Kaito Sasaki

Dielectric Relaxation Time of Ice-Ih with Different Preparation.

Dielectric relaxation process of ice-Ih has been investigated by many researchers. Pioneering studies focused on the temperature dependence of the dielectric relaxation time, τice, were reported by Auty in 1952 [ Auty, R. P.; Cole, R. H. J. Chem. Phys . 1952 , 120 , 1309 ] and Johari in 1981 [ Johari, G. P.; Whalley, E. J. Chem. Phys. 1981 , 75 , 1333 ]. However, the temperature dependences of τice found in these studies are not in agreement. While Auty et al. reported a single Arrhenius temperature dependence of τice for the entire 207-273 K temperature range, Johari et al. reported changes in the temperature dependence of τice at 230 and 140 K. In this study, the temperature dependence of τice is investigated by broadband dielectric spectroscopy for ice prepared by three different procedures. For all investigated ices, a dielectric relaxation process is observed, and τice decreases with increasing temperature. Temperature dependence of τice with rapid crystallization shows the same properties at temperatures down to 140 K as that reported by Johari et al. On the other hand, ice obtained by slow crystallization exhibits the same temperature dependence of τice as those reported by Auty et al. We suggest that the difference between the temperature dependences of τice found by Auty et al. and Johari et al. can be controlled by preparation conditions. That is, the growth rate of the ice crystal can affect τice because a slow growth speed of the ice crystal induces a smaller impurity content of ice, giving rise to an Arrhenius temperature dependence of τice.

Glass transition of partially crystallized gelatin-water mixtures studied by broadband dielectric spectroscopy

The glass transition of partially crystallized gelatin-water mixtures was investigated for gelatin concentrations of 40 and 20 wt. % by broadband dielectric spectroscopy (BDS) in wide frequency (10 mHz-50 GHz) and temperature (113-298 K) ranges. Three dielectric relaxation processes were clearly observed. The origin of each relaxation process was the same as that observed for partially crystallized bovine serum albumin (BSA)-water mixtures [N. Shinyashiki et al., J. Phys. Chem. B 113, 14448 (2009)]. The relaxation process at the highest frequency is originated from uncrystallized water (UCW) in the hydration shell of gelatin. Its relaxation time is almost the same as that of water in uncrystallized system; water in various binary aqueous mixtures and confined water in nanoscale region. The relaxation process at the intermediate frequency is originated from ice, and its relaxation time and strength were similar to those for the relaxation of pure ice, particularly above 240 K. The glass transition temperature Tg, is defined by BDS measurement as the temperature at which dielectric relaxation time τ, is 100-1000 s. The relaxation process at the lowest frequency, Tg is approximately 200 K, is originated from the cooperative motion of water and gelatin. This relaxation is strong and has a similar relaxation strength to that of hydrated BSA. At Tg for the relaxation process involving the cooperative motion of gelatin and water, the temperature dependence of the relaxation process of UCW crosses over from Vogel-Fulcher behavior to Arrhenius behavior with decreasing temperature. A characteristic property of the gelatin-water mixture is a change in the temperature dependence of the relaxation time of the relaxation processes of hydrated gelatin at approximately 260 K.

Glass Transition and Dynamics of the Polymer and Water in the Poly(vinylpyrrolidone)–Water Mixtures Studied by Dielectric Relaxation Spectroscopy

In this study, broadband dielectric spectroscopy and differential scanning calorimetry (DSC) measurements are performed to study the dynamics of water and polymers in an aqueous solution of poly(vinylpyrrolidone) (PVP) with concentrations of 60, 65, and 70 wt % PVP in a temperature range of 123-298 K. Two distinct relaxation processes, l- and h-processes, which originate from the segmental chain motion of PVP and the primary relaxation process of water, respectively, are observed simultaneously. The relationship between l- and h-processes and their temperature dependences mimic those of the α-process and Johari-Goldstein β-process, which are observed in ordinal glass formers. The relaxation time of the l-process, τl, obeys the Vogel-Fulcher (VF)-type temperature dependence, and the glass-transition temperature of the l-process, Tg,l, which is defined by the temperature that is reached in a τl of 100-1000 s, shows good agreement with the calorimetric Tg obtained by DSC. The temperature dependence of the relaxation time of the h-process, τh, exhibits a crossover from VF to Arrhenius behavior at the so-called fragile-to-strong transition (FST) of water at Tg,l. The temperature dependence of the relaxation strength of the h-process, Δεh, increases with a decrease in temperature from 298 K to Tg,l. Below Tg,l, Δεh is nearly constant or slightly decreases with decreasing temperature. According to previous studies on aqueous solutions of sugars and alcohols, the Δε of the ν-process, which originates from local motion of water, decreases with decreasing temperature above the Tg of the α-process, which originates from the cooperative motion of the solute and water. Therefore, the l-process in the PVP-water mixture is not a result of the cooperative motion of PVP and water but rather a result of the polymer-polymer cooperative motion of PVP. In addition, agreement among Tg,l, the temperature of the FST of water, and calorimetric Tg suggests that the FST of water occurs at Tg.

Dynamics of Uncrystallized Water, Ice, and Hydrated Protein in Partially Crystallized Gelatin–Water Mixtures Studied by Broadband Dielectric Spectroscopy

The glass transition of partially crystallized gelatin-water mixtures was investigated using broadband dielectric spectroscopy (BDS) over a wide range of frequencies (10 mHz to 10 MHz), temperatures (113-298 K), and concentrations (10-45 wt %). Three dielectric relaxation processes (processes I, II, and III) were clearly observed. Processes I, II, and III originate from uncrystallized water (UCW) in the hydration shells of gelatin, ice, and hydrated gelatin, respectively. A dynamic crossover, called the Arrhenius to non-Arrhenius transition of UCW, was observed at the glass transition temperature of the relaxation process of hydrated gelatin for all mixtures. The amount of UCW increases with increasing gelatin content. However, above 35 wt % gelatin, the amount of UCW became more dependent on the gelatin concentration. This increase in UCW causes a decrease in the glass transition temperature of the cooperative motion of gelatin and UCW, which appears to result from a change in the aggregation structure of gelatin in the mixture at a gelatin concentration of approximately 35 wt %. The temperature dependence of the relaxation time of process II has nearly the same activation energy as pure ice made by slow crystallization of ice Ih. This implies that process II originates from the dynamics of slowly crystallized ice Ih.

Dielectric Relaxation of Ice in Gelatin–Water Mixtures

Broadband dielectric spectroscopy measurements were performed on partially crystallized gelatin-water mixtures with gelatin concentrations of 1-5 wt % for temperatures between 123 and 298 K to study the dynamics of ice. These systems contain only hexagonal ice. Nevertheless, four dielectric relaxation processes of ice were observed. At temperatures below the crystallization temperature, a loss peak was observed, and it separated into four loss peaks at around 225 K. Using the temperature and concentration dependencies of these relaxation processes, we confirmed that these four processes originated from ice. For the relaxation time of ice, τice, the deviation of the temperature dependence of τice from the Arrhenius type is larger for the relaxation process at the higher-frequency side. For the temperature dependence of τice for the dominant process, three temperature ranges with different activation energies, Ea, were investigated. The intermediate-temperature range of τice with the smallest Ea decreased as the gelatin concentration increased; therefore, τice of the dominant process changed from the relaxation process with the smaller τice to that with the larger τice as the gelatin concentration increased. In addition, the relaxation process of ice with larger τice values was found to have larger values of Ea. These results suggest that a higher gel network density affects the temperature dependence of τice.

Glass transition and dynamics of poly(vinyl pyrrolidone)-water mixture

Broadband dielectric measurements of poly(vinyl pyrrolidone) (PVP)-water mixture were performed in a frequency range of 10 mHz - 50 GHz and at temperatures between 118 K and 318 K. The relaxation processes caused by the reorientational motion of water molecules (h-process) and the local chain motion of PVP (m-process) were observed without crystallization of water. The relaxation time of the m-process, τm, obeys the Vogel-Fulcher law, and the glass transition temperature, Tg, of PVP in the mixture, at which τm being 100 s is 237 K. The relaxation time of the h-process, τh, obeys the Vogel-Fulcher law above Tg = 237 K, and it turns to obey the Arrhenius law below Tg. The relaxation strength of the m-process, Δem, increases with decreasing temperature. The relaxation strength of the h-process, Δeh, increases with decreasing temperature above the crossover temperature, TC (TC = 272 K), and it turns to be almost constant below TC. The temperature dependences of τm and τh are the same as those of the α- and th...

Dynamics of water and hydrated gelatin in partially crystallized mixtures

Gelatin-water mixtures with gelatin concentrations in a range of 10 – 40 wt% were investigated by broadband dielectric spectroscopy measurements in wide frequency (1 mHz – 50 GHz) and temperature (113 – 298 K) ranges. Three dielectric relaxation processes were observed. The temperature dependences of the three relaxation processes observed for the gelatin-water mixtures are similar to those observed for the BSA-water mixtures. The fastest relaxation process is originated from the uncrystallized water (UCW) in hydration shell and its relaxation time is the same to that of the UCW in various uncrystallized binary water mixtures. The intermediate relaxation process is originated from ice and its temperature dependence of the relaxation time and strength resemble pure ice relaxation process especially above 240 K. The slowest relaxation process is originated from hydrated gelatin. The strength of the slowest relaxation process is large, and it is similar to that of the relaxation process of hydrated BSA. The ...