Water sorption-induced crystallization, structural relaxations and strength analysis of relaxation times in amorphous lactose/whey protein systems

Water sorption-induced crystallization, α-relaxations and relaxation times of freeze-dried lactose/whey protein isolate (WPI) systems were studied using dynamic dewpoint isotherms (DDI) method and dielectric analysis (DEA), respectively. The fractional water sorption behavior of lactose/WPI mixtures shown at aw ≤ 0.44 and the critical aw for water sorption-related crystallization (aw(cr)) of lactose were strongly affected by protein content based on DDI data. DEA results showed that the α-relaxation temperatures of amorphous lactose at various relaxation times were affected by the presence of water and WPI. The α-relaxation-derived strength parameter (S) of amorphous lactose decreased with aw up to 0.44 aw but the presence of WPI increased S. The linear relationship for aw(cr) and S for lactose/WPI mixtures was also established with R2 > 0.98. Therefore, DDI offers another structural investigation of water sorption-related crystallization as governed by aw(cr), and S may be used to describe real time effects of structural relaxations in noncrystalline multicomponent solids.

1H and 19F NMR relaxation time studies in (NH4)2ZrF6 superionic conductor

1H and 19F spin-lattice relaxation times in polycrystalline diammonium hexafluorozirconate have been measured in the temperature range of 10–400 K to elucidate the molecular motion of both cation and anion. Interesting features such as translational diffusion at higher temperatures, molecular reorientational motion of both cation and anion groups at intermediate temperatures and quantum rotational tunneling of the ammonium group at lower temperatures have been observed. Nuclear magnetic resonance (NMR) relaxation time results correlate well with the NMR second moment and conductivity studies reported earlier.

H-1 and F-19 NMR relaxation time studies in (NH4)(2)ZrF6 superionic conductor

H-1 and F-19 spin-lattice relaxation times in polycrystalline diammonium hexafluorozirconate have been measured in the temperature range of 10-400 K to elucidate the molecular motion of both cation and anion. Interesting features such as translational diffusion at higher temperatures, molecular reorientational motion of both cation and anion groups at intermediate temperatures and quantum rotational tunneling of the ammonium group at lower temperatures have been observed. Nuclear magnetic resonance (NMR) relaxation time results correlate well with the NMR second moment and conductivity studies reported earlier.

A molecular theory of collective orientational relaxation in pure and binary dipolar liquids

A molecular theory of collective orientational relaxation of dipolar molecules in a dense liquid is presented. Our work is based on a generalized, nonlinear, Smoluchowski equation (GSE) that includes the effects of intermolecular interactions through a mean‐field force term. The effects of translational motion of the liquid molecules on the orientational relaxation is also included self‐consistently in the GSE. Analytic expressions for the wave‐vector‐dependent orientational correlation functions are obtained for one component, pure liquid and also for binary mixtures. We find that for a dipolar liquid of spherical molecules, the correlation function ϕ(k,t) for l=1, where l is the rank of the spherical harmonics, is biexponential. At zero wave‐vector, one time constant becomes identical with the dielectric relaxation time of the polar liquid. The second time constant is the longitudinal relaxation time, but the contribution of this second component is small. We find that polar forces do not affect the higher order correlation functions (l>1) of spherical dipolar molecules in a linearized theory. The expression of ϕ(k,t) for a binary liquid is a sum of four exponential terms. We also find that the wave‐vector‐dependent relaxation times depend strongly on the microscopic structure of the dense liquid. At intermediate wave vectors, the translational diffusion greatly accelerates the rate of orientational relaxation. The present study indicates that one must pay proper attention to the microscopic structure of the liquid while treating the translational effects. An analysis of the nonlinear terms of the GSE is also presented. An interesting coupling between the number density fluctuation and the orientational fluctuation is uncovered.

Molecular theory of dielectric relaxation in a dense binary dipolar liquid

A molecular theory of dielectric relaxation in a dense binary dipolar liquid is presented. The theory takes into account the effects of intra- and interspecies intermolecular interactions. It is shown that the relaxation is, in general, nonexponential. In certain limits, we recover the biexponential form traditionally used to analyze the experimental data of dielectric relaxation in a binary mixture. However, the relaxation times are widely different from the prediction of the noninteracting rotational diffusion model of Debye for a binary system. Detailed numerical evaluation of the frequency-dependent dielectric function epsilon-(omega) is carried out by using the known analytic solution of the mean spherical approximation (MSA) model for the two-particle direct correlation function for a polar mixture. A microscopic expression for both wave vector (k) and frequency (omega) dependent dielectric function, epsilon-(k,omega), of a binary mixture is also presented. The theoretical predictions on epsilon-(omega) (= epsilon-(k = 0, omega)) have been compared with the available experimental results. In particular, the present theory offers a molecular explanation of the phenomenon of fusing of the two relaxation channels of the neat liquids, observed by Schallamach many years ago.

Dielectric relaxation in bismuth layer-structured BaBi4Ti4O15 ferroelectric ceramics

The dielectric properties of BaBi4Ti4O15 ceramics were investigated as a function of frequency (10(2)-10(6) Hz) at various temperatures (30 degrees C-470 degrees C), covering the phase transition temperature. Two different conduction mechanisms were obtained by fitting the complex impedance data to Cole-Cole equation. The grain and grain boundary resistivities were found to follow the Arrhenius law associated with activation energies: E-g similar to 1.12 eV below T-m and E-g similar to 0.70 eV above T-m for the grain conduction; and E-gb similar to 0.93 eV below T-m and E-gb similar to 0.71 eV above T-m for the grain boundary conduction. Relaxation times extracted using imaginary part of complex impedance Z `'(omega) and modulus M `'(omega) were also found to follow the Arrhenius law and showed an anomaly around the phase transition temperature. The frequency dependence of conductivity was interpreted in terms of the jump relaxation model and was fitted to the double power law. (C) 2010 Elsevier B. V. All rights reserved.

Carbon-13 and proton relaxation study of backbone dynamics of poly(vinyl acetate) in solution

The dynamics of poly(vinyl acetate) in toluene solution has been examined by C-13 and proton relaxation. C-13 spin-lattice relaxation time and nuclear Overhauser enhancement measurements were carried out as a function of temperature at 50.3 and 100.6 MHz. The spin-lattice relaxation times for backbone protons were measured at different temperatures at 200 MHz. The relaxation data have been analyzed using the Hall-Weber-Helfand (HWH) model, which describes backbone dynamics in terms of conformational transitions and the Dejean-Laupretre-Monnerie (DLM) model, which includes bond librations in addition to conformational transitions. The parameters obtained from the analysis of C-13 relaxation data were utilized to predict the proton relaxation data. The DLM model was found to be more successful in reproducing the experimental results. To study the influence of libration further, proton relaxation data for poly(vinyl acetate) over a wider range of temperature reported in the literature were analyzed by these two models. The DLM model could reproduce the experimental data at all temperatures whereas the HWH model was found to be successful only in accounting for the experimental data at high temperatures. The results demonstrate the importance of including the librational mode in the description of the backbone dynamics in polymers.

Carbon-13 relaxation study of chain segmental motion and side-chain internal rotations of poly(isobutyl methacrylate) in solution

The dynamics of poly(isobutyl methacrylate) in toluene solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed using the Dejean-Laupretre-Monnerie (DLM) model, which describes the dynamical processes in the backbone in terms of conformational transitions and bond librations. The relaxation data of the side chain nuclei have been analyzed by assuming different motional models, namely, unrestricted rotational diffusion, three site jumps, and restricted rotational diffusion. The different models have been compared for their ability to reproduce the experimental spin-lattice relaxation times and also to predict the behavior of NOE as a function of temperature. Conformational energy calculations have been carried out on a model compound by using the semiempirical quantum chemical method, AM1, and the results confirm the validity of the motional models used to describe the side-chain motion.

Structural, dielectric relaxation and piezoelectric characterization of Sr2+ substituted modified PMS-PZT ceramic

Pyrochlore phase free [Pb0.94Sr0.06] [(Mn1/3Sb2/3)(0.05)(Zr0.53Ti0.47)(0.95)] O-3 ceramics has been synthesized with pure Perovskite phase by semi-wet route using the columbite precursor method. The field dependences of the dielectric response and the conductivity have been measured in a frequency range from 50 Hz to 1 MHz and in a temperature range from 303 K to 773 K. An analysis of the real and imaginary parts of the dielectric permittivity with frequency has been performed, assuming a distribution of relaxation times. The scaling behavior of the dielectric loss spectra suggests that the distribution of the relaxation times is temperature independent. The SEM photographs of the sintered specimens present the homogenous structures and well-grown grains with a sharp grain boundary. The material exhibits tetragonal structure. When measured at frequency (100 Hz), the polarization shows a strong field dependence. Different piezoelectric figures of merit (k(p), d(33) and Q(m)) of the material have also been measured obtaining their values as 0.53, 271 pC/N and 1115, respectively, which are even higher than those of pure PZT with morphotropic phase boundary (MPB) composition. Thus the present ceramics have the optimal overall performance and are promising candidates for the various high power piezoelectric applications. (C) 2011 Elsevier B.V. All rights reserved.

Relaxation and jump dynamics of water at the mica interface

The orientational relaxation dynamics of water confined between mica surfaces is investigated using molecular dynamics simulations. The study illustrates the wide heterogeneity that exists in the dynamics of water adjacent to a strongly hydrophilic surface such as mica. Analysis of the survival probabilities in different layers is carried out by normalizing the corresponding relaxation times with bulk water layers of similar thickness. A 10-fold increase in the survival times is observed for water directly in contact with the mica surface and a non-monotonic variation in the survival times is observed moving away from the mica surface to the bulk-like interior. The orientational relaxation time is highest for water in the contact layer, decreasing monotonically away from the surface. In all cases the ratio of the relaxation times of the 1st and 2nd rank Legendre polynomials of the HH bond vector is found to lie between 1.5 and 1.9 indicating that the reorientational relaxation in the different water layers is governed by jump dynamics. The orientational dynamics of water in the contact layer is particularly novel and is found to undergo distinct two-dimensional hydrogen bond jump reorientational dynamics with an average waiting time of 4.97 ps. The waiting time distribution is found to possess a long tail extending beyond 15 ps. Unlike previously observed jump dynamics in bulk water and other surfaces, jump events in the mica contact layer occur between hydrogen bonds formed by the water molecule and acceptor oxygens on the mica surface. Despite slowing down of the water orientational relaxation near the surface, life-times of water in the hydration shell of the K ion are comparable to that observed in bulk salt solutions. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4717710]

Dielectric relaxation, phase transition and Rietveld studies of perovskite Pb0.94Sr0.06](Mn1/3Sb2/3)(0.05)(Zr0.52Ti0.48)(0.95)]O-3 ceramics

The frequency-dependent dielectric relaxation of Pb0.94Sr0.06](Mn1/3Sb2/3)(0.05)(Zr0.52Ti0.48)(0.95)]O-3 ceramics, synthesized in pure perovskite phase by a solid-state reaction technique is investigated in the temperature range from 303 to 773 K by alternating-current impedance spectroscopy. Using Cole-Cole model, an analysis of the imaginary part of the dielectric permittivity with frequency is performed assuming a distribution of relaxation times. The scaling behavior of the imaginary part of the electric modulus suggests that the relaxation describes the same mechanism at various temperatures. The variation of dielectric constant with temperature is explained considering the space-charge polarization. The SEM indicates that the sample has single phase with an average grain size similar to 14.2 mu m. The material exhibits tetragonal structure. A detailed temperature dependent dielectric study at various frequencies has also been performed. (C) 2013 Elsevier B.V. All rights reserved.

Dielectric relaxation and anti-ferromagnetic coupling of BiEu03 and BiGd03

BiEuO3 (BE) and BiGdO3 (BG) are synthesized by the solid-state reaction technique. Rietveld refinement of the X-ray diffraction data shows that the samples are crystallized in cubic phase at room temperature having Fm3m symmetry with the lattice parameters of 5.4925(2) and 5.4712(2) A for BE and BG, respectively. Raman spectra of the samples are investigated to obtain the phonon modes of the samples. The dielectric properties of the samples are investigated in the frequency range from 42 Hz to 1.1 MHz and in the temperature range from 303 K to 673 K. An analysis of the real and imaginary parts of impedance is performed assuming a distribution of relaxation times as confirmed by the Cole-Cole plots. The frequency-dependent maxima in the loss tangent are found to obey an Arrhenius law with activation energy similar to 1 eV for both the samples. The frequency-dependent electrical data are also analyzed in the framework of conductivity formalism. Magnetization of the samples are measured under the field cooled (EC) and zero field cooled (ZFC) modes in the temperature range from 5 K to 300 K applying a magnetic Field of 500 Oe. The FC and ZFC susceptibilities show that BE is a Van Vleck paramagnetic material with antiferromagnetic coupling at low temperature whereas BG is an anti-ferromagnetic system. The results are substantiated by the M-11 loops of the materials taken at 5 K in the ZFC mode. (C) 2014 Elsevier B.V. All rights reserved

I. Electron spin relaxation studies of manganese(II) complexes in acetonitrile. II. Nuclear spin relaxation studies of bromine in tetrabromomanganese(II) in acetonitrile

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn⁺²3d⁵ complexes, Mn(CH₃CN)₆⁺², MnCl₄^-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn⁺² complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et₄NCl-₄^-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et₄N⁺…MnCl₄^-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu₄NBr-MnBr₄^-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu₄N⁺…MnBr₄^-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr₄^-2 + Br^- = MnBr₄^-2 + Br^-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d⁵ electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d⁵ spin states of ion-paired MnBr₄^-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, ^Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Relaxation behavior of polymer blends with complex morphologies: Palierne emulsion model for uncompatibilized and compatibilized PP/PA6 blends

This paper deals with the dynamic rheological behavior of polypropylene/polyamide6 (PP/PA6) uncompatibilized blends and those compatibilized with a maleic anhydride grafted PP (PP/PP-g-MAH/PA6). The terminal relaxation times of the blends predicted by the Palierne emulsion model were compared with those obtained from experimental relaxation time spectra. The Palierne model succeeded well in describing PP/PA6 uncompatibilized blends with relatively low dispersed phase contents (10 wt%) and failed doing so for those of which the dispersed contents were high (30 wt%). It also failed for the compatibilized ones, irrespective of the dispersed phase content (10 or 30 wt%) and whether or not interface relaxation was taken into consideration. In the case of the uncompatibilized blend with high dispersed-phase content, interconnections among inclusions of the dispersed phase were responsible for the failure of the Palierne model. As for the compatiblized blends, in addition to particle interconnections, the existence of emulsion-in-emulsion (EE) structures was another factor responsible for the failure of Palieme model.

Determining adsorbate configuration on alumina surfaces with 13C nuclear magnetic resonance relaxation time analysis

Relative strengths of surface interaction for individual carbon atoms in acyclic and cyclic hydrocarbons adsorbed on alumina surfaces are determined using chemically resolved 13C nuclear magnetic resonance (NMR) T1 relaxation times. The ratio of relaxation times for the adsorbed atoms T1,ads to the bulk liquid relaxation time T1,bulk provides an indication of the mobility of the atom. Hence a low T1,ads/T1,bulk ratio indicates a stronger surface interaction. The carbon atoms associated with unsaturated bonds in the molecules are seen to exhibit a larger reduction in T1 on adsorption relative to the aliphatic carbons, consistent with adsorption occurring through the carbon-carbon multiple bonds. The relaxation data are interpreted in terms of proximity of individual carbon atoms to the alumina surface and adsorption conformations are inferred. Furthermore, variations of interaction strength and molecular configuration have been explored as a function of adsorbate coverage, temperature, surface pre-treatment, and in the presence of co-adsorbates. This relaxation time analysis is appropriate for studying the behaviour of hydrocarbons adsorbed on a wide range of catalyst support and supported-metal catalyst surfaces, and offers the potential to explore such systems under realistic operating conditions when multiple chemical components are present at the surface.