Partial molal volumes of ions in organic solvents from ultrasonic vibration potential and density measurements. III. Dimethylsulfoxide

The partial molal volumes of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Cl^–, Br^–, I^–, and NO ₃ ^- in DMSO at 25°C have been determined from ultrasonic vibration potential data and density data for solutions of uni-univalent electrolytes. Hepler's semiemprirical equation has been used to split ionic partial molal volumes into geometric and electrostrictive contributions. The results obtained in this work confirm the conclusion of our previous studies, namely, that the contribution of electrostriction is essentially determined by the properties of that layer of atoms, 0.3 to 0.4 nm thick, in contact with the ion and by the degree of steric hindrance of the poles of the dipole of the solvent molecule. On the other hand, the geometric contribution depends on the size of the solvent molecule and also on the arrangement of the solvent molecules about the ions. It is shown that the geometric contribution to the partial molal volume of ions is largely increased when ions cannot come close enough to the poles of the solvent-molecule dipole, owing to steric hindrance.     

Internal dynamics of the LaI3 molecule. II. Thermal average structure of the molecule and mean square vibration amplitudes

The structural parameters of the effective r _g configuration of the LaI₃ molecule were calculated using the DFT/B3LYP method. The difference between the calculated values of r _e (La-I) and r _g (La-I) is mostly due to the anharmonicity of the ν₁ and ν₂ vibrations and does not exceed the error in determining the distance r _g (La-I) in the electron diffraction experiment. Inclusion of the anharmonicity of the ν₂ and ν₄ deformation vibrations in calculations leads to decreased amplitudes l(I…I) and shrinking effect δ(I…I) compared to the respective values obtained in the harmonic approximation. The LaI₃ molecule proved to be more rigid than predicted by B3LYP calculations.     

Significant change in water contact angle of electrospray‐synthesized SiO2 films depending on their surface morphology

Amorphous SiO₂ films were deposited by means of an electrospray technique. The relation between the water contact angle (WCA) of the deposited SiO₂ films and the surface morphology is investigated. The feeding rate of the electrospray process greatly affects the morphology of the synthesized SiO₂ films. There is also a significant change in the WCA on the surface of the films: the rougher the surface, the greater the WCA. A model based on the Cassie–Baxter formulation is used to explain the change observed in the WCA on the SiO₂ films. Copyright © 2012 John Wiley & Sons, Ltd.     

FREE VIBRATION ANALYSIS OF LATTICE SANDWICH BEAMS UNDER SEVERAL TYPICAL BOUNDARY CONDITIONS

Free vibration problems of lattice sandwich beams under several typical boundary conditions are investigated in the present paper. The lattice sandwich beam is transformed to an equivalent homogeneous three-layered sandwich beam. Unlike the traditional analytical model in which the rotation angles of the face sheets and the core are assumed the same, different rotation angles are considered in this paper to characterize the real response of sandwich beams. The analytical solutions of the natural frequencies for several typical boundary conditions are obtained. The effects of material properties and geometric parameters on the natural frequencies are also investigated.     

Calculation of the vibration–rotational transition intensities of water molecules trapped in an argon matrix: stretching O–H vibrations spectral region

The frequencies and intensities of vibration–rotational transitions of water molecules in an argon matrix were calculated for temperatures of 6 and 30 K. The rigid asymmetric top approximation was used with available literature values of the effective rotational constants in the ground and excited vibrational states. The calculations were carried out by taking into account the existence of a non-equilibrium population distribution between the rotational levels of ortho- and para-water isomers. It was assumed that the temperature relaxation of the population of rotational levels is independent of the ortho- and para-isomers. Comparison of the results of the theoretical calculations with experimental literature data shows good agreement for the majority of the rotational structure lines for symmetric and antisymmetric stretching vibrations both in the frequency values and in the values of the relative intensities.     

Insight into industrial PLA aging process by complementary use of rheology,HPLC, and MALDI

Nowadays, there is a growing availability of biodegradable industrial materials intended to food contact applications whose service life behavior needs to be further investigated. This article is focused on the degradation of two materials based on polylactic acid. The correlation between the rate of degradation and the amount of trapped degradation products was investigated applying three characterization techniques in parallel, namely rheology, high‐performance liquid chromatography (HPLC), and matrix‐assisted laser desorption/ionization (MALDI). The rate of degradation was studied through the evaluation of their rheological properties and calculation of the number of average molecular weights, and weight‐average molecular weights. Water‐soluble oligomers and lactic acid were quantified by HPLC‐ultraviolet. Changes in cyclic and linear oligomers were monitored by MALDI‐time‐of‐flight mass spectrometry. Specimens of 4‐mm thickness of each biopolymer were subjected to hydrolysis in deionized water up to 6 months at two temperatures, simulating service conditions of food packaging. The diminution in viscosity and consequently in molecular weight distribution (20–60%) showed the degradation of the molecular structure of both polylactic acids. The chain scission was followed through the increasing values of lactic acid and hydrolyzed oligomers (twofold to eightfold), and the predominant signal of the linear oligomers over the cyclic ones with aging. Rheology, HPLC, and MALDI showed to be complementary tools to better understand the changes in the molecular structure. The obtained results showed the necessity of adding suitable stabilizers for each particular food packaging application. Copyright © 2013 John Wiley & Sons, Ltd.     

Ethylenically unsaturated polycarbosiloxanes for novel silicone hydrogels: synthesis,end‐group analysis,contact lens formulations,and structure–property correlations

A series of novel mono‐ethylenically unsaturated polycarbosiloxanes macromonomers as compatibilizer materials for soft silicon hydrogels were prepared from the anionic ring‐opening polymerization (AROP) of 2,2,5,5‐tetramethyl‐2,5‐disila‐1‐oxacyclopentane followed by methacrylation. The characterization was performed by end‐group analysis and included the determination of molecular weight, molecular weight distributions, end‐group functionality, and impurity profiles using gas chromatography‐mass spectrometry, gel permeation chromatography, nuclear magnetic resonance, and matrix‐assisted laser desorption/ionization time of flight mass spectrometry. The synthetic procedure was optimized to minimize the formation of any dimer that would have the potential to act as a low molecular weight cross linker. In addition, the novel di‐ethylenically unsaturated polycarbosiloxanes were synthesized by cationic polymerization. Use of these silicone derivatives was explored in the formulation of contact lenses, and the structure–property relationship was examined. When copoymerized with hydrophilic monomers, these were able to give transparent and wettable films with desired properties, particularly a low moduli for contact lenses. Contact lens with high modulus is often shown to impart a higher degree discomfort when worn upon the eye. It was clear from the structure–property relationship that the modulus and the tensile strength of the formulated material depend on the nature and length of the polycarbosiloxane used and may be tuned for the purpose as needed. Copyright © 2013 John Wiley & Sons, Ltd.     

Non‐contact evaluation of the electrical conductivity of thin metallic films by eddy current microscopy

An eddy current microscopy technique to evaluate the electrical conductivity of thin metallic films in a non‐contact manner is reported. A narrow track formed in an approximately 100 nm thick Au film was prepared, and a Co–Cr coated magnetic tip was driven to oscillate above the track both with and without current passing through the track. Despite the absence of current, the electromagnetic interaction between the tip and the stray magnetic field from the track gave rise to a phase delay in the probe. This was due to an eddy current being induced within part of the track. Moreover, measurements of the phase change in the probe oscillation for different metallic films with thicknesses of about 100 nm found this to be proportional to the electrical conductivity of the film. Finally, the electrical conductivity of an Al film was evaluated using the eddy current microscopy technique. Copyright © 2012 John Wiley & Sons, Ltd.     

Vibration of strings with nonlinear supports

The dynamic string motion, which displacement is unilaterally constrained by the rigid termination condition of an arbitrary geometry has been simulated and analyzed. The treble strings of a grand piano usually terminate at a capo bar, which is situated above the strings. The apex of a V-shaped section of the capo bar defines the end of the speaking length of the strings. A numerical calculation based on the traveling wave solution is proposed for modeling the nonlinearity inducing interactions between the vibrating string and the contact condition at the point of string termination. It was shown that the lossless string vibrates in two distinct vibration regimes. In the beginning the string starts to interact in a nonlinear fashion with the rigid terminator, and the resulting string motion is aperiodic. Consequently, the spectrum of the string motion depends on the amplitude of string vibrations, and its spectral structure changes continuously with the passage of time. The duration of that vibration regime depends on the geometry of the terminator. After some time of aperiodic vibration, the string vibrations settle in a periodic regime where the resulting spectrum remains constant.