The apparent molar volume , isentropic compressibility , and apparent molar adiabatic compression values have been calculated using densities and velocities of sound data. Both, and vary non‐linearly at lower concentration of surfactant and tend to achieve linearity at higher concentration of surfactant in presence of saccharides. From the surface tension data, parameters like surface excess , minimum area occupied by the surfactant molecule at the saturated air/solution interface and surface film pressure have been computed. The effect of additives on these parameters has been discussed in terms of different types of the interactions pertaining in the micellar system. An attempt has also been made to draw an inference regarding the effect of these additives on the critical micelle concentration of the surfactant.     

Synthesis,Characterization and Aqueous Properties of a New Hybrid Fluorocarbon Cationic Surfmer

A novel hybrid fluorocarbon cationic surfmer has been synthesized and its aggregation and surface properties have been studied by surface tension, electrical conductivity, steady‐state fluorescence, Rayleigh light scattering, dynamic light scattering and transmission electron microscopy. Through surface tension, electrical conductivity, steady‐state fluorescence and Rayleigh light scattering measurements, the effectiveness of surface tension reduction, the maximum surface excess concentration, the minimum area occupied per surfactant molecule at the air/water interface, the micropolarity and aggregation number of micelles were investigated. The results shows that the surfmer has superior surface activity and lower micropolarity than other surfmers. The critical micelle concentration at different temperatures and a series of thermodynamic parameters (, , and , , , and ) of micellization were evaluated. The thermodynamic parameters showed that the micelle formation was entropy‐driven in the temperature range of 15–40 °C. The size and morphology of the aggregates were also confirmed by dynamic light scattering and transmission electron microscopy.     

Counterion-Induced Cationic Flexible Nanoparticle Catalytic of Piperidinolysis of Phenyl Salicylate

The removal of PSa^? from bulk aqueous phase to the pseudo‐micellar phase by halobenzoate counterion X is responsible for the monotonic increase in k_obs (pseudo first‐order rate constants) with the increase in the values of [MX] where MX = sodium salts of 2‐, and 4‐halobenzoic acids. The values of ion exchange constants, or for X = 2‐ and 4‐halobenzoate ions in the presence of tetradecyltrimethylammonium bromide (TTABr) were calculated from the apparent catalytic rate constants, ^Xk_cat which represent the catalytic effect of CFN. Larger values of or were observed for X = 4‐halobenzoate ions than that for X = 2‐halobenzoate ions due to isomeric factors. The values of or determined in the presence of TTABr were compared with previously determined or values in the presence of cetyltrimethylammonium bromide (CTABr). The values of or are nearly 8 ~ 9‐fold larger for 4‐IBz^?, 4‐BrBz^? and 4‐ClBz^? compared to the respective values of X = 2‐IBz^?, 2‐BrBz^? and 2‐ClBz^?. The values of or for X = 4‐FBz^? is nearly 3‐fold larger than that for X = 2‐FBz^?. The values of or for X = 2‐ and 4‐halobenzoates are significantly smaller in the presence of TTABr than these in the presence of CTABr nanoparticles.     

Mixed Micellization and Interfacial Properties of Ionic Liquid‐Type Imidazolium Gemini Surfactant with Amphiphilic Drug Amitriptyline Hydrochloride and its Thermodynamics

The thermodynamics of mixed micellization of amitriptyline hydrochloride (AMT) with ionic liquid‐type imidazolium gemini surfactant ([C₁₀‐4‐C₁₀im] Br₂), was investigated at different mole fractions and temperatures by surface tension measurements. The deviation of the critical micelle concentration (CMC) from the ideal critical micelle concentration (CMC * ), micellar mole fraction () from ideal micellar mole fraction (), the values of interaction parameter () and activity coefficients () (for both mixed micelles and mixed monolayer) explained the non‐ideal behavior (i.e., synergistic behavior) of binary mixtures. The excess free energy (?G_ex) for the AMT‐[C₁₀‐4‐C₁₀im] Br₂ binary mixtures explained the mixed micelles stability in comparison to micelles of [C₁₀‐4‐C₁₀im] Br₂ and pure AMT. Interfacial parameters, i.e., Gibbs surface excess (), minimum head group area at air/water interface (), free energy of micellization (), and standard Gibbs energy of adsorption (?G_ads^o) were also evaluated for the systems. The standard entropy of adsorption (?S_ads^o) was found higher than the standard entropy of micellization (?S_m^o) at all mole fractions of AMT (α₁).     

Study of Micellization of Sodium Dodecyl Sulfate in Non-Aqueous Media Containing Lauric Acid and Dimethylsulfoxide

Interactions between dimethylsulfoxide (DMSO), lauric acid (LA) and anionic surfactant, sodium dodecyl sulfate (SDS) in non‐aqueous media have been studied in detail using conductometric, volumetric, and ultrasonic speed techniques. Conductivities, densities and ultrasonic speeds of 1 × 10^?3 to 11 × 10^?3 m SDS solutions in a mixture of LA (0.10 m) and DMSO between 298.15 and 313.15 K have been measured. The experimental data have been correlated against temperature and concentration of SDS using standard relations. The critical micelle concentration (CMC) values have been determined by using different methods like conductance, density and ultrasonic speed. All the methods yielded identical CMC values. The measured data were used to calculate various useful thermodynamic parameters like standard free energy, , enthalpy, , and entropy, , of micelle formation. From the density data of the surfactant, the change of the apparent molar volume upon micellization has been calculated. Density and ultrasonic speed data were used to evaluate the apparent molar adiabatic compressibility for the micelle of the surfactant at different temperatures over a wide concentration range.     

Imidazolium‐Based Ionic Liquid as Modulator of Physicochemical Properties of Cationic,Anionic, Nonionic,and Gemini Surfactants

The aggregation morphology of 2 cationic surfactants (cetyldimethylethanolammonium bromide and cetyldiethylethanolammonium bromide), an anionic surfactant (sodium dodecylbenzenesulfonate), a nonionic surfactant (Triton X‐100), and 2 gemini surfactants (16‐4‐16,2Br^?[butanediyi‐1,4‐bis(dimethyldohexylammonium bromide)] and 16‐6‐16,2Br^?[hexanediyi‐1,6‐bis(dimethyldohexylammonium bromide)]) in the presence of the ionic liquid (IL) 1‐ethyl‐3‐methylimidazoliumbromide [Emim][Br] is studied using various techniques such as surface tension, conductivity, and UV–visible and fluorescence spectroscopy. Increasing the concentration of [Emim][Br] results in a decrease in the critical micelle concentration (CMC) value of the surfactants. Various interfacial properties, namely the surface excess concentration (Г_max), minimum area per molecule at the air–water interface (A_min)_, and surface pressure at the CMC (π_cmc), as well as the thermodynamic parameters such as free energy of the given air/water interface (), Gibbs free energy of micelle formation (), Gibbs free energy of micellization per alkyl tail (), Gibbs energy of transfer (), and standard free energy of adsorption () were also investigated. The aggregation number (N_agg) was determined by the fluorescence method. It was observed that N_agg decreased with increasing weight‐percent of the IL.     

Synthesis and Investigation of Surface Active Properties of Counterion Coupled Gemini Surfactants

Three counterion coupled gemini (cocogem) surfactants in the series 1,6‐bis(N,N‐alkyldimethylammonium) adipate, referred as n‐6‐n (n = 12, 14, 16), were synthesized, purified and characterized by ¹H NMR and ¹³C NMR. Their physicochemical properties were investigated by electrical conductivity and surface tension measurements. The degree of ionization, critical micelle concentration (CMC), surface excess at the air/solution interface (Γ_max), minimum area per surfactant molecule at the air/solution interface (A_min), surface tension at the CMC (γ_CMC), and pC₂₀ (negative log of the surfactant molar concentration, required to reduce the surface tension of water by 20 mN m^?1) were calculated. Increase in tail length of the surfactants increases the efficiency of surfactants to decrease the surface tension of water. Thermodynamic parameters, viz. molar free energy at the maximum adsorption attained at CMC (G_min), standard Gibb's energy of micellization (), and standard Gibbs energy of adsorption (), were also calculated. The and values show that the monomers were preferred to be adsorbed at the air/water interface and then in the micellar formation in the bulk. Additionally, fluorescence measurements were used to find the aggregation number. Other relevant surface properties (Krafft point, emulsion stability, foaming ability, micellar stability and dye solubilization ability) were also evaluated. These results suggest that with respect to emulsion formation, micellar stability and dye solubilization, the cocogem with a 16‐carbon chain gives better results, producing 89 % more stable foams and shows better aggregational behavior.     

Synthesis and Micellization of Organosilicon Gemini Quaternary Ammonium Surfactants

A novel class of organosilicon gemini quaternary ammonium surfactant alkyl‐α, ω‐bis(diethyl‐methyl‐dimethoxy‐silopropyl ammonium bromide) (α, ω = 1,4; 1,6; 1,8) was synthesized and characterized by ¹H‐nuclear magnetic resonance (NMR) and elemental analysis. It is found that the quaternization reaction has two steps: first single quaternization and then double quaternization. The effect of solvent on convert ratio has the following sequence: polar aprotic solvents > polar protic solvents > aromatic solvents. The electrical conductivity of aqueous solution was measured at 20, 25, 30 and 35 °C, and the thermodynamic properties of , and were calculated according to the mass action model and Gibbs equation. It is shown that the enthalpy driven and entropy driven are almost equal in the micellization of [SiC₃‐4‐SiC₃]Br₂ and [SiC₃‐6‐SiC₃]Br₂, but in the micellization of [SiC₃‐8‐SiC₃]Br₂, the enthalpic contribution becomes significant and the effect of thermal is greater than the degree of order in the micellization.     

First‐Principles Study of Sc1−xTixF3 (x ≤ 0.375): Negative Thermal Expansion,Phase Transition,and Compressibility

We present the first‐principles investigation of (x ≤ 0.375). Controllable thermal expansion of is achieved by different Ti contents. The negative thermal expansion (NTE) behavior is weakened gradually with increasing Ti content, which is consistent with experimental measurements. The Jahn–Teller effect plays an important role in the cubic‐to‐rhombohedral phase transition, which stems from the enhanced energy stability when the 3d orbitals of cation split into triply degenerate and sets. The unusual thermal stiffening of is found, which is similar to that of and but contrary to other NTE materials.     

Investigation and modelling of damping mechanisms of magnetorheological elastomers

Damping in MREs is considered to be ascribed to viscous flow of the rubber matrix, interfacial damping at the interface between the magnetic particles and the matrix and magnetism induced damping. In this study, individual components in MREs that contribute to material damping were investigated. A model was developed to include viscous flow of the rubber matrix, interfacial damping and magnetism induced damping to give the total damping capacity of MREs ( )It was found that depends on frequency, iron sand content, strain amplitude and is independent of the applied magnetic field over saturation magnetization. The proposed model was assessed experimentally using a series of isotropic and anisotropic MREs. Comparison between tan δ with showed that matched the experimental trends with average percentage difference of 8.1% and 21.8% for MREs with modified iron sand unmodified iron sand, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43247.     

Mixed‐Norm Spaces and Prediction of SαS Moving Averages

Suppose that is an i.i.d. symmetric α‐stable noise, 1 < α < 2, and consider the moving average process given by . Conditions are obtained for the convergence rate of the moving average series, as well as that of the inverted (autoregressive) representation . These conditions are expressed in terms of the associated function and its reciprocal belonging to certain mixed‐norm spaces of functions on the open unit disc. Properties of these spaces are explored. Criteria are also derived for the rate of mixing in a certain sense.     

Enhanced Energy Storage of Dielectric Nanocomposites at Elevated Temperatures

Enhancing the performance of dielectric capacitors toward higher energy density and higher operating temperatures has been drawing increased interest. Therefore, in this investigation, research efforts were dedicated to the fabrication and characterization of nanocomposites in order to enhance the energy density at both room temperature and elevated temperature. The dielectric capacitors are fabricated using nanocomposites composed of BaTiO nanoparticles with polyimide (PI) matrix aiming at combining the high relative dielectric permittivity of the ceramic filler and the high breakdown strength of the polymeric matrix. Dielectric energy storage performance is assessed for nanocomposites with volume fractions ranging from 0 to 20% under operating frequency from 20 Hz to 1 MHz and temperatures ranging from 20 to 120C. It is observed that with the increase of temperature, the capacitance increased while the energy density slightly decreased but significantly higher than pure polymer samples. The highest energy density was found for BaTiO/PI nanocomposites with 20% volume fraction, 9.63 J/cm at 20C and 6.79 J/cm at 120C. Overall, testing results indicate that using nanocomposites of BaTiO/PI as a dielectric component shows promise for implementation to preserve high energy density values up to temperatures of 120C.     

A New Covariance Function and Spatio‐Temporal Prediction (Kriging) for A Stationary Spatio‐Temporal Random Process

Consider a stationary spatio‐temporal random process and let be a sample from the process. Our object here is to predict, given the sample, for all t at the location s _o. To obtain the predictors, we define a sequence of discrete Fourier transforms using the observed time series. We consider these discrete Fourier transforms as a sample from the complex valued random variable . Assuming that the discrete Fourier transforms satisfy a complex stochastic partial differential equation of the Laplacian type with a scaling function that is a polynomial in the temporal spectral frequency ω, we obtain, in a closed form, expressions for the second‐order spatio‐temporal spectrum and the covariance function. The spectral density function obtained corresponds to a non‐separable random process. The optimal predictor of the discrete Fourier transform is in terms of the covariance functions. The estimation of the parameters of the spatio‐temporal covariance function is considered and is based on the recently introduced frequency variogram method. The methods given here can be extended to situations where the observations are corrupted by independent white noise. The methods are illustrated with a real data set.     

Micellar Properties of Surface Active Ionic Liquid Lauryl Isoquinolinium Bromide and Anionic Polyelectrolyte Poly(Acrylic Acid Sodium Salt) in Aqueous Solution

The complex formation between anionic polyelectrolyte poly(acrylic acid sodium salt) [NaPAA] and surface active ionic liquid (SAIL) lauryl isoquinolinium bromide [C₁₂iQuin][Br] in aqueous media has been investigated by surface tension, isothermal titration calorimetry (ITC), and conductance. The self‐assembled structures have been characterized using dynamic light scattering (DLS) and turbidity measurements. A range of surface parameters have been calculated from tensiometric measurements including critical micelle concentration (CMC), surface excess concentration (Γ_cmc), surface pressure at the interface (Π_cmc), minimum area occupied at air–solvent interface (A_min), adsorption efficiency (pC₂₀), and surface tension at the CMC (γ_cmc). The thermodynamic parameters, i.e., standard enthalpy of micellization , standard free energy of micellization (), and standard entropy of micellization () have also been evaluated. Four different stages of transitions, corresponding to the progressive formation of NaPAA–[C₁₂iQuin][Br] complex (C₁)_, critical aggregation concentration (CAC), critical saturation concentration (C₃) and CMC have been observed owing to strong electrostatic and hydrophobic interactions. The results obtained from DLS and turbidity measurements show that size of the aggregates first decreases and then increases in the presence of polyelectrolyte. The binding isotherms obtained using isothermal titration calorimetry (ITC) show the concentration dependence as well as the highly cooperative nature of interactions corresponding to formation of polyelectrolyte–SAIL complexes.     

Mechanism of the Inhibitory Effect of Hydroxytyrosol on Lipid Oxidation in Different Bulk Oil Systems

The autoxidation of purified triacylglycerols obtained from fish, canola, and olive oils in the presence of different concentrations of hydroxytyrosol at 60–100 °C was evaluated by different kinetic parameters including the stabilizing factor (F) as a measure of effectiveness, the oxidation rate ratio (ORR) as a measure strength, and the antioxidant activity (A) which combines the F and ORR parameters. The overall performance of hydroxytyrosol was attributed to the main reaction of chain termination () as competed with the main oxidation reaction of chain propagation () and, additionally, the antioxidative side reactions of chain propagation ( and ), and the pro‐oxidative side reaction of chain initiation () in some cases.     

Comparison of the Composition and Structural Parameters of W/O Microemulsions Containing Gemini Imidazoliums with Those Containing Monomeric Analogues

The composition and structural parameters of W/O microemulsions containing the gemini surfactant 1,4‐bis(3‐alkylimidazolium‐1‐yl) butane bromide [(C_n‐4‐C_n)Br₂, n = 12, 14, 16] + pentan‐1‐ol + octane + water and W/O microemulsions containing the ionic liquid surfactant 1‐alkyl‐3‐methylimidazolium (C_nmimBr, n = 12, 14, 16) + pentan‐1‐ol + octane + water were studied and compared. The mole fractions of the n‐alkyl alcohol at the interfacial layer in (C_n‐4‐C_n)Br₂ based microemulsion systems are always larger than those in C_nmimBr based microemulsion systems. However, the mole fractions of the n‐alkyl alcohol in the oil phase are nearly the same for both the microemulsion systems. The (C_n‐4‐C_n)Br₂ based microemulsion systems have greater absolute values of the free enthalpy values than that for C_nmimBr based systems. In the (C_n‐4‐C_n)Br₂ based microemulsion systems, a large number of cosurfactants at the interfacial layer is conducive to the formation of a smaller droplet W/O microemulsion. The effects of n‐alkyl alcohols, alkanes, salinity and temperature on the composition and structural parameters of the (C_n‐4‐C_n)Br₂ based and C_nmimBr based microemulsion systems were also investigated and discussed.     

Effect of Surface Concentration of Lu on Oxygen Permeation of Polycrystalline Alumina at High Temperatures

The effect of Lu surface concentration on oxygen permeation in polycrystalline α‐alumina wafers was determined at 1773 K under limited oxygen potential gradients (Δ), where the two surfaces of the wafer were deliberately subjected to different oxygen partial pressures [ (I) ?  (II)]. When oxygen permeation occurred mainly by oxygen GB diffusion under a Δ generated by a combination of low values, the Lu‐coating on the (I) [ (II)] surface decreased [increased] the oxygen permeability constants. When Δ was the result of a combination of high values, where oxygen permeation proceeded mainly by aluminum GB diffusion, the oxygen permeability constants were decreased only by the Lu‐coating on the (I) surface. The analysis of mass transfer parameters, such as the chemical potentials, GB diffusion coefficients, and fluxes of aluminum and oxygen in the wafers, suggested that ambient oxygen molecules were effectively attracted toward Lu‐coated surfaces exposed to low‐ environments, leading to a change in oxygen permeability.     

Grain Boundary Curvatures Measurements in Annealed Yttria‐Stabilized Zirconia (3Y‐TZP) and Their Relation to Mean Grain Size

It was determined that the mean grain boundary radius of curvature in 3 mol% yttria‐stabilized zirconia isothermally annealed without and with a DC electric field  = 18 V/cm was uniquely proportional to the mean linear intercept grain size , the proportionality constant α = 3/2 being in accord with the Rios‐Fonseca stereological model.     

Forced convection boiling in a stator–rotor–stator spinning disc reactor

Boiling of a pure fluid inside the rotor–stator cavities of a stator–rotor–stator spinning disc reactor (srs‐SDR) is studied, as a function of rotational velocity ω, average temperature driving force and mass flow rate . The average boiling heat transfer coefficient h_b increases a factor 3 by increasing ω up to 105 rad s^?1, independently of and . The performance of the srs‐SDR, in terms of h_b vs. specific energy input ?, is similar to tubular boiling, where pressure drop provides the energy input. The srs‐SDR enables operation at Wm , yielding values of h_b not practically obtainable in passive evaporators, due to prohibitively high pressure drops required. Since h_b is increased independently of the superficial vapor velocity, h_b is not a function of and the local vapor fraction. Therefore, the srs‐SDR enables a higher degree of control and flexibility of the boiling process, compared to passive flow boiling. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3763–3773, 2016     

Temperature-Dependent Mechanism of Antioxidant Activity of o-Hydroxyl,o-Methoxy,and Alkyl Ester Derivatives of p-Hydroxybenzoic Acid in Fish Oil

The autoxidation of purified fish oil in the presence of different concentrations of o‐hydroxyl, o‐methoxy, and alkyl ester derivatives of p‐hydroxybenzoic at 35–55 °C was evaluated by different kinetic parameters including the stabilizing factor as a measure of effectiveness, the oxidation rate ratio as a measure of strength, and the antioxidant activity which combines the two parameters. Methyl gallate as the most reactive antioxidant participated only in the main reaction of chain termination (ROO· + InH ROOH + In·). Gallic acid, ethyl protocatechuate, protocatechuic acid, vanillic acid, and syringic acid, were able to protect fish oil against oxidation in terms of the extent of their participation in the pro‐oxidative side reactions of chain initiation (InH + ROOH In· + RO· + H₂O and InH + O₂ In· + HOO·) and the antioxidative side reactions of chain propagation (In· + ROO· In‐OOR and In· + In· products).