The Johari-Goldstein beta-relaxation of water

There is a plethora of experimental data on the dynamics of water in mixtures with glycerol, ethylene glycol, ethylene glycol oligomers, poly(ethylene glycol) 400 and 600, propanol, poly(vinyl pyrrolidone), poly(vinyl methylether), and other substances. In spite of the differences in the water contents, the chemical compositions, and the glass transition temperatures Tg of these aqueous mixtures, a faster relaxation originating from the water (called the nu-process) is omnipresent, sharing the following common properties. The relaxation time tau(nu) has Arrhenius temperature dependence at temperatures below Tg of the mixture. The activation energies of tau(nu) all fall within a neighborhood of 50 kJ/mol. At the same temperature where mixtures are all in their glassy states, the values of tau(nu) of several mixtures are comparable. The Arrhenius temperature dependence of tau(nu) does not continue to higher temperatures and instead it crosses over to a stronger temperature dependence at temperatures above Tg. The dielectric relaxation strength of the nu-process, Deltaepsilon(nu)(T), has a stronger temperature dependence above Tg than below, mimicking the change of enthalpy, entropy, and volume when crossing Tg. These general property of the nu-process (except for the magnitude of the activation energy) had been found before in the secondary relaxation of the faster component in several binary nonaqueous mixtures. Other properties of the secondary relaxation in these nonaqueous mixtures have helped to identify it as the Johari-Goldstein (JG) secondary relaxation of the faster component. The similarities in properties lead us to conclude that the nu-processes in water mixtures are the JG secondary relaxations of water. The conclusion is reinforced by the processes behaving similarly to the nu-process found in 6 A thick water layer (two molecular layers) in fully hydrated Na-vermiculite clay, and in water confined in molecular sieves, silica hydrogels, and poly(2-hydroxyethyl methacrylate) hydrogels.     

Broadband dielectric study of dynamics of polymer and solvent in poly(vinyl pyrrolidone)/normal alcohol mixtures

Broadband dielectric measurements of poly(vinyl pyrrolidone) (PVP)-monohydroxyl alcohol mixtures of various normal alcohols with the number of carbon atoms per molecule ranging from 1 to 9 were made in the frequency range of 20 Hz to 20 GHz at 25 degrees C. Two relaxation processes due to the reorientation of dipoles on the PVP and alcohol molecules were observed. The relaxation process at frequencies higher than 100 MHz is the primary process of alcohols, and that at frequencies lower than 10 MHz is attributed to the local chain motion of PVP. For mixtures of alcohol molecules that are smaller than propanol, the relaxation time of the alcohol increases with increasing PVP concentration, whereas for mixtures of alcohol molecules larger than butanol, the relaxation time of the alcohol decreases with increasing PVP concentration. The increase in the density of hydrogen-bonding sites upon the addition of PVP reduces the relaxation time of alcohol in the mixture, and vice versa. The relaxation time of the local chain motion of PVP increases with PVP concentration and solvent viscosity. Different time scales of the molecular motions of polymer and solvent coexist in homogeneous mixtures with hydrogen-bonded polar solvent and polymer.     

Broadband dielectric investigation on poly(vinyl pyrrolidone) and its water mixtures

Broadband dielectric spectroscopy and differential scanning calorimetry measurements have been performed to study the molecular dynamics poly (vinyl pyrrolidone) and its water solutions in a wide range of concentrations (0 wt %20 wt % suggesting that this dynamical process is dominated by water-water interactions. In addition, the temperature dependence of the water relaxation times exhibits a crossover from non-Arrhenius to Arrhenius behavior during cooling throughout the glass transition range, which has been interpreted as due to the constrains imposed by the rigid polymer matrix on the water molecules dynamics.     

Contrary hydration behavior of N-isopropylacrylamide to its polymer, P(NIPAm), with a lower critical solution temperature

The number of hydrated water molecules per N-isopropylacrylamide in homogeneous aqueous solution was determined to be a constant with a value of 5-6 below and above the lower critical solution temperature, LCST (32 degrees C), of its polymer, poly(N-isopropylacrylamide), by high-frequency dielectric relaxation techniques.     

The glass transition and dielectric secondary relaxation of fructose-water mixtures

Broad-band dielectric measurements for fructose-water mixtures with fructose concentrations between 70.0 and 94.6 wt% were carried out in the frequency range of 2 mHz to 20 GHz in the temperature range of -70 to 45 degrees C. Two relaxation processes, the alpha process at lower frequency and the secondary beta process at higher frequency, were observed. The dielectric relaxation time of the alpha process was 100 s at the glass transition temperature, T(g), determined by differential scanning calorimetry (DSC). The relaxation time and strength of the beta process changed from weaker temperature dependences of below T(g) to a stronger one above T(g). These changes in behaviors of the beta process in fructose-water mixtures upon crossing the T(g) of the mixtures is the same as that found for the secondary process of water in various other aqueous mixtures with hydrogen-bonding molecular liquids, polymers, and nanoporous systems. These results lead to the conclusion that the primary alpha process of fructose-water mixtures results from the cooperative motion of water and fructose molecules, and the secondary beta process is the Johari-Goldstein process of water in the mixture. At temperatures near and above T(g) where both the alpha and the beta processes were observed and their relaxation times, tau(alpha) and tau(beta), were determined in some mixtures, the ratio tau(alpha)/tau(beta) is in accord with that predicted by the coupling model. Fixing tau(alpha) at 100 s, the ratio tau(alpha)/tau(beta) decreases with decreasing concentration of fructose in the mixtures. This trend is also consistent with that expected by the coupling model from the decrease of the intermolecular coupling parameter upon decreasing fructose concentration.     

Water properties in the super-salt-resistive gel probed by NMR and DSC

The so-called "super-salt-resistive gel", or poly(4-vinylphenol) (P4VPh) hydrogel, of different water contents ( H = 97-51%) was prepared by cross-linking with different amounts of ethylene glycol diglycidyl ether. 1H NMR spectroscopy was used to investigate the dynamic properties of water in the gel samples in terms of the spin-spin relaxation. The T2 values in those hydrogels were analyzed by assuming a two-component system, namely, T 2(long) and T2(short), and their fractions were obtained. In the higher water content region (75% < or = H < or = 97%), T2(long) for P4VPh gel was almost constant or even slightly increased with decreasing temperature. On the other hand, T2(long) for poly(vinyl alcohol) (PVA) gel (80% < or = H < or = 96%) significantly decreased with decreasing temperature, showing a natural behavior for water mobility in common hydrogels. Water in P4VPh gels of lower water contents ( H = 70% and 51%) also showed intriguing behaviors: the T2 values are much larger than those of gels with higher water contents and decreased with decreasing temperature only in the lower temperature range (<10 degrees C). The fraction of T2(long) values of P4VPh gel showed another contrast to those of PVA gel; the latter decreased with decreasing water content (normal behavior), while in the former gel the highest fraction (ca. 60% at 20 degrees C) was observed for a sample with the lowest water content ( H = 51%). On the other hand, the results of DSC measurements for P4VPh gel were less specific than those of T2 and comparable to those of common hydrogels such as PVA; with decreasing water content, the total amounts of free water and freezable bound water per polymer mass (g/g) decreased, while the amount of nonfreezing water per polymer also decreased.     

Analysis of rapid chain dynamics in isochronal dielectric measurements of polymers

Fast dynamics within the microwave frequency range (approximately gigahertz) in polymer systems as a function of temperature (in the range from 20 to 190 degrees C) were studied using high frequency dielectric spectroscopy. The frequency of radiation was varied from 0.5 to 18 GHz. The isochronal dielectric loss data were taken to eliminate the complexity arising from the frequency-independent, temperature-dependent background loss in the condensed phase. These studies were conducted for poly(caprolactone) (PCL), poly(ethylene oxide) (PEO), poly(ethylene oxide) with methoxy end group (PEO-CH3), PLA-b-PEO-b-PLA triblock copolymers, and several polymers with high glass transition temperatures. These polymers possess glass temperatures ranging from -62 degrees C (PCL) to 110 degrees C (PMMA). One broad relaxation process was found only for polymers (PCL, PEO, and PLA-b-PEO-b-PLA) with low glass transition temperatures. The effect due to end groups was investigated by comparing the results of PEO with hydroxy versus methoxy end groups. The measured relaxation process was determined not to be associated with end groups. The results from temperature-dependent dielectric spectroscopy indicate that the relaxation process follows an Arrhenius T dependence suggesting that it is due to local motions. The activation energy of the relaxation process was measured and investigated based on the coupling model. The results suggest that the observed relaxation process behaves as a Johari-Goldstein beta relaxation.     

Relaxation phenomena in poly(vinyl alcohol)/fumed silica affected by interfacial water

Interaction of poly(vinyl alcohol) (PVA) with fumed silica was investigated in the gas phase and aqueous media using adsorption, broadband dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization current (TSDC), infrared spectroscopy, thermal analysis, and one-pass temperature-programmed desorption (OPTPD) mass-spectrometry (MS) methods. PVA monolayer formation leads to certain textural changes in the system (after suspension and drying) because of strong hydrogen bonding of the polymer molecules to silica nanoparticles preventing strong interaction between silica particles themselves. This strong interaction promotes associative desorption of water molecules at lower temperatures than in the case of silica alone. Interaction of PVA with silica and residual water leads to depression of glass transition temperature (T(g)). There are three types of dipolar relaxations at temperatures lower and higher than the T(g) value. A small amount of adsorbed water leads to significant conductivity with elevating temperature.     

Dielectric relaxation in a water-oil-triton X-100 microemulsion near phase inversion

A mixture of water (10 mM KCl), toluene and Triton X-100 (40:40:20 wt %) shows temperature-dependent phase inversion. The phase inversion has been studied by dielectric spectroscopy over a frequency range of 10 Hz to 1 GHz. At temperatures above about 37 degrees C, dielectric relaxation appeared around 10 MHz, which was due to interfacial polarization in a water-in-oil type emulsion. The dielectric relaxation drastically changed between 30 and 25 degrees C. With decreasing temperature, the intensity of dielectric relaxation increased steeply below 30 degrees C to attain a peak at 27 degrees C, where that change was associated with an increase in low-frequency conductivity by about three orders between 30 and 26 degrees C. The dielectric behavior has been interpreted in terms of interfacial polarization with a percolation model in which spherical water droplets, arranged in array in a continuous oil phase, are randomly connected with their nearest neighbors using water bonds.     

Dielectric dispersion in water + 2-hydroxypyridine solid mixtures

The complex electric permittivity was measured in water + 2-hydroxypyridine (2HP) solid mixtures as a function of concentration, temperature and frequency. Just after freezing of diluted mixtures, (mole fraction of 2HP < 0.2) pronounced dielectric dispersion in the MHz region was observed. The dispersion disappears on cooling between -30 and -40 degrees C in a first-order phase transition. The dispersion was explained in terms of the movement of a guest molecule (2HP) in a clathratelike structure of ice.     

Broadband dielectric study of dynamics of poly(vinyl pyrrolidone)-ethylene glycol oligomer blends

Broadband dielectric measurements for blends of poly(vinyl pyrrolidone) (PVP) and ethylene glycol oligomer (EGO) from 0 to 40 wt % PVP were carried out at 25 degrees C in the frequency range from 20 Hz to 20 GHz. The EGOs used in this study were ethylene glycol (EG), diethylene glycol (2EG), and PEG400 (MW = 400). For the PVP-EG, -2EG, and -PEG400 blends, relaxation processes caused by the motion of EGO in the GHz range and the micro-Brownian motion of the PVP chain at 10 kHz-1 MHz were observed. Although the PVP-EGO blend is miscible, relaxation processes caused by the molecular motion of EGO and the local chain motion of PVP were observed individually. The relaxation time of the local chain motion of PVP showed a strong PVP concentration dependence and a solvent viscosity dependence, which are similar to those reported so far for the solutions in nonpolar solvents.     

Noncontact dielectric friction

Dielectric fluctuations are shown to be the dominant source of noncontact friction in high-sensitivity scanning probe microscopy of dielectric materials. Recent measurements have directly determined the friction acting on custom-fabricated single-crystal silicon cantilevers whose capacitively charged tips are located 3-200 nm above thin films of poly(methyl methacrylate), poly(vinyl acetate), and polystyrene. Differences in measured friction among these polymers are explained here by relating electric field fluctuations at the cantilever tip to dielectric relaxation of the polymer.     

Hydrogen network fluctuations of associating liquids: dielectric relaxation of ethylene glycol oligomers and their mixtures with water

Complex dielectric spectra of ethylene glycol and of various derivatives as well as of mixtures of water with an ethylene glycol oligomer and with a poly(ethylene glycol) dimethyl ether oligomer have been measured. The spectra can be well represented by a Cole-Cole [Cole and Cole, J. Chem. Phys. 9, 341 (1941)] spectral function. The extrapolated low frequency (static) permittivity of this function has been evaluated to yield the effective dipole orientation correlation factor of the liquids. The relaxation time of the ethylene glycols displays a characteristic dependence upon the ratio of concentrations of hydrogen bond donating and accepting groups, indicating two opposing effects. With increasing availability of hydrogen bonding sites effects of association and also of dynamical destabilization increase. Both effects exist also in the mixture of water with the oligomers. They are discussed in terms of a wait-and-switch model of dipole reorientation in associating liquids. Another feature in the dependence of the dielectric relaxation time of poly(ethylene glycol)/water mixtures upon mixture composition has been tentatively assigned to precritical demixing behavior of the binary liquids in some temperature range.     

Dielectric spectroscopy study on ionic liquid microemulsion composed of water, TX-100, and BmimPF6

We report here a broadband dielectric spectroscopy study on an ionic liquid microemulsion (ILM) composed of water, Triton X-100 (TX-100), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)). It is found that the phase behavior of this ILM can be easily identified by its dielectric response. The dielectric behavior of the ILM in the GHz range is consistent with that of TX-100∕water mixtures with comparable water-to-TX-100 weight ratio. It consists of the relaxations due to ethylene oxide (EO) unit relaxation, hydration water dynamics, and∕or free water dynamics. The water content dependence of the EO unit relaxation suggests that this relaxation involves dynamics of hydration water molecules. In the IL-in-water microemulsion phase, it is found that bmimPF(6) molecules are preferentially dissolved in water when their concentration in water is lower than the solubility. An additional dielectric relaxation that is absent in the TX-100∕water mixtures is observed in the frequency range of 10(7)-10(8) Hz for this ILM. This low-frequency relaxation is found closely related to the bmimPF(6) molecule and could be attributed to the hopping of its cations∕anions between the anionic∕cationic sites.     

Hydration and dynamic behavior of poly(N-isopropylacrylamide)s in aqueous solution: a sharp phase transition at the lower critical solution temperature

The number of hydrated water molecules per poly(N-isopropylacrylamide) monomer unit in homogeneous aqueous solution was determined to be 11 exactly and anew below the lower critical solution temperature of 32 degrees C employing high-frequency dielectric relaxation techniques.     

The degree of dispersion of poly(vinyl alcohol) in water/n-propanol solutions

It is demonstrated that, although addition of n-propanol to aqueous poly(vinyl alcohol) solutions prevents their aging, the polymer is not present in a molecularly dispersed form. Further, it is shown that viscometry is not a suitable method to study the degree of dispersion of poly(vinyl alcohol) in water or water/n-propanol solution. The results of turbidity measurements as a function of poly(vinyl alcohol) concentration, n-propanol concentration and time suggest that it is a change of solvent quality rather than a specific interaction between polymer and n-propanol that is responsible for the suppression of aging effects.     

Effect of temperature and solvents on stereospecific polymerization of vinyl alkyl ethers catalyzed by aluminum sulfate–sulfuric acid complex

The effect of polymerization temperature and solvents was determined on the crystallinity of polymers of vinyl isobutyl ether and of vinyl n-butyl ether prepared with aluminum sulfate–sulfuric acid complex catalyst. Principally, the methyl ethyl ketone (MEK)-insoluble fractions of these polymers were used for characterization. Density, per cent crystallinity by x-ray diffraction, infrared ratio, and dilatometric volume contraction of these polymer fractions were used as criteria of crystallinity. The MEK-insoluble fractions of poly(vinyl n-butyl ethers) prepared in carbon disulfide in the temperature range of ?30 to +25°C did not show any significant difference in the values of the above crystallinity parameters. The polymer obtained at 50°C. was less crystalline than the rest of the polymers. The MEK-insoluble fractions of poly(vinyl isobutyl ethers) prepared at 0–50°C. in carbon disulfide and n-heptane solvents also did not significantly differ in their degree of crystallinity. They were, however, decidedly less crystalline than the MEK-insoluble fractions of the corresponding polymers obtained at ?20°C. These data a indicate that on increasing the temperature of polymerization the crystallinity of the polymers was either unchanged or decreased slightly. The polymerizations of vinyl n-butyl ether and vinyl isobutyl ethers were also carried out in binary mixtures of carbon disulfide with n-heptane, chlorobenzene, and MEK. Generally, increasing the concentration of carbon disulfide increased the inherent viscosities of polymers as well as the weight percentage of their MEK-insoluble fractions. The MEK-insoluble fraction of poly(vinyl isobutyl ether) prepared in carbon disulfide-MEK mixture (volume ratio 2:1) was isotactic and highly crystalline. Likewise, the MEK-insoluble fractions of two polymers of vinyl n-butyl ether prepared in MEK itself were also isotactic and highly crystalline. Compared to poly(tetramethylene oxide), these latter fractions exhibited less dependence of rate of crystallization upon temperature. Consequently, at low degrees of supercooling they crystallize much more rapidly than does poly(tetramethylene oxide).     

Superabsorbant hydrogels based on xanthan and poly(vinyl alcohol): 1. The study of the swelling properties

The swelling properties of some superabsorbant composite hydrogels, based on xanthan and poly(vinyl alcohol) and crosslinked with epichlorohydrin, were studied. The maximum swelling degree of the hydrogels and the swelling rate constant were determined as a function of the hydrogel's composition (the % of poly(vinyl alcohol) in the polymer mixture and the amount of crosslinking agent), the crosslinking reaction conditions (the time and the temperature of the crosslinking reaction), and the composition of the swelling solutions (the glycerin/water ratio and the concentration of the electrolyte).     

Carbon-13 spin-lattice relaxation study of linear polymers in solution

Proton-decoupled, partially relaxed, Fourier-transform NMR of ¹³C in natural abundance was used to determine spin-lattice relaxation times of individual carbons of polyisobutylene, polyacrylonitrile, poly(vinyl chloride), and poly(vinyl alcohol) in solution. It is shown that the relaxation times are independent of the difference in stereochemical configuration. From the values of the nuclear Overhauser enhancement factor it is shown that the relaxation times are independent of the difference in stereochemical configuration. From the values of the nuclear Overhauser enhancement factor it is shown that the excess spin energy from equilibration of all the ¹³C, even of quaternary carbons, in the polymers dealt with here is transferred to the lattice mainly through ¹³C-¹H dipolar interactions. It is shown that the segmental motions responsible for the spin-lattice relaxation of the polymer skeleton in solution can be described by the isotropic model within a good approximation, except for poly(vinyl alcohol) at low temperature. The activation energies of skeletal and internal methyl motions are estimated from the temperature dependence of the correlation time. Differences in the ¹³C line widths for individual carbons of polyisobutylene are discussed briefly.